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I lli ABSTRACTS OF CHEMICAL PAPERS. Organic Chemistry. Purification of Amy1 Iodide. By H. MALBOT (Bull. SOC. Chim. [33 1 604).-Amy1 iodide may be completely freed from the alcohol which distils over in its preparation by treatment with an equal volume of concentrated hydrochloric acid which dissolves this im- purity ; the alcohol may be recovered by subsequently diluting the 11 y drochloric solution. Carbonylhydroferrocyanic Acid and Carbon ylferrocyanides. By J. A. MULLER (Ann. Claim. Phys. [GI 17 93-102).-The author has previously described a new class of ferrocyanides and ferri- cyanides in which the group CO is substituted for KCN ( A bstr. 1887 649). The crude violet precipitate (Znc. cit.) which still contains ferrocyanide is treated with a warm solution of potassium carbonate the liquid filtered and when cold slightly acidified with acetic acid and mixed with excess of lead acetate.After remaining for a day the liquid is again filtered the filtrate mixed with a slight excem of potassium rubonate and boiled. The traces of lead which remain in the filtrate from the lead carbonate are removed by means of hydrogen snlphide after slightly acidifying with acetic acid. Carbo?ryZh?ldroferrocyania acid HaeCO( CN) is obtained by the action of hydrogen sulphide on the copper salt and when the solu- T. G. N.ORGANIC CEEMISTRP. 117 tion is evaporated over potassium hydroxide in the dark the acid separates in colourless platy crystals with an acid taste and an astringent after-taste. It is acid to litmus and decomposes alkaline carbonates. When the aqueous solution is boiled the acid decom- poses with formation of a violet-blue precipitate and evolution of a large quantity of hydrocyanic acid but no ca.rbonic anhydride is evolved and neither formic acid nor ferrocyanide is formed.The sodiunz salt is obtained in the same manner as the potassium salt (Zoc. cit.) and crystallises with 6 mols. H,O in very pale-yellow monoclinic needles which become anhydrous at 110". The insoluble carbonylferrocyanides are obtained from the alkaline salts by double decomposition. The silver salt precipitated by excess of silver nitrate in presence of a small quantity of acetic acid forms a white curdy precipitate which rapidly becomes black even in the dark. After being washed with water it contains no potassium.It is slightly soluble in dilute mineral acids with evolution of hydrocyanic acid but is practically insoluble even in boiling acetic acid. Potassium hydroxide converts it into potassium carbonylferrocyanide and silver oxide. It retains water after being dried in a vacuum and at 100" to 110" i t slowly decomposes still retaining a small quantity of water. At a dull red heat decomposition is rapid cyanogen and hydrogen cyanide being evolved. If in the preparation of the salt the alkaline carbonyl- ferrocyanide is in excess the precipitate only becomes slightly grey but it retains potassium nitrate and possibly some silver nitrate. The .uranium salt (U02)3(FeCOCy5)2 + 5H,O from uranium nitrate and the potassium salt is an orange-yellow gelatinous sub- stance which retains no potassium and is only slightly soluble in water b u t somewhat more boluble in dilute acetic acid.At 70" i t forms a ruby-red granular solid which re-acquires the yellow colour when powdered ; at 110" it becomes black and partially decomposes but still retains a small quantity of water. The cobult sult forms a lilac precipitate which contains 3.5 mols. H20 and retains potassium even after prolonged washing its compo- sition being represented by the formula (Co,.,,K,,.,,)FeCO(CN),. I t is slightly soluble in water and is decomposed by cold dilute nitric acid. I n a dry vacuum or when gently heated i t is partizlly dehydrated and becomes deep-blue. This change takes place even in boiling water but the salt is rehydrated on cooling. It retains a small quantity of water even at 110".The copper salt forms a yello wish-green gelatinous precipitate insoluble in dilute nitric or sulphuric acid. I t retains no potassium becomes dehydrated with change of colour when gently heated and at 110" forms a somewhat hygroscopic dark-brown powder which undergoes slight decomposition at this temperature but still retains a small quantity of water. The ferric salt is obtained from the potassium salt and ferric chloride as a violet precipitate which is free from potassium and when dried at a moderate temperature forms a very friable resinous mass with a brilliant conchoidal fracture of very high metallic lustre. It alters even below looo and undergoes profound change a t 100" t o118 ABSTHACTS OF CEEMICAL PAPERS. 110".After being dried in a vacuum it retains 12 to 13 per cent. of water. The violet precipitate dissolves in an aqueous solution of oxalic acid forming a solution with a magnificent violet colour but i t is not soluble in acetic lactic succinic tartaric or citric acid. It dissolves however in solutions of the normal aalts of these acids wen in presence of a small quantity of free acid. The solutions are almost colourless or have only a slight violet tinge but on the addition o t sulphuric acid carbonylferrocyanide is again formed and is precipitated or remains in solution according to the nature of the acid present. The violet precipitate of the ferric salt is not soluble in solutions of poibassiurn chloride or nitrate or in very dilute phosphoric or sulphuric acid but is distinctly soluble in solu- tions of sodium hydrogen phosphate.It is slightly decomposed by potassium sulphate and the liquid becomes acid ; it decomposes potassium hydrogen carbonate even a t 25") carbonic anhydride being en)lved. Analysis of the salt shows that it contains more ferric iron than is required by the formula a result probably due t o the presence of ferric oxide which was contained in the ferric chloride solution used in the preparation of the salt and cannot be removed by washing. Precipitation of t h e alkaline salt with ferric chloride solution of known strength followed by a determination of the iron in the filtrate also showed that the amount of iron precipitated was greater than the calculated quantity. All these results poink to the existence of a trivalent acidic radicle of the formula FeCO( CN),.The insoluble carbonylferrocyanides resemble the insoluble ferrocyanides in retaining small quantities of water which cannot be expelled without decomposing the salt. C. H. B. Note hy A:bsimctor.-It is interesting to compare the properties of ferric carbonylferrocymide with those of soluble Prussian-blue (Guignet AbsDr. 1889 475). Vinyl Alcohol a Constant Constituent of Ethyl Ether. By T. PQLECK and K. TH~MMEL (Ber. 22 2863-2880).-When a soh- tian of mercury oxychloride in pure sodium or potassium carbonate is shaken for 10-20 minutes with ether from the most varied sources a yellowish-white amorphous precipitate is always produced in small quantities varying from 0939-6.64 per cent. The samples employed had generally a neutral reaction liberated iodine from a solution of potassium iodide gave a brown coloration with potash and were free from acetaldehyde; after having been shaken with the mercury solution the ether gave no coloration with potash.The white precipitate has the composition CH,:CH*OHg*O*Hg,Cl and may be named vinyl oxymercurochloride. It turns yellow a t loo" becoming colourless again on cooling and a t about 170" it swells up like mercury thiocyanate with evolution of a gas which burns with a blue flame. It is insoluble in water alcohol and ether ; when freshly precipitated it dissolves freely in hydrochloric acid nitric acid and 11 ydrocyanic acid but when dry it dissolves completely only on boiling even in concentrated hydrochloric acid.When boiled for a long time with potash it is converted into a greenish-black powder which is in- C. H. B.ORGANIC CHEMISTRY. 119 soluble in potash and the alkaline solution contains a colourless compound which is precipitated on adding nitric acid. The greenish-black compound has the composition CHiC.Hg,(OH),,Hg,!OH)2 and is named '' acetylenemercurg." It dissolves in concentrated acetic acid forming a crystalline acetate arid i t is soluble in nitric acid and in aqua regia but insoluble in hydrochloric acid. It explodes very violently when heated (at about 157") but not by percussion. The acetate CHiC.Hg.,(OAc),,Hg(OAc) is obtained when the black powder is dissolved in concentrated acetic acid and the filtered solu- tion evaporated. It decomposes at loo" or when boiled with water and it is insoluble in ether and acids except acetic acid ; if the acetic acid solution is diluted a colourless compound is precipitated and mercury remains in solution.When hydrogen sulphide is passed into the acetic acid solution a yellowish or colourless precipitate is produced and the precipitate turns greenish-black after some days. The acetate is decomposed by warm potash being reconverted into the black explosive compound. The colourless compound which is precipitated on adding nitric acid fo the alkaline solution of vinyl oxymercurochloride (see above) has the composition CHiC*HgO,HgCI and is named acetyler~ernerciiry ozy- chloride. It is an amorphous powder iiisoluble in hydrochloric acid nitric acid ammonia aud alkaline carbonates but readily soluble in potash jielding a solution which is coloured yellow by hydrogen sul- phide; it is not explosive and when heated it volatilises leaving a carbonaceous residue.When ether is distilled with phenylhydrazine the distillate gives no coloration with potash and no precipitate with the mercury solution ; the residue contains ethylidene phenylhydrazine. Vinyl oxynierciirochloride (see above) is decomposed by bromine yielding bromal hydrate or bromoform and formic acid according to the length of time during which the reaction takes place. When treated with a solution of iodine in potassium iodide this vinyl-corn- pound gives iodoform and when triturated with dry potassium iodide an energetic reaction takes place the dark-coloured explosive substance being formed.If vinyl oxymercurochloride is suspended in water and treated with potassium iodide the mixture turns yellow or greyish- green and the solution becomes strongly alkaline ; on adding hydro- chloric acid a reddish-brown powder is precipitated. When excess of hydrogen sulphide is passed into water containing the vinyl- compound in suspeusion r-trithioacetaldchyde (m. p. 75-76") identical with the compound obtained by Marckwald (Abstr. 1888 127) is formed ; a small quantity of a very volatile unpleasant smell- ing oil probably thioacetaldehyde (compare Marckwald Zoc. &.) is also produced. Vinyl oxymercurochloride is decomposed by ammonium sulphide with separation of mercuric sulphide yielding acetamide and probably also traces of thioacetamide.It is only slowly osidised by chromic acid and potassium permanganate yielding acetic acid carbonic anhydride and small quantities of formic acid. When a large quantity of ether is repeatedly submitted to fractional120 ABSTRACTS OF CHEMICAL PAPERS. distillation two liquids boiling a t 30-:31" and 37-38' respectively are obtained ; both these liquids give a copious precipitate with the mercury solutioii but they are generally obtained in small quantities only owing t o polymerisation taking place during the distillation. The lower boiling liquid has an ethereal odour and a neutral reaction b u t it soon becomes acid owing to the formation of acetic acid; it does not liberate iodine from pot<assium iodide until it has undergone oxidation a fact which indicates the formation of hydrogen peroxide.The higher boiling liquid has a slight ethereal odour does not alter on keeping has a neutral reaction and unlike the lower boiling liquid is not oxidised by potassium permanganate. An ammoniacal solu- tion of silver nitrate is not reduced by either of the two liquids but both give a brown coloration with potash ; the lower boiling liquid only reduces alkaline copper solutions and yields iodoform with potassium iodide. Vinyl ethyl ether gives a precipitate with the mercury solution referred to above but the precipitate differs from vinyl oxymercuro- chloride in composition and in not forming an explosive compound when treated with potash. Vinyl chloride and vinyl iodide in alcoholic solution give pre- cipitates from which explosive substances are obtained by treatment with potash.The above experiments show that the substance which is present in ether and which is precipitated by the merciiry solution is vinyl alco ho 1. When air containing ozone is passed for a long time through pure ether or when pure et,her is shaken for a long time with hydrogen per- oxide it yields subsequently a precipitate of vinyl oxymercurochloride. A violent reaction occurs when pure ether is added drop by drop to anhydrous chromic acid a liquid distilling which if the operation is carefully conducted smells only slightly of ether but has on the other hand a peculiar aldehyde-like odour. When the distillate is fractionated a liquid boiling a t 3 3 O probably a polymeride of vinyl alcohol is obtained. It has a neutral reaction does not liberate iodine from potassium iodide and does not give a brown coloration with potash but it yields a copious precipitate with the mercury solution ; it resembles the liquid boiling a t 37-38" (see above) in its ot h er proper ties. Vinyl alcohol and hydrogen peroxide are formed when pure ether is exposed to direct sunlight either alone or in contact with water ; the presence of hydrogen peroxide can be recognised by the chromic acid rea c tio n.Commercial ether gives only a slight blue coloration with dilute chromic wid solution but on agitating with air an intense blue colora- tion is produced. The formation of hydrogen peroxide i n this way accounts for the explosions which sometimes occur when ether which has been kept for a long time is distilled.Synthesis of some Glycerols by means of Hypochlorous Acid. By S. REFORMATZKY (J. pr. Cliem. [2] 40 3 9 6 4 1 9 ; compare Abstr. 1885 882).-A chlorhydrin C6Hl3O2C1 is obtained on adding by F. S . I(.ORGANIC CHENISTRT. 121 degrees a solution of hypochlorous acid free from chlorine to allyl di- methyl carbinol(20 grams) and some ice-water in a retort cooled by ice (compare Orloff Abstr. 1886 138 681). When the odour of hypo- chlorous acid has nearly disappeared a little sodium thiosulphate is added to destroy the last traces of it the liquid is filtered and then shaken with ether which extracts the chlorhydrin (23 grams) ; it is a thick liquid. To obtain t'he corresponding gZyceroZ C6H1403 potassium hydroxide (25 grams) is added to the residue in the retort without previously extracting the chlorhydrin and the mixture is distilled until t wo-thirds have passed over ; the residue is nearly all evaporated in a dish the excess of potassium hydroxide neutralised with sulphnric acid and the excess of the latter with dry sodium carbonate ; evaporation is then continued to dryness and the residue extracted with 95 per cent.alcohol ; the solution is mixed with ether which throws down foreign matters and then evaporated to obtain the glycerol (80 per cent. of theory). It distils atlabout 198" at a pressure of 60-65 mm. and is a colourless sweet thick liquid soluble in water and alcohol but not in ether. The acetate C6H1,(OAc)3 is obtained by heating the glycerol (3 grams) with acetic anhydride (9 grams) at 100" in a tube for 10 hours and evaporating off the excess of the latter; it is a mobile liquid insoluble in water soluble in alcohol and ether.When oxidised by nitric acid the glycerol yields a triatomic mono- basic acid containing 6 atcms of carbon. Potassium permanganate oxidises the glycerol to hydroxjvaleric acid. A c,L?orhydrin C8H12C102 is prepared from allyl diethyl carhinol in the same way as from allyl dimethyl carbiiiol and from this the cor- responding glycerol C8H,,(OH) is obtained ; it is a colourless thick bitter liquid soluble in water alcohol and ether and boiling at 2OP-207" under 55-60 mm. pressure. An acetyl-derivative C8Hl5O3Ac3 was obtained. Ally1 methyl pmpyl carbinol yields a chlorhydrin C,Hl,(OH)2Cl as a somewhat thick colourless liquid.The corresponding glycerol C8H15(OH)3 is a thick colourless liquid easily soluble in water and alcohol sparingly in ether and boiling at 210" under 60 mm. pressure. An acetyl-derivative was obtained. Unsuccessful attempts were made to prepare a glycerol from allyl dipropyl carbinol and a glycerol by the hydrolysirj of diallyl carbinol by cold sulphuric acid. A chlorhydrin C,HlI(OH)3C1 was obtained from diallpl carbinol by the action of hypochlorous acid but it gave no glycerol; A. G. B. - Identity of Brain Sugar with Galactose. By H. THIERFELGER (Zeit. physiol. Chem. 14 209-216 ; compare Brown and Morris Trans. 1890,57,57j.-Bayer and Liebrich (Virchow's Arch. 39,183) first described a carbohydrate in the brain which they obtained from protagon. Since then Otto (ibid.41 272) Geoghegan (Zed. physiol. Ghem. 3 337) and Thudichum (Abstr. 1882 537) obtained one by treating cerebrin with hydrochloric acid. The last- named observer prepared it in a crystalline form and termed it cerebrose. I n the present research the sugar wits prepared from122 ABSTRACTS OF OHEMICAL PAPERS. cerebrin by the action of 2 per cent. sulphuric acid. It reduces Fehling's solution yields mucic acid on oxidation with nitric acid and thus resembles galactose which is the only glucose that yields mncic acid on this treatment. In its melting point specific rotation fermentation and phenylhydrazine-compound its properties are also the same as those of galactose. The mother substance of this sugar in the brain has yet to be isolated. By MAQUENNE (Ann.Chim. Phys. [6] 17 495-500).-Eucalyptus honey is secreted by a peculiar species of black bee which constructs enormous hives on the summits of the gigantic Eucalypti of Australia. Some of these hives furnish as much as 5000 kilos. of crude honey each. It is a thick syrup similar in appearance to ordinary honey but containing a somewhat smaller proportion of crystals and i t has a strong aromatic odour. It consists essentially of levulose and dextrose in practically the same proportions at^ in invert sugar with a small quantity of aromatic substances and traces of gum insoluble in alcohol. No peculiar sugar could be detected. The Precipitation of Colloid Carbohydrates by Salts. By J. POHL ( Z e d . physiol. C'hem. 14 151-164).-'l'he neutral salts used in the separation of prote'ids can also be employed for the sepa- ration of plant mucilages and other colloid carbohydrates.Those examined in the present research can be grouped as follows :- A. Those not precipitable by saturation with neutral salts :-Gum arabic and sodium arabinate. B. Those precipitable by saturation with ammonium snlphate :- The mucilages of tragacanth althea linseed and cydonia. Gum tragacanth is also distinguishable from gum arabic by its lesser solubilities. Cydonia mucilage is a mixture of cellulose and a car- bohydrate very like gum tragacauth. C. Those precipitable by saturation with ammonium snlphate am- monium phosphate and potassium acetate :-Carragheen mucilage. D. Those precipitable by saturation with sodium snlphate mag- nesium sulphate ammonium sulphate and ammonium phosphate :- Soluble starch lichen starch dextrin salep mucilage and pectin.These forms of carbohydrates are further distinguished by the per- centage of salt necessary for the commencement of precipitation ; thus tragacanth requires complete saturation with ammonium sulphate for its precipitation that is 53.5 grams of salt to every lo0 C.C. of solution. Salep mucilage begins to be precipitated by 40.4 grams and soluble starch by 24.1 grams of the same salt per 100 C.C. of solution. Further by fractional precipitation with mag- nesium sulp hate salep mucilage can be differentiated into two varieties named a and B. These two varieties further differ in the W. D. H. Eucalyptus Honey. C. H. B. inel ting-points of their phenyl hydrazine-compounds. W.D. H. Oxalenediamidoxime and Oxaleneanilidoximamidoxime. By W. ZINKEISEN (Ber. 22 2946-2957.)-Vxalenediamidozime OH*N:C (NH,)*C( NH,) :NOOH is prepared by gradually adding cyan- aniline (LOO parts) to a solution of hydroxylamine hydrochlorideORQ ANIC OHEMISTRY. 123 (50 parts) in 90 per cent. alcohol (500 parts). The amount of sodium carbonate necessary to liberate the hydroxylamine is then added and the whole filtered from the sodium chloride. The filtrate is evapo- rat.ed down a little well shaken when cold and left for some hours ; the diamidoxime which separates is dissolved in boiling water and boiled with animal cha,rcoal. It crystallises in dazzling white con- centrically-grouped lanceolate crystals melts at 196" (uncorr.) with evolution of gas is sparingly soluble in alcohol insoluble in ether chloroform benzene and light petroleum readily soluble in hot water ; it dissolves in acids and bases.The aqueous solution with copper sulphate ferric chloride and Fehling's solution gives a grass- green flaky precipitate a deep brownish-red coloration and a dirty precipitate respectively. The hydrochloride forms slender colourless prisms insoluble in absolute alcohol and ether. The dibenzoyl- derivative Cl6€II4N4O4 obtained by gradually adding the finely- powdered dioxime to hot benzoic chloride crystallises in slender slightly-yellow plates melts at 217" is insoluble in water ether benzene and light petroleum readily soluble in chloroform sparingly in alcohol. It is insoluble in hydrochloric acid and in alkali but dissolves unchanged in acetic and in cold strong sulphuric acids.TIT -n7 Ozalenediazoximedibenzy 1 C P h < ~ ~ > C * C < A ~ ~ >CPh is formed when oxalenediamidoxime is heated for a long time with an excess of benzoic chloride. It crystallises from chloroform in slender white needles melts at 246" is soluble in benzene insoluble in water alcohol ether and in strong hydrochloric acid and alkalis ; but readily soluble in strong sulphuric and acetic acids. When heated above its melting point it sublimes without decomposition. Diacetyloxalenediamidoxime CBH10N401 prepared by gradually adding the powdered diamidoxime to boiling acetic anhydride crys- stallises in needles melts at 184-187" dissolves readily in alcohol sparingly in benzene and is insoluble in chloroform ether and light petroleum.Acids and bases readily decompose it. When heated for a long time with acet'ic anhydride oxalenediazoximedietlieny I C,H,N,O is obtained. This ci-ystallises in colourless needles melts a t 164-165" dissolves in alcohol and chloroform less readily in hot water and benzene ; and is insoluble in ether and light petroleum. It sublimes in long slender needles. Oxalenediamidoziine diethy1 ether OEt.N:C (NH,)*C(NH,):N*OEt is prepared by boiling an alcoholic solution of oxalenediamidoxime (1 mol.) with ethyl iodide (2 mols.) and the calculated amount of sodium ethoxide for three hours in a reflux apparatus evaporating the whole to half its original bulk treating with water and filtering. It is washed several times with water dissolved in boiling alcohol and sufficient water added to produce a slight turbidity.It crystal- lises in slender colourless matted needles melts at 114-115' dis- solves readily in alcohol ether chloroform and benzene sparingly in hot water. The hydrochloride crystallises well. Ozalenediazoximedipropenyldicarboxylic acid,124 ABSTRACTS OF CHEMICAL PAPERS. is obtained by heating an intimate mixture of oxalenedismidoxime (1 mol.) and succinic anhydride (2 mols.) at 140-150" dissolving the product in hot dilute aqueous soda and precipitating with hydrochloric acid. It crystallises from boiling water in almost colourless needles melts at 200" dissolves sparingly in hot water readily in alcohol and chloroform and is insoluble in ether and benzene.The alkali salts are readily soluble in water Oxalenediurarnidoxitn e 0HnN:C (NK*CO*NH,)*C (NH*C 0-NH,) :N*OH prepared by adding a saturated solution of potassium cyanide (2 mols.) t o a hydrochloric acid solution of oxalenediamidoxime (1 mol.) crystallises from very dilute alcohol in slender white needles melts at 191-192" with decomposition dissolves sparingly in hot water readily in alcohol and is insoluble in ether benzene and chloroform. Et h y 1 oxalenediamidorirne d icarbonat e C8 H,,N Os is formed when finely powdered dry oxnlenediamidoxime (1 rnol.) is slightly heated o n a water-bath with ethyl chlorocarbonate for 20 minutes. It crys- tallises from water in long thin needles melting at 168"; i t is sparingly soluble in hot water and soluble in alcohol ether and in acids and bases.Oxaleneanilidoximamidoxime OH-N C (NHPh)*C (NHPh)jN*O H is formed as bye-product in the action of cyananiline on hydroxylamine and is best prepared by gradually adding solid cyananiline t o an alcoholic solution of hydroxylamine hydrochloride (2 rnols.) filtering from the ammonium chloride and evaporating down until crystals separate. When cold it is again filtered from the oxalenediamidoxime and evaporated almost to dryness. The crystals which separate affer a long time are crystallised from boiling water. It forms colourless hexagonal plates melts at 180° and has almost exactly the same pro- perties as oxalenediamidoxime except that it dissolves more readily in alcohol and seems to be less stable. The precipitate with copper sulphate has a less pure colour than that which the diamidoxime gives. The hydrochloride crystallises in slender colourless needles which become green when exposed to air.The dibenzoyl-derivative CozH,,N,04 prepared by heating oxaleneanilidoximamidoxime (1 mol.) with benzoic chloride (2 mols.) on a water-bath crystallises from dilute alcohol in slender slightly-yellow matted needles melts at 189" is insoluble in water arid light petroleum soluble in alcohol benzene and chloroform. When boiled with alkalis i t is gradually decomposed but does not change when boiled for a short time with hydrochloric acid. Both acids and bases dissolve it readily. Oxaleneani2idoximazoxime ethenyl OH*N:C(NHPh)*C<FO>CMe N is obtained by dissolving oxaleneanilidoximamidoxime in hot acetic anhydride filtering when cold washing repeatedly with cold water and dissolving in boiling water containing a little alcohol.It crys- tallises in slender colourless needles melts at 172" dissolves in alcohol ether and benzene rather sparingly in hot water. It is dissolved by both acids and bases and is less stable than the double nzoxime o bt ained from oxalenediamidoxime. N. H. M.ORQANlC OHEJIJSTRY. 125 Succinenediamidoxime. 296 7) .-Succinenediamidoxime By F. SEMBRITZKI (Bey. 22 2958- 0H.N C ( NHz) CHz* CH,*C (NH,):N* 0 H is prepared by adding a strong solution of hydroxylamine hydro- chloride (2 mols.) and sodium carbonate (1 mol.) to an alcoholic solution of ethylene dicyanide (1 mol.) and keeping the mixture for three or four days in a well-closed vessel.It is then filtered from the crystals of the diamidoxime and! sodium chloride and left to evaporate in a warm place. The sodium chloride is dissolved in cold water and the remaining diamidoxime recrystallised from hot water. It forms transparent monoclinic crystals a b c = 1.2'744 1 0.9269 ; /j = 79" .50' melts at 188" with evolution of ammonia and is sparingly soluble in hot alcohol insoluble in cold water ether acetone benzene and chloroform. It yields salts with acids and with bases; the hydrochdoride is white and dissolves in absolut,e alcohol ; the copper salt is bright-green; the silver salt is white but a t once becomes dark when exposed to light and is completely reduced when heated with formation of a silver mirror. The dihenzoyl-derivative Cl9HI8N4O4 crystallises from amyl alcohol in small white needles melts a t 192" is insoluble in water alcohol ether chloroform and benzene &c.and does not unite with acids and alkalis. Succin enediazoximedibewzeny 1 is obtained when the above dibenzoyl-derivative is heated with water for five hours at 150-160". It crystallises in needles melts a t 158-159" is soluble in benzene and hot alcohol sparingly soluble in ether insoluble in water light petroleum and chloroform. Diacet y Esuccinenediamidoxime CsH1aN4O4 crystal1 i ses from absolnt e rtlcohol in white monoclinic scales a b c = 2.2998 1 0.9105 ; p = 82" 58'; i t melts at 167-168O is soluble in hot water and in acids insoluble in ether benzene and in alkalis. The diethyl sa.lt OEt.N:C(NH,).CEI,*CH,*C(NHz):N*OEt prepared by digesting the equivalent amounts of succinenediamidoxime sodium ethoxide and ethyl iodide for some hours crystallises in colourless needles nielts at 119" dissolves readily in water alcohol ether and chloroform is insoluble in light petroleum and is soluble in acids but not in a1 kalia.S u c c i n e n e a ~ u r a m i t l ~ i m e C,&,NsO4 is readiJy obtained by mixing concentrated aqueous solutions of the hydrochloride of the diamid- oxirne and potassium cyanate. It crystallises with 2 mols. H,O in needles which soften a t 100-105"; the anhydrous salt melts a t 163.5 wit.h decomposition is soluble in hot water insoluble in cold water alcohol ether and benzene &c. unites readily with acids but is sparingly soluble in cold alkalis. Succineneimidodioxime I >NH is formed in small quan- tity in the preparation of succinenediamidoxime but is obtained alone when the mixture is digested for several dayq at 60-70". It C H,-C (N.0 H) CH2.C (N*OH)126 ABSTRACTS OF CHEMICAL PAPERS.crystallises with 2 mols. H20 and resembles the diamidoxime in its properties and solubility. When dissolved in aqueous potash the solution becomes first blue then green. With ferric chloride a dark-violet coloration is produced. The copper salt is dirty green ; the silver salt C4H5N30zAq2 forms small lustrous plates which detonate when heated leaving a residue of silver. The dibenzoyl- derivative CI,H,,N,O melts at 187-189" with previous blackening is soluble in benzene and hot alcohol insoluble in water ether and chloroform does not unite with acids but dissolves in hot alkalis with decomposition.The diacetyl-derivative C8HllN3O4 is a white crystalline powder melts a t 170 -171" dissolves in water alcohol ether and chloroform sparingly in benzene and is insoluble in light petroleum. N. H. M. Glutarenediamidoxime and its Derivatives. By J. BIEDERMANN (Ber. 22 2967-2973).-Trimethylene cyanide is conveniently pre- pal-ed by digesting trimethylene bromide dissolved in 96 per cent. alcohol ( 5 parts) with a slight excess of finely ppwdered pgtassium cyanide for eight hours on a water-bath filtering and distilling off five-sixths of the nlcohol. The residue is treated with an equal volume of ether. The ethereal alcoholic layer is separated from the aqueous evaporated down and the resulting yellowish oil distilled under diminished pressure.Glutarenediamidoxiwe CHz[ CH2*C(NH2):N*OH J2 is obtained to- gether with glutarenimidodioxime when equivalent amounts of hydroxylamice hydrochloride sodium carbonate and trimethylene dicyanide dissolved in aqueous alcohol are digested for 10 hours at 60-70". A part of the diamidoxime separates on cooling. The mother liquor is evaporated to dryness extracted with boiling water the solution allowed to cool filtered and again evaporated to dry- ness. The residue now consists of sodium chloride glutarenimido- dioxime and a small amount of the dinmidoxime. Glutarenediamid- oxime crystallises from water in well-formed lustrous prisms (with 1 mol. H20) dissolves readily in hot water and alcohol less in ether and chloroform and is dissolved by acids and bases.It gives a red- dish-brown coloration with ferric chloride. The diacefyl-derivative C9H,6Nb04 crystallises in microscopic slender colourless needles melts at 115" and is readily soluble in hot water and alcohol insoluble i n ether chloroform benzene &c. Glutarenediuzoximsdiethenyl CH2( CH2*C<N>CMe) N*O is prepared by boiling a solution of glutarenediamidoxime in acetic anhydride evaporating down dissolving the crystals which separate in benzene and precipitating with light petroleum. It forms slender colourless needles melting at 138-139". .-,H,>CH is obtained by extracting the residue from the preparation of the diamidoxime with hot absolute alcohol; the solution is evaporated and the residue dissolved in chloroform and precipitated with light pet.roleum.It melts at 193" without decomposition is very sparingly soluble in C(N*OH)*CH GEutnrenimidodioxime NH<ORQANIC CHEMISTRY. 127 alcohol ether and chloroform insoluble in benzene and light petro- leum soluble in both acids and alkalis and gives a red-violet colora- tion with ferric chloride. The picrute crystallises from alcohol in splendid yellow needles melting at 175" with decomposition ; the hydrochloride forms white needles. The diczcetyl-compound C,H13N,01 is a white crystalline powder melts at 127" is readily soluble in water alcohol ether? and chloroform sparingly in benzene and is readily dissolved by acids and alkalis. The benzoyl-compound C,,H,,N,O crystallises in stellate groups of needles melts at 179-180" is soluble in hot alcohol and benzene almost insoluble in water ether and chloroform.When trimethylene dicyanide is treated with hydroxylamine (1 mol.) at the ordinary femperature. a compound having the formula C5H,N,0 (which is the formula of y-cyanobutenylam.doxime) is obtained. It crystallises in colourless needles melts at 103" is readily soluble in hot water and alcohol very sparingly in ether chloroform and benzene. With ferric chloride it gives a red coloration but neither Pehling's solution silver nitrate nor lend acetate gives a pre- cipitate. It h& only basic properties being insoluble in dkalis. - N. H. M. Hydroxamic Acids of the Fatty Series. By C. HOFFMANN (Ber. 22 29562856) .-Acetohydroa*mic acid OH*CMe:NOH and not ethenylamidoxime as previously stated (compare Abstr.1887 911) is formed when acetamide (1 mol.) is treated with hydroxylamine hydrochloride (1 mol.) in cold concentrated aqueous solution. The mixture is kept until i t no longer reduces Fehling's solution then acidified with acetic acid and mixed witb excess of copper acetate ; the precipitated copper salt is washed suspended in alcohol decom- posed with hydrogen sulphide and the filtrate evaporated. It sepa- rates from dilute alcohol and hot water in crystals containing 4 mol. H,O melts at about 58-59" and is very readily soluble in water and alcohol but insoluble in ether. It loses its water over sulphuric acid under rediiced pressure and then melts a.t 87-88'. It has a neutral reaction gives a dark cherry-red coloration with ferric chloride and reduces ammoniacal silver nitrate solution in the cold.Formamide seems to react with hydroxylamine and sodoacetanilide and benzamide but only at ft higher temperature and even then very slowly ; benzhydroxamic acid wag obtained in rhombic plates melt- ing at 124-125". Intramolecular Change of Allylcarbamides into Isomeric Bases. By S. GABRIEL (Ber. 22 2984-2991).-PropyEene-~-thio- carbamide CHMe<Fi!,:g)> is formed when allylthiocarbamide (m. p. 74" ; 1 gram) is heated with fuming hydrochloric acid (sp. gr. = 1.1 7 ; 3 c.c.) at 100" for an hour and the clear liquid evaporated on a water-bath. The syrup is treated with 33 per cent. aqueous potash and extracted with benzene. It has an unpleasant distinctly basic odour and when distilled decomposes with formation of hydro- gen sulphide and ammonia.It is soluble in water. The p l a t i ~ ~ o - F. s. K.128 ABSTRACTS OF CHEMICAL PAPERS. chloride (CaH,N2S),,H2PtC1 forms orange-yellow crystals ; the trurochloride crystallises in yellow indented needles ; the picrate melts at 198-200" and is sparingly soluble. When the base is oxidised by means of hydrobromic acid and bromine-water (Abatr. 1889 848) P-methyltaurocarbamic acid S0,H*CHMeCH2-NH*CO*NH2 is formed ; this crystallises in colourless crusts readily soluble in hot water. ~ - M e t k y l t a w i n e SOaIT*CHMe*CH2*NH is obtained by heating the acid (5 grams) with crystdlised baryta (20 grams) and water (20 c.c.) for five hours at 140-150". It crystallises in rhombic plates which swell up when heated.Propyle?iethiocarbarrLide m ethiodide CaH6N2S,MeI prepared by evapo- rating a mixture of the base dissolved in methyl alcohol and methyl iodide melts a t 171-172". p-Dzwtethyltaurine SO,H*CHMee CH2*NHMe is obtained by treating the above methiodide with strong potash and extracting the base with benzene. The base (15 grams) is then dissolved in water (300 c.c.) neutralised with hydrobromic acid treated with bromine- water (2 litres) and heated on a water-bath until the oil which sepa- rates is redissolved. The whole is evaporated to dryness dissolved in hot water (15 c.c.) and allowed to cool. Crystals of dimethyltaurocarb- amic acid SO,H*CHMe*CH,.N Me*C0.NH2 (about 3 grams) separate ; these melt at 230-240". The filtrate from these crystals is evapo- rated down and heated with water (15 c.c.) and baryta (30 grams) a t 150-160" for three hours.The product is freed from barium evaporated to dryness and dissolved i n absolute alcohol (40 c.c.). It is then further piirified from the potassium bromide still remaining by means of platinic chloride. It crystallises from 96 per cent. alcohol in flattened prisms melts a t 220-223" and is extremely soluble in water. P~opylenecnrbamide CHMe< CH,,NH > is formed by the oxida- The picrate crystallises in long lust'rous O*C( NH) tion of allylcarbamide. needles melting at 185-186'. N. H. M. Ethylenelactic Acid. By M. STEGFRIED (Ber. 22 2711-2717 j. -The mother liquors from the crystalline zinc paralactate prepared from (horse) flesh contain as has been previously shown by Wislicenus (Annulen 167 302) small quantities of a zinc salt which does not crystallise. The author finds that this amorphous zinc salt is a salt of acetyllactic acid.When it is dissolved in alcohol and reprecipitated with ether i t is prtrtially converted into a basic salt from which acetyllactic acid can be obtained in colourless needles melting a t 166-167". This formation of zinc acetyllactate is ex- plained by the facts that flesh extract always contains traces of acetic acid and that acetyllactic acid is produced in small quantities when an aqueous solution of zinc paralactate is boiled with zinc acetate. ,4cetytZactic acid OAc*CHMe*COOH is also formed in small quan- tities when paralactic acid is repeatedly evaporated with 30 per cent. acetic acid.It can be obtained in somewhat larger quantities by gradually adding finely divided zinc paralactate (1 part) to anhydrousORGXSIC CHEMISTRY. 129 zinc acetate (4 parts) heated to its melting point and keeping the mixture in a liquid condition until it forms a homogeneous paste. The melt is digested with hot water the cold solution treated with dilute sulphuric acid and quickly extracted with pure ether; the resulting syrup dissolved in water the filtered solution evaporated with glacial acetic acid (+ vd.) and the crystals which separate are spread on a porous plate. Acetyllactic acid can also be prepared by heating paralactic acid (1 part) with glacial acetic acid (1 part) and sodium acetate (1% parts) at 180" for four hours ; it is isolated as already described.The acid prepared by these methods has the same melting point and the same crystalline form as that obtained from flesh extract. It is readily soluble in alcohol and most ordinary solvents but when kept it becomes insoluble in alcohol does not melt below 300° and decomposes at a higher temperature but without melting ; t h i s inso- luble modification is only slowly hydrolysed by alkalis whereas the original acid (m. p. 166-167') is readily decomposed even by water. The acid prepared synthetically and that obta.ined from flesh do not rotate the plane of polarisation. When acetyllnctic acid prepared from paralactic acid is boiled with soda it is decomposed into acetic acid and optically inactive lactic acid ; the occurrence of the latter in flesh extract a fact which has been observed by Heintx may be due to the previous formation of acetyllactic acid.Lactic acid yields an acetyl-derivative identical with the compound described above in crystalline form in melting point and in its hehaviour with solvents ; the same acetyl-derivative can also be obtained in small quantities by carefully decomposing ethyl rtcetyl- lactate with cold water. F. S. K. Conversion of Pentamethylene-derivatives into Benzene- Pyridine- and Thiophen-derivatives. By A. HANTZSCH ( Ber. 22 2827-2843).-A compound of the composition C ti,CI,BrO is formed when trichloropenteiiediliydroxycarboxylic acid (1 part) is heated for a few minutes a t 100" witsh bromine (5 parts) and water (5 parts) (compare Abstr. 1889 853). It cryat,allises in well-defined quadratic prisms melts a t 8T0 and is readily solulde in alcohol and ether but rather sparingly in water.I t quickly loses 1 mol. H,O when kept over sulphuric acid a second molecule of water being very slowly given off under the same conditions. The anhydrous compound can also be obtained by recrystallising the hydrate from hot chloroform from which it separates in hexagonal prisms melting at 136". Chluro- bromanilic acid is formed when the hydrate is warnted with excess of alkali but a portion is completely decomposed; this reaction takes place quantitatively when the hydrate is boiled with a concentrated solution of sodium carbonate the cliaracteristic red crystals of the sodium salt of chlorobromanilic acid separating From the hot solution. The hydrate does not combine with phenylhpdrazine it gives the sariie decomposition-products as trichloropentened i hy droxyca rhoxylic acid when heated at l:W" with excess of bromine and water and it is reconverted into the original acid when reduced with a small quantity VOL.LVIII. k130 ABSTRACTS OF CHEMICAL PAPERS. of sodium amalgam in alcoholic solution. These facts seem to show thgt this bromo-compound is a pentene-derivative of constitiition analogous to that of trichloropentenedihydroxTcarboxylic acid but. the following experiments point to a totally different constitution. It i s not acted on by concentrated sulphuric acid with formation of an open-chain ketone acid as is the case with the pentenecarboxylic acid. It has no well-defined acid properties only a feeble acid reaction rind dissolves in sodium carbonate without evolution of carbonic anhy- dride and not more readily than in water. Tt can be extracted from slightly alkaline solutions with ether and it cannot be accurately titraked with barjta and phenolpbthdeyn.Its electrical conductivity was examined b i Ostwaid and found to be seventy that of the original acid a fact b-hich shows beyond two compounds are analogously constituted. The this bromo-compound is therefore most probably times less thak doubt that the constitution of p-Chloropyridine is formed when n fiolution of l.2-chlorodi keto- pentamethglene is boiled with ammonia or when a solution of the sodium-derivative is boiled with any ammonium salt. The reaction is hest cai~ied out by adding ammonium acetate to a warm s:iturated solution of the sodium-derivative and heating the mixture to boiling when chloropyridine distils with the steam. This pyridine-deri- vntive is identical with the /3-chloropyridine obtained by Ciamician from chlorcform and potassium-pyrroline.@-Chloropyridiwe picrate crystallises in slender yellow needles melt- ing at 135" with previous softening. The ?r,ercvrochZo?-ide crystallises in fimall colourless needles melting a t about 180". The aurochloride forms moss-like needles and deromposes at about 200". a Thioplrenaldehyde is produced when 1.2-chlorodiketopenta- methylene is treated with hydrogen sulphide at a temperature below loo" and the reaction Cakes place almost quantitatively when hydrogen snlphide is passed into a solution of the sodium-derivative heated to 30-40" and finally to boiling; the aldehyde distils with the steam.and only small quantities of resinous products remain. The thiophenaldehyde thus obtained gives all the characteristic colour reactions for this compound and it is converted into tohe corrcspond- ingacid on exposure to the air. It combines with hydroxplamine yielding the aldoxime (m. p. 12SJ) and with phenylhydrazine forming the hydrazone which melts a t 134.5". Decompcsition-products of Chloranilic Acid. By A . HAXTZSCH (Ber. 2 2 2841-2833) -Tetrac?i 1o.l.oketotl.ihydroz~penturn ethy Zenecarb- oxylic acid I >C(OH)*COOH is produced when chlor- anilic acid (8 mol.) or t~ichlorodiketopentamethylenehydroxycarb- nxylic acid (1 mol.) is treated with sodiiim hypochlorite but the formation takes place slowly and only in neutral solutions (compare Abstr.1888 1190). It is best prepared by dropping a solution of sodium hSpochlorite into a cold aqueous solution of pure F. S. K. co - CCl C(OH),.CCI,ORQANIC CHEhlISTRY. 131 potassium chloranilate until the colour disappears then adding a volume of the hypochlorite solution equal to or rather larger thin Chat already employed and keeping the mixture for 24 hours ; it is then treated with concentrated hydrochloric acid extracted at least foiir times with ether and the crude product spread on a porous plate. It crystallises in small colourless needles melts and is completely de? composed a t 216" and is very readily soluble in water and alcohol ; it genemlly crystallises with 2 mola H20 both of which it loses slowly when kept over sulphuric acid.It resembles the original trichlorinated acid in appearance and is like the lattw completely decomposed by aPkalis yielding oxalic acid. It does not combine with orthotoluylenediamine or with phenylhydrazine and it is very stable towards oxidising agents ; it isnot acted on by boiling bromine-water only very slowly by potassium chloi-ate and hydrochloric acid and i t crystallises unchanged from hot concentrated nitric acid. It is not acted on by hot sulphuric acid in which it is only very sparingly fioluble. It is a bibasic acid and measuremenfs of its electrical con- ductivity show that it is a simple chloro-substitution derivative of the trichlorinated mid. The ammom'um salt. C6H2C1406(NH4)2 + H20 crystallises in short prisms melting at 147-148" with decomposition when an alcoholic solution of the acid is saturated with ammonia arid allowed to evaporate in the air; The barium salt crystallises well and is very readily soluble in acetic acid and moderately easily in water.The lead sil'uer and mercuric salts are amorphous and sparingly soluble but the mercurous salt crystallises well. The acid gives a red coloration witrh ferric chloiide. When the acid is heated with excess of bromine and water at 130" it is decomposed into carbonic anby- dride oxalic acid and tetrachlorodibromacetone. Chlorod~ketoyentameChyleneh~droxycarboxylic acid ~O'cHcl> C(OK)COOH CO-CH is obtained when a well-cooled nmmonical solution of the correspond- ing triclilol-o-derivative i s treated with zinc-dust in small portions a t a! time until there is no further development of heat ; the solution is then filtered acidified extracted with ether and the crudeacid purified by converting i b ivt,o the ammonium salt It crjs- tallises from ether in colourless microscGpic needles melbs at 147" with decomposition and behaves with solvents like the other acids of this class.The ammonium salt CBIE,C14(NH4) L crystallises from water in whkb i t is readily soluble in short thick prisms and de- composes at ahout 140° but has no well-defined melting point. Solutions of lead silver and mercurous salts produce precipitates in neutral solutions of the ammonium salt ; when orbhotoluglenediamine hydrochloride is added to a warm concentrated solution of tlie ammonium salt a yellowish-green azine is precipitated and pheriyl- hydrazine acet.ate precipitates an oily hydrazone which gradually solidities.When the acid is treated with concentrated sulphuric acid i t yields a syrupy acid probably chlorodiacetylglyoxplic acid and when warmed with excess of bromine it is decoriiposed i n t o chloro- The yield is small. k t L132 ABSTHAOTs OF CHk MlCAL PAPERS. pentahmmacetone (m. p. 91-92?') carbonic anhydride and oxalic acid. Dichlorodik~to~~en~ameth~leneh~droxycarboxylic acid can be obtained in like manner from the curroesponding tetrachloro-derivative but the yield is very small ; it is a syrup and is decomposed by concentrated soda in the cold yielding large quantities of oxalic acid. Te fra ch lo rodiacrty Zg l p x y Zic acid C 0 0 H*C (0 H)2.C C12-C 0.C 0.C H CI is obtained when triclilorodiacetyl~lyoxylic acid (1 mol.) is treated with sodium hypochlorite (1 mol.) as described above.It cyystal- lises in sniall colourless needles melts at 146-147" with decomposi- tion and is very readily soluble in all ordinary solvents. It forms an aziiie a.nd a crystalline hydra.zone and it is readily decomposed by sodium hypochlorite. Dichlorc~pyruriic acid C H C12-CO*COOH is obtained when tetra- chlorodiacetylglyoxylic acid (1 mol.) is treated with sodium hypo- chlorite (1 mol.) in neutral aqueous sohition. It crystallises in needles with 6 mol. H20 melts at :8-79" and loses its water over sulphnrie acid i t is very readily soluble in water but is reprecipitated on adding concentrated hydrochloric acid.It combi ties with phenylhydrazine forming a hydrazone which contains chlorine. Zromodiehloropyruvic acid CBrCl,*CO*COOH can be prepared by heating the preceding compound with bromine and water at 120" ; i t soparates from water with 3 niols. H 2 0 in colourless crystals loses its water over sulphuric acid and is immediately decomposed into bromo- dichlorosnethane and oxalic acid when treated with cold alkalis. F. S. K. Two Isomeric Syrnmetrical Dimethylglutaric Acids. By N. ZELINSKY (Bey. 22 'L82Y-2827) .-Ethyl dimeth!/ldicyar~oglutarate CH2[ CMe( CN)-COOEt] is formed when ethyl sodocyano-a-pro- pionate ( 2 mols.) is treated with methylene iodide ( 1 mol.) in alcoholic solution ; the yield of the crude product is about 50 per cent. of the theoretical quantity.It boils a t 282-288" with otlly slight decomposition (at 165-170" under 10-12 mm.) but could not be obtained pure. When boiled for 10-12 hours with moderately coricentrated hydrochloric acid it yields two isomeric symmetrical dimethylglutaric acids CH2(CHMe.COOH) which can be separated by fractional crystallisation. The one melts a t 202-104" the other at 128"; the silver salts C,Hl,Ag,04 of both acids are moderately Rtable and undergo no change when heated a t 100". Dipher! ylglutaric acid (symmetrical) has been prepared by the author and Feldmann and is a t present under investigation. Dimethyladipic acid (symmetrical) seems to exist in two isomeric m odifimtions. I?. S. K. Dicarboxylic Acids C,H,,O,. By I(. AUWERS and V. MEPER (Bey. 22 3005).-Of the two acids obtained by the action of silver on ethyl a-bromisobutyrate (Abstr. 1889 1143). the volat,ile acid is tetvamethylsuccinic acid whilst the non-volatile acid is symmetrical dimetbyladipic acid C,H4((;HMe*COOH)2 (compare Zelinsky pre-ORGANIC CHEMISTRY. 133 ceding abstract). According to Hell (Ber. 10 2229) a portinn of tlie a-bromisobutgric acid decomposes into hydrogen bromide and methyl- acrylic acid which unite according to Fittig and Engelhorn (Annalen 200 65)) to form p-bromisobutyric acid. The normal product of the action of silver on the lattar would be the above dimethyladipic acid. I n order to test the correctness of this view the authors are studying /3-bromisobutyric acid and especially its behaviour towards silver. N. H-.M. Allylethylsuccinic Acids. By E. HJELT (Ber. 22 2906).- Allylbutenyltricarboxylic acid was heated until the evolution of carbonic anhydride ceased and the residue was crystallised from boiling water. Two isomeric nllylethy lsuccinic acids C,H,,O were obtained. The pnm-acid crystallises in small rhombic scales sparingly solable (1 110) i n water and melts a t 1.;5-156"; the anti-acid crystallises in srnall plates more readily soluble (1 37) in water and melts at 110-115". L. T. T'. Action of Bromine on Ethyl Oxalacetate. (Ber. 22 2912-2915) .-EtlhyZ ddbrornozalacetate COOEt*CO.CBr,*COOEt is formed by b a t i n g a solution of the acetate in an indifferent solvent with a slight excesq of bromine. It forms a colourless oily liquid which boils at 165 -168" under '20 mm.pressure; it is in- soluble in water and gives no coloration with ferric chloride. It is easily decomposed! by bases the resolution taking place between tho ketone- and dibromo-groups. Ammonia for instance yields oxamide dibromacetamide and alcohol ; whilst phenylhydrazine yields oxalic diphenylhydrazide (CO-N,H,Ph),. Etli y l monobromoxalacetafe COO E t*CO*CHBr.COOE t is obtained by the action of ex:tctly the theoretical quantity of bromine on pure ethyl oxslacetate in carbon bisulphide solntion ; its purification is possible by fractional distillation in a vacuum but is most easily effected by the cryst:tllisation of the sodium-derivative. It is an oil boiling a t 144-147" under 8-12 mm. pressure. Its alcoholic solu- tion is coloured intensely red by ferric chloride.Attempts to isolat,e the acid COOH*CO*CH( OH)*COOH by substituting hydroxyl for the bromine proved futile although this acid seems to be formed but immediately decomposed again. By W. WISLICENUS L. T. T. Tricarballylic Acid. By W. 0. EMERY (Be?.. 22 2920-2924). -Tricarballylic chloride C6H6C1303 prepared by the action of phos- phoric chloride on the acid forms a thick pale-yellow oil boiling with slight decomposition at 140" under 14 mm. pressure. Tricct7-6- allylanilide C,H,(COWHPh) obtained by the action of aniline on the chloride crystallises in very thin white needles melting a t 252". Trimethyl tricarballylate C,H,(COOMe)J is a colonrless liquid boiling at 150" under 13 mm. pressure ; sp. gr. = 1.18281 a t 20J (water at 4" = 1). With concentrated aqueous ammonia it yields tricabally 1-134 ABSTRACTS OF CHEMICAL PAPERS. am;& C3H5(OON R?) which crystallises in long prisms easily soluble in water very sparingly .in alcohol ether chloroform &c.and melt- i n g with decompositian at 205-203" t o a black liquid. L. T. T. Phenylthiophen. By A. RGNARD (Compt. rend. 109,699-700). - When a mixture of the vaponrv of toluene and sulphur in equal propor- tions by weight is passed through an iron 6ube heated to dull redness thc products are hxdrogen sulphide carbon bkulphide and a blackish .substance which solidifies on cooling. If the latter is distilled i t yields some carbon bisnlphide and unaltered toluene and a yellow solid substance which is purified .by repeat,ed crystallisation from alcohol. A portion of the product is only very slightly soluble in alcohol and consists of another thiophen-derivative. PhenyZthiophen CISH3Ph forms brilliant white plates which melt at 170" sublime easily and boil a t about 30U".It is only slightly soluble in cold alcohol more soluble in boiling alcohol very soluble in benzene light petroleum chloroform arid carbon bisulphide but le<s soluble in ether. With isatin and sulphuric acid it gives a blue coloration and with phenanthraquinone and sulphuric acid a green coloration. Chromic acid in presence of acetic acid converts it into benzoic acid. ~)ibro1)7ophenlllthiop~n CJ&I3rC4SHar is obtained by the action of excess of bromine and forms vexy small white crystals which melt at 195" and are almost insvluble i n all ordinary solvents but dissolve to some extent in carbon bisulphide.It gives a green coloration with phenan;tbraqninone and sulphuric acid and when oxidised yields parabrmbenzoic acid melting at 251". D1:,/itro~l/e~yZthio~hen C,H4N02*C4SH2*N0 is obtained by the gradual addition of phenylthiophen to fuming nitric acid. It forms a. yellow non-crystallisable powder which melts a t 1789 is almost insoluble in all ordinary solvents and whm oxidised yields para- aitroberizoic acid melting a t 2332. PhenllLth~o~hendisulpl~onic acid is formed'by heating phenylthiophen with ordinary sulphuric acid at a temperature of 50" to 60"; i t yields a barium salt which is very soluble in water and very difficult to crystal lise. Phe122/tthio~~e~te~rasZLlpkonic acid is obtained by the action of Nord- hausen acid on phenylthiophen; its barium salt is veiy soluble in water.C. H. B. Derivatives of Ethylbenzene. By W. SUTDA (Ber. 22 2919-2920).-With regard to Sempohwski's work (this vo!. p. 5!) the author points out that oi*thethylphenol and its sulphonic acid have already been described by Suida and Plohn (Abstr. 1881 268) and others. 11. 1'. T. Xylylene Sulphides. By E. HJmfr (Rer. 22 2904-2905).- Ortho-xylylene sulphide described by Leser (Abstr. 1884 1313) crystallises a t O" but is very unstable changing quickly into a blackORGAN10 CHEMISTRY. 135 resin. The ~nercuroc7~Zoride ( CsH6S)2,HgC12 crystallises in soft long needles. A platinochloride and a bromide were also obtained Ortho- xyl y 1 methy lsulphine iodide S c6H &I forms yellowish crystals melting a t 154-155". When this iodide is treated with water and silver oxide a strongly basic sulphonium hydroxide is formed.When mets- and para-xylylene sulphides are treated with potas- sium sulphide insoluble white amorphous compounds are formed. The author has not yet obtained them quite pure btit analyses leave little doubt but that they are the corieaponding rneta- aild para- xcy ly lene sulp hides. Ethereal Oil of Betel-leaves. By J. F. EFKMAN (Be)-. 22 2736-2754. Compare Bertram and Gildemeister Abstr. 1889 863).-The leaves of CImiica BsfEe Mip. when distilled with water yield a small quantity of a yellowish-green oil which has a burning taste a peculiar pleasant smell and is feebly laevorotatorg. Wheu shaken with concentrated potash it is partially dissolved and on adding sulphuric acid to the solution a phenol (chavicol) is pre- cipitated.The portion insoluble in aikali can be separitted by fractioiial distillation into two principal portions boiling at 175 -190" and 255-265" respectively. Chavicol C9Hlo0 is a colourless liquid boils at about 237" atid is soluble in alcohol ether chloroform and light petroleum in all proportions but only sparingly in water and ammonia. With ferric chloride the aqueous solution gives a blue coloration which disap- pears on adding alcohol. Molecular- weight determinat,ions by Raoult's rnet,hod vapour-density determinations carried out in an atmosphere of hydrogen under reduced pressure a n d an examination of its re- fractive properties showed that the molecular formula of this phenol is CgHl,O.It is a powerful antiseptic its action on bacteria being five times as strong as that of phenol and about twice as strong as that of eugeiiol. The ethyl-derivative CgH,*OEt prepared by Iieating chnvicol with potash and ethyl iodide in alcoholic solution is a colourless liquid boiling at about 232" ; when oxidised with chromic acid i t yields parethoxyhenzoic acid (m. p. 195"). Its molecular formula was found to be C11H140 by the same methods a s those employed in the case of chavicol. The methy1-derivative CgHg.OMe prepared in like manner is a colourless liquid boiling a t about 226 ; its molecular weight determined optically was found to be 151. When oxidised with potassium permangannte it yields anisic acid and an acid of lower melting point probably pammethoxyphenyl- acetic acid. The fraction boiling a t 115-190" and insoluble in alkali (see abovc) probably contains several terpenes perhaps also cymeue and cineole but i t is free from pinene; no pure compound could be isolated from the mixture.The fraction boiling a t 255-265" contains a colourless sesqui- terpene C1,HZ4 boiling at about 260". GLiavicol has most probably the constitution OH*C,H,-CH,*CR:CH [= 1 :.4] as is shown by its chemical properties aud also by its low refractive power. L. T. T.136 ABSTRACTS OF CHEMICAL PAPERS. An optical examination of isosafrole and isoeugenol showed that both compounds probably contain the propenyl-gr&p-CH:CHMe. F. S. K- ~- -. __ Safrole. By T. POLECK (Bet-. 22 2861-2863).-When safrole is oxidised with potassium permanganate i t yields piperonal piperonylic acid formic acid acetic acid oxalic acid and carbonic anhydride but no propionic acid is formed as stated by Scliiff (Abstr.1884 1338) ; this result is in accordance with the view that safrole is the methylene ether of an allyldihydroxybenxene. Phloroglucinol. By Z. H. SKRAUP (Molzatsh. 10 721-725) .- The author has previously described the actio2 of benzoic chloride on phloroglucinol in presence of elkalis (Abstr. 1889 1152) and has now by careful fractional crystallisation of the product from benzene succeeded in obtaining the following compounds in a state of purity. DireswcinyZ tetra benzoate Cl2H6O4Bzd is readily soluble in hot benzene and crystallises from i t on cooling in prisms melting at 199".PhZo?-o- glucinyl tribenzoate C,H,O,Bz is insoluble in water only slightly soluble in alcohol and crystallises from benzene in plates or scales melting a t 173-174". Commercial phloroglucinol may best be purified by first converting it by means of potassium hydrogen carbonate into phloroglucinol- carboxylic acid (which may be obtained free from other compounds by taking advantage of the fact that it is soluble with difficulty in a solution of potassium carbonate and alcohol) and afterwards repro- ducing the phloroglucinol by boiling t'he pure carboxylic acid with water (compare Will Abstr. 1885 906). F. S. K. G. T. M. Action of Alkalis and Ammonia on Halogen-substituted Quinones. By F. KEHRMANN (J. pr. Chem. [2] 40 365-375).- Paradiethoxydichloroquinone (Abstr.1889 707) melts a t 97-98" ; it has the same formula as Stenhouse's ethyl chloranilate obtained by the action of ethyl iodide on silver chloranilate but is not identical with it. The author distinguishes the former as the P-compound and the latter as the a-compound. Both are obtained by the action of potassium ethoxide on clrloranil but the /%compound largely pre- dominates when the solutirrn is weak and the temperature low. If the reaction for preparing the ,!3-compound (Zoc. cit.) is allowed to proceed near the boiling point of alcohol a considerable quantity of the a-compound crystallises wi t,h the P-compound and may be separated from i t by fractional crystallisation from hot alcohol in which the a-compound is more soluble as small red needles melting at 104-105".The a-compound cannot be changed into the /3-compound or vice vers6 by crystallisation. The p- and a-methyl-compounds are also both produced by the action of potassium methoxide on chloranil the /%compound pre- dominating when the temperature is lower. By crystallisation from benzene the dimethoxydichloroquinone (/I-compcjund) is separated a t first either as grains or needles melting a t 157-158" not 130' (loc. cit.). The methill chloranilate (a-compound) separates from the mother liquor of the p-compoilnd in leafy crystals melting atORGANIC CHEMISTRY. 137 141-142" and identical with those obtained by t h e action of methyl iodide on silver chloranilate. By acting on the z-ethyl-compound with ammonia and with aniline chloranilamide and chloranilanilide are obtained respectively ; they are identical with the amide and anilide produced by the action of ammonia and aniline on chloranil and are therefore paradiamido- paradichloroquinone [O C1 (NHE,) = 1 4 2 5 3 61 and para- dianilidoparadichloroquinone [02 C1 (NHPh) = 1 4 2 5 3 ti] respectively. When the /3-ethyl-compound is heated with excess of aniline in alcohol for some time it becomes dark-green and dark-green crystals with a violet iridescence separate.With ammonia instead of auiline a deep-violet colour is produced and by diluting the alcoholic solution with water dark violet needles are obtained. When the p-compound is heated with excess of aqueous potash most of it is converted into potassium chloranilate ; but i f dilute potash is added drop by drop in slight excess to a cold alcoholic solution the liquid becomes suc- cessively violet yellow-red and colourless ; if now heated it becomes permanently violet and a violet potassium salt may be crystallised out.When the i3-compoand is shaken with stannous chloride in ethereal solution the ,3-quinol only is obtained but if an acetic acid soluti*on is so treated both the /3-quinol and a - q u i d are obtained. The a-compound yields only the r-quinol. a- Uiethoxydichloroquinol melts a t 151-152" not 148-150" (Zoc. p- Diethoxydichloroquinol forms lustrous colourless leaves or needles melting a t 108-109"; in water they melt a t 70" the greater part dissolving and separating again on cooling. a- Diwet hox ydichloroguino l forms short colourless prisms melting a t 195-196" soluble in the ordinary solvetits except water.p- Din7 ethoxydichZoropuintZ forms colourless prisms melting at 156- 157". A. G. 13. These matters are still under investigation. cit.) . Paratoluidine Oxalate. By E. BORYEMANN (Bm. 22 2710) .- Paratoluidine oxalate C,H,KH2,C,0sH2 crystallises with + mol. of water. F. S. K. Action of Bromine on Paratoluidine in the Presence of Concentrated Sulphuric Acid. By R. HAFNER (Ber. 22 2902-2904 ; compare this vol. p. 37).-125 grams of bromine was added to a solution of 30 grams of paratoliiidine in 400 grams of sulphuric acid and the whole allowed t l ) remain for 10 days. A good deal of paratoluidine remained unchanged whilst metabromopara- t,oluidine and orthobromoparatoluidine were formed.Sulphuric acid therefore seems to have a tendency to promote the formation of B meta-derivative as was noticed (Zoc. cit.) with chlorine-derivatives. L. T. T. Action of Aluminium Chloride on Dirnsthylaniline. By H. GIKAUD (Hull. SOC. Chim. [ 31 1 691-69~3).-81uminium chloride and dimethylaniline combine with developmznt of heat and yield a,138 ABSTRACTS OF CHNMICBL PAPFRS. substance which crystallises in long prisms melting at 88" ; no reac- tion however obtains when the original compounds are heated in sealed tubes a t 250' for 10 hours. Dimethylaniline when heated with excess of aluminium chloride in presence of air yields a base which crystallises from alcohol in small felted needles melting a t 195" and colowed green by oxidising agents ; it is a tetramethylbenzidine N~~ez*C6H,*C68,*NMe2. From dimethylaniline containing dimethyltoluidine by similar treatment a base melting a t 90" coloured blue-violet by oxidising agents and which appears to be tetraniethyldi~midophenylmethane is obtained.The author is continuing the research. T. G. N. Condensation of Phenylenediamines with Butaldehydes. By LASSAR-COHN (Bey. 22 2724-2i%).-A compound CIOHI4N2 is formed when orthophenylenediamine (10.8 grams) is mixed with a yuantity of alcohol insuflicient f o r corriplete solution and then treated with isobutaldehyde (7*6 grams) ; the mixture is boiled for a short time and the crystalline compound which separates on cooling is purified by pouring its a.lcoholic solntivn into warm water. It sub- limes in cvlourless needles melts at 233" and is very readily soluble in alcohol but almost insoluble in ether.The hydrochloride CloH,,N,,HC1 crystallises from water and alcohol melts a t 184" has not poisonous properties and forms a golden PZatinochloride An isomeric compound is obtained in like manner from isobutalde- hyde and metnphenylenediamine ; it melts a t 216" and separates from benzene and chlo~of~nm in crusts. The yZutirLochEoride has the composition ( CIOHIINz)~,HZ PtCI6. Isobutaldehyde and paraphenylenediamine yield an oily base the platinochloride of which has the composition (C,HL4N2),,H,PtC16 but neither the base nor the hydrochloride could be obtained in crystals. Normal butaldehyde does not react with orthophenylenedismint! in solution in absolute alcohol. F. S. K. (Cia H,,N,),,H,PtCI,.Fluorescent Derivatives of Aromatic Metadiamines. By H. SCHIFF and A. VANNI (A7~9mZen 253 319-335; compare Schiff ArLtraZe,i 140 97 and 159 64) .-Mettttoluylenedinmine combines wit 11 oenanthaldshyde yielding a compound of the composition C,H6N,(C,HI4),; if the reaction takes place in the cold the alcoholic solution of t9he product is only slightly fluorescent until after the additmion of a few drops of hydrochloric acid When metatoluylene- diamiue is warmed for a few hours with a slight excess of oensnth- aldehyde an orange vitreous mass is obtained the alcoholic solution of which is highly fluorescent. This product consists of a portion readily soluble in cold ;ilcohol probably methyltetrahydrodibutyl- phenanthroline and a portion which is only sparingly soluble ; they both resemble the original product are very stable and are not de- composed by warm hydrochloric acid.A red compound probably dibut8yloctohyclrophenanthroline is formed when cmianthaldehyde is added to a warm alcoliolic solution of metapheiiy!enediamine hydrocliloride and the solution shows 8rORGAKIC CHEMISTRY. 139 green fluorescence ; a thick oil remains on evaporation readily soluble in benzene but more sparingly in ether and insoluble in water. The ylutinochloride seems to have the composition ( C&32N2)2,H,PtC16. Acetaldehyde or paraldehpde combines with metaphenylenedia- mine hydrochloride in alcoholic solution forming a red semi-solid com- pound the solutions of which are deep-orange and especially when dilute show a green fluorescence.On adding ammonia to an aqueous solution of the crude product the free base probably dimethyltetra- hydrophenanthroline is precipitated in the form of a reddish- brown unstable powder. The p-lntinoclcloride ( C14HlsNz),,&PtC~ is an orange amorphous compound which dissolves sparingly in alcohol yieldiiig a highly fluorescent solution. When the base is oxidised with potassium perrnauganate it jields an acid and this like the base itself gives considerable quantities of pyridine-derivatives on distillation. Metaphenylenediamine and metatoluylenediamine hydrochlorides give analogous compounds (alkyl hydrophenanthroline salts) with other aldehydes of' the fatty series. Sal ;c y 1 olmetap hmylen sd itrmiiAe hydrocldoride C 6H4 (N :C H. C 6H4' OH) 2 H C1 prepared by treating phenylenediamine hydrochloride with salicylic aldehyde in alcoholic solution is an orange crystalline compound.The free base is a yellow flocculent substance soluble in alcohol and hydrochloric acid ; it4 is decomposed by acids or by prolonged boiling with water. The plutinochloiide (CzoHls0,N2),B2PtC16 is a cinnabar- red powder. SalicyloZ?netatoZuylenediamine C7H,@:CHC6H4*OM) crystallises from a mixture of alcohol and benzene in long yellow needles and is readily soluble in ether and benzene but only sparingly in alcohol. It has only feeble basic properties is soluble in moderately concen- trated potash aud is converted into a low-melting acetyl-derivative by acetic acid. Cuminoliiietatoluylenediamivae C7H6(N:CH*C6H4Pr) is a yellow crystalline powder melts at about 99" with decomposition and is very readily soluble in benzene and ether ; it has no basic properties and its soiutions do not fluoresce.Ciitnamaldehyde combines with metaphenylenedinmine hydro- chloride i n warm alcoliolic solution yielding an orange unstable powder most probably tetrahydrodiphenylphenanthroline hydro- chloride. Cinnamaldehyde and metaloluyienediamine hydrochloride under the same conditions give a red microcrystalhe salt the very dilute solutions of which show a feeble fluorescence; the platino- chlovide is a yellowish-red crystalline powder soluble in alcohol. Cinnamolmt.tntoluylenedinmine C7H6 (N 1CH.C kl :CHPh) is pre- cipitated BS an orange powder when cinnamaldehyde is treatrd with metatolulenediamine in dilute alcoholic solution ; it melted at about 380" but could not be obtained in a pure condition. It com- bines with bromine ('2 mols.) yielding a red unstable powder. Amidophenyleneoxamic acid combines with fatty aldehydes in alcoholic hydrochloric acid solution yielding compounds which show140 ABSTRACTS OF OHEMICAL PAPERS.a slight green fluorescence. When fhe ammonium salt of this acid is treated with a mixture of furfuraldehyde and aniline hydrochloride a red dye is formed. Para phen y 1en ediamine and or t ho tc 11 u ylened i amine do not give fluorescent condensation-products with aldehydes of the fatty series. F. S. K. Azotoluenes and Azoxytoluenes. By J. V. JANOVSKY (Monatsh. 10 535-601 ; compare Abstr. this vol. p. 392 and 865). Mononitro- parazotoluene is best obtained by heating a t 30" a mixture of azotol- uene with one-fifth of its weight of nitric acid of sp.gr. 1-43. It may be recrystallised from alcohol melts at 80" and has the formula- 3 1 4 1 NO,*CsH,Me*N,*CsH,Me since on reduction with tin and hydrochloric acid it yields a mixture of paratoluidine and P-toluylendiamine [Me (NH,) = 1 3 41 melt- ing a t 88". If in the above mentioned operation the temperature is allowe6 to rise above 30" or if it stronger acid is used dinitroamtoluene [Me (NO,) N = 1,l 3,3 4,4] melting at 114" is formed. On re- duct>ion with alcoholic stannous chloride this yields P-toluylendi- amine and must consequently be regarded as the symmetrical com- pound Tha two trinitroszotoluenes previously described (Zoc. cit.) which melt a t 1:B" and 139" respectively are both converted on reduction into 6-toluylendiamine and the sa,me triarnidotoluene [Me (NH,) = 1 2 3 41 the hydrochloride of which crystallises in scales which become coloured on exposure to the air; they must con- sequently be regarded as physical isomerides having respectively the formulE- G.T. M. Amidoximes and Azoximes. By F. TIEMBNN (Ber. 22 294%- 2946).-This paper gives a sliort r4sume' of the work previously done on the subject of diamidoximes and diazoximes by the author and his collaborators. The oxaleneamidoximes snccineneamidoximes glutnreneamid- oximes isoplitlialeneamidoximes and hometerep h thalet~eamidoximes are soluble in boiling water and alcohol very sparingly so in ether. Their aqueous solutions show very strongly the characteristic arliid- oxime reactions.The hydrochlorides of the diamidoximes coil tain 'L mols. of hydrogen chloride and are highly crystalline but easily lose a part of the hydrogen chloride. The replacement of the two hydro- gens of the twc; oximide-groups takes place in a normal way but hitherto all attempts to displace only one of these atoms have proved unavailing. The acid derivatives of the diamidoximes NO( COR) :C (NH,)*R"*C(NH) :NO*COR pass less easily into the azoximes than the corresponding derivativesORGAN [C CHEJIISI'RY. 141 of monamidoximes. The diazoximes so formed have the general formula <CR:N>C*R'"C<N.CR>. The diamidoximes of such 0 -N N - 0 dicarboxylic acids as easily forin irnides decompose very readily into imido-dioximes of the f o r m u l e thiis forming compounds with 5- and 6-atom closed rings which are soluble in water are sometimes basic sometimes acid in character and usually yield stable silver-derivatives.When hydroxylamine (1 niol.) acts on such dinitriles as yield imidodioximes ( 1 mol.) basic derivatives are formed isomeric with cyano-amidoximes. The constitution of these compounds is not yet fu Ily provcd but as an example that obtained from orthocyanobenzyl cyanide is probably represented h-j the formula- L. T. T. Formation of Benzaldoxime. By B. LACHOWICZ (Bey. 22 2H87 -2888) .-Benzaldoxime is best prepared by triturating hydro- berizamide (1 mol.) with hydroxylamine hydrochloride ; the reaction is at an end in 10 to 1.5 minutes and on adding water the benzald- oxime is precipitated as an oil.Amidoximes and Azoximes. By F. TIEMANN (Bey. 22 2758- 276l).-The author makes a few general remarks on the papers of Biedermann (this vol. p. 175) Spilkcr (next abstract) and Miller (this vol. p. 144). Nitrogen-derivatives of Salicylic Acid. By A. SPILRER (Beg.. 22 2767-2790).-Salicylamide is best prepared by heating ethyl salicylate a t 100" w i t h concentrated ammonia; it melts at 138". Dibi.omosaZ;cyZamide OH.C6H,Br,*CONH prepared by treating a warm concentrated aqueous solution of the amide with excess of bromine-water crystallises from dilute alcohol in colourless needles mdts at 183" with decomposition and is readily soluble in alcohol ether and alkalis more sparingly in benzene and chloroform. I n aqueous alcoholic solutions ferric chloride produces a reddish-violet coloration.Salicy Zothiamide OH.CsH4-C SNH2 is obtained together with several other compounds when the amide is melted with phosphorous penta- sulphide. It cr~stallises from hot water in colourless needles melts at 117-118" and is readily soluble in alcohol ether chloroform benzene bof water and alkalis. It is slowly converted into the amide when boiled with water or alkalis. Ferric chloride in dilute aqueous solu- tions produces a violet coloration and a brownish- black precipitate is formed on heating. Lead acetate copper sulphate and silver nitrate also produce precipitates in the cold or on warming ; these compounds darken in colour wit,h separation of the metal. Salicylonitrile OH.C,H,.CN is best prepared by distilling the F.S. K. F. S. I(.142 ABSTRACTS OF CHEMfCAL PAPERS. thiamide under reduced pressure ; it crystallises in colourlees needles melts at 98" boils a t 195" (I80 mm.) and is readily soluble in alcohol ether benzene and chloroform but only spayingly in cold water. With ferric chloride aqueous solutions give a violet coloration and with bromine-water a colourless crystallirle precipikate. The compound (m. p. 195") obtained by Grimaux (Bull. SOC. Chirn. 13 26) by heat- ing salicylamide with phosphoric anhydride and also by Ahrens (Ahstr. 1588 266) from orthamidophenol by Sandmeyer's reaction is not salicylonitrile although the latter can be obtained by both these me tlh od s . Dihromosali~~yZt~iamids OH*C6H2Brz*CS-NH2 is obtained when the thiamide is treated with excess of bromine i n dilute alcoholic solution ; if a solution containing salicylthinmide and salicylamide is gradnally treated with bromine-water monobmmosalicyl thiamide is precipitated first the nmide remaining in solution.Dibromosalicylthinmide crystallises from alcohol in dark-violet microscopic needles melts at about 230" with previous softening and is moderahely easily soluble in alcohol ether benzene and chloroform. yielding violet solutions but is insoluble in water ; it dissolves unchanged in alkalis forming a dark-violet solution. In alcoholic solutions silver nitrate copper sulphate and lead acetate produce dark-red precipitates. Xalicenylamidoxime OH*C,H,*C (NH?):NOH prepared by boiling tlie thiamide with hydroxylamine hydrochloride alrd sodium carbonate in dilute alcoholic solubion crystallises from water and benzene in thick colourless needles melts a t 98-99" and is readily soluble in alcohol ether chloroform acids and alkalis ; in aqueous solutions ferric chloride p~*odrtces an intense violet coloration Fehling's solution and copper sulphate a greenish precipitate and silver nitrate on warming a metallic mirror.The hydrochloride C7H6NzOz,HC1 melts at 175" and is very madily soluble in water. The platiizochloride forms small ill-defined crystals and is readily soluble in water and alcohol. The sodiwm-derivative C7H6N2O2Na3 is precipitated as R colourless hygroscopic powder when the amidoxime is treated with sodium ethmide in alcoholic solution and a large volume of ether then added.The compound C7H7N202Na is obtained in like manner when sodium ethoxide (1 mol.) is employed i t is a colourless crystal-line substance and is very hygroscopic. The copper-compound has the composition CI4HI4N4OJC~. prepared from dibromosalicenylthiamide in like manner crystallises from dilute alcohol in colourless plates melts a t 180" and is readily soluble in alcohol ether acids and alkalis but more sparingly in chloroform benzene and light petroleum and very sparingly in water. In alcoholic solutions copper sulphate produces a gi-eenish precipitate ferric chloride a reddish-violet coloration ; alkaline solntions reduce silver nitrate and give a green precipitate with Fc hl in g ' s s ol u ti o n . The c y ~ p er - derivative ( C H ,N 0 B r 2) C u i s sparingly soluble in watei.an0 alcohol. Snlicenylamidozimesul~hunic acid So3H*C6H3( OH)-C(NH,) :NOH is Dih-0 mosa lice n y lam id oxhe 0 H*C6H?B rz*C (NIX2) :NOH,ORQANlC CHEMISTRY. 143 obtained when the aniidoxime is heated with concentrated sulplturic acid a t ahnut 150"; it separates from boiling water iii colourlescl crystals does not melt below 250" and is insoluble in alcohol ether chloroform and benzene and only very sparingly soluble in cold water. The salts of the alkalis and alkdine earths are readily soluble in water. The barium salt (C7H7N2S05)2Ba separates from hot water in colourless ill-defined cr~stnls. B c n z n y lsa7'icea y lamidoaime OH*C6H,*C (NH,) KOBz crydallises from dilute alcohol in needles melts a t 173" and is readily soluble in ether alcohol chloroform and benzene sparingly in alkalis and insoluble in water and acids. J t gives a reddish-violet coloration with ferric chloride and a precipitate with bromine-water.The acetyl-derivative OH*C,H,~C(NH2):NOAc crystallises from warm water in colourless plates melts a t 117" and is reRdily soluble in alcohol ether alkalis and acids but only sparingly in chloroform benzene and water ; in dilute alcoholic solutions ferric chloride produces a reddish-viol& coloration and bromine-water a colourless precipitate rralicen~lbenzen~taxox~~e OH*CsH4*C<- N>CPh prepared by boiling the benzoyl-derivative for a long time with water or heating it alone a t 180". separates hom hot dilute alcohol in crystals melts at 128" and i s readily soluble in alcohol ether chloroform and benzene but insoluble in water.I n dilute alcohol~c solutions copper sulphate produces a green bromine-water a colourless precipitate and ferric chloride a violet coloration which quickly disappears. The eth,enyZ- azozime C9H,N,O2 prepared by heating the acctyl-derivative a t 125" or by boiling i t with water or acetic anhydride crystallises from dilute alcohol in colourless needles melts at 77" and is readily soluble in alcohol ether chloroform benzene and alkalis but only sparingly in water. It gives the usual reactions with ferric chloride copper sulphate and bromine-water. Dibenzoy ZsaZiceny lamidoxime OBz*C,H,*C( NH,) :NORz i 8 obtained together with d h y l benzoate when the amidoxime is treated with benzoic chloride and sodium ethoxide in alcoholic.ethereal solution It separates from dilute alcohol in coIourless ill-defined crystalfi melts at 127" and is readily soluble in alcohol ether benzene and chloroform but insoluble in water and acids ; i t gii-es H colourless precipitate mith bromine-water and i t is decomposed by alkalis. N - 0 The corresponding azoxime OBz*C,HI*C<-N>CPh can be pre- pared by boiling the dibenzoyl-derivative with water or by heating it above 150" ; also by treating salicenylbenzenylazoxime with benzoic chloride and sodium ethoxide in alcoholic solution. It crystfilliscs from alcohol in colourless needles melts at 120". and is readily soluble in benzene ether and chloroform but insoluble in watc.1. and acids; it is decomposed by warm alkalis and it gives a colourless precipitate with bromine-water. DiacrtylsaZicenyZamidoxirme OAc*C,H,.C(NH,):NOAc is formed together with the corresponding azoxime when the amidoxime is treated with sodium ethoxide and acetic chloride in ice-cold ethereal NO144 ABSTRACTS OF CHEMICAL PAPERS.solution but it cannot be obtained in a pure state. The azoxime C,,H,,,N,O is best prepared by treating sodosalicenylethenylazoxime with acetic chloride in alcoholic ethereal solution. It crystallises from dilute alcohol in colourless needles melts at 74' and is very readily soluble in alcohol ether chloroform and light petroleum but only sparingly in water; i t gives a colourless precipitate with bromine-water and it is quickly decomposed by alkalis. Sa licen y Zet hy lamidoxime OH* C6H,* C (NH,) :NO E t is formed together with its ethyl-derivative when the amidoxime is heated with sodinm ethoxide and ethyl iodide in alcoholic solution.I t is a colourless oil boils at 278" (at 220' under 150 mm.) and is readily soluble in acids and alkalis but insoluble in waher. and only sparingly soluble in light petroleum. In dilute alcoholic solutions ferric chloride pro- duces a violet coloration and bromine-water a colourless precipitate. The ethylderivative OEt*C,jH*-C(NH,):NOEt is a colourless oil boils a t 195" (180 miu.) and is readily soluble in acids but insoluble in water and alkalis. SaZiceny7etl~yZamidozime chZoride OH.C6H4*CC1:NOEt prepared by warming the preceding compound with sodium nitrite in dilute hydfochloric acid solution is a colourless oil boils at 233-234" (at 178 under about 'LO mm.),and is readily soluble in alkalis but insoluble in water and dilute acids ; it gives a reddish-violet coloration with ferric chloride and a colourless precipitate with bromiiie-water.Salicenylphenyluramidoxime OH*CsH,.C (NOH)*NH*CO.KHPh pre- pared by triturating tlie arnidoxime with phenylcarbimide crystal- lises from dilute alcohol in colourless plates melts at 119" with de- composition when heated quickly and is readily solnble in alcohol ether and alkalis moderately easily in benzene chloroform and acids and insoluble in water ; it gives the usual reactions with ferric chloride and bromine-water. Salicenylethylamidoxime and its ethyl-derivative combine with phenylthiocarbimide yielding compounds which are insoluble in water and do not crystallise well.Salicenylamidoxime combines energetically with phenylthiocarbimide forming the thiouramidoxime and diphenylthiocarbamide. SaZicen~lu~amidoxime OH.CGH4.C (NOH) -NH*CONH2 crystallises from dilute alcohol in colourless plates melts at 148" with decomposi- tion and is readily soluble in alcohol benzene acids and alkalis moderately easily in ctiloroform and ether and sparingly in water ; it gives a reddish-violet or reddish- brown coloration with ferric chloride. F. S. K. Anisenyl-. Salicenyl- and Methylsalicenyl-amidoxime. Ry J. A. MILrAEii (Be,.. 22 2790-2801).-Anisaldoxime melts at 64" ; Westenberger (Abstr. 1884 581) gives 45' as the melting point of this compound. AniRonitrile melts at 61-62' ; Henry (Ber. 2 6 6 i ) found tlie melting point to be 56-57'.Aiaisenylamidoxi?ne OMe*CsH4*C( N H,):NOH is prepared by heat- ing anisonitrile for 6-8 hours at about 90' with hydroxylamine hydrochL )ride and sodium carbonate i n dilute alcoholic s o h tion ; the yield is 81 per cent. of the theoretical quantity. It crystallises fromORG.QNIC CHEMISTRY. 145 benzene in scales and from hot water in needles melts at 122-123" and is readily soluble in alcohol ether chloroform acids and alkalis sparingly in hot benzene and hot water and almost insoluble in light petroleum. The hydrochzoride C8H,oN202,HCI is crystalline melts at 168" with decomposition and is soluble in alcohol but insoluble in ether. The ethyl-derivative Cl,oHIIN20? crystalliscs from dilute alcohol in prisms melts a t 51-52" and is readily soluble in alcohol ether benzene and chloroform but insoluble i n light petroleum.The acetyl-derivative. CI0Hl2N2O3 crystallises from dilute alcohol in prisms melts at 106" and is readily soluble in alcohol and chloro form but. only sparingly i n benzene and ether. The nzoxime O&fe*C6HI*cN>CMe N-0 prepared by heating the acetyl-derivative alone or with water or with acetic anhydride crystnllises in colour- less needles melts a t 68" and is readily soluble in alcohol ether benzene and chloroform but more sparingly in light petroleum. OMe.C6H4*C<NH > CHMe is ob- tained by dissolving the amidoxime in aqueous acetaldehyde ; it crys- tallises from alcohol in colourless needles melts a t l27*So and i a readily soluble in alcohol ether benzene and cliloroform but only sparingly in light petroleum.Ethyl anisenyZainidoximecarbo.~ylate OMe*CGH4*C (NH,) :NO.COOEf prepared by treating the amidoxime with ethyl chlorocarbonate in cold chloroform solution crystallises from dilute alcohol in colourless plates melts at 119-120" and is readily soluble in alcohol but more sparingly in ether and benzene. Aniseny lcarbonylamidoxime OMe*C6H4gC<~r-r > CO crystallises from dilute alcohol in colourless scales melts a t 208" and is readily soluble in alcohol ether and chloroform but only sparingly in benzene and light petroleum. BenzoylaiLisen?/la?nic2oxi~e C,5H,4N203 separates from dilute alcohol in crystals melts at 148' and is readily soluble in alcohol ether chloroform and benzene but insoluble in light petroleum. Anisenylbenzsnylazoxime OMe-C6H4*C<KH>CPh No0 prepared by heating the preceding cornpourid alone or with water or by dissolv- ing i t in concentrated sulphuric acid crystallises in colourless plates melts a t 1025 and is readily soluble in alcohol ether chlorofoym and benzene.No0 Etkylideneaniseny Z a m i ~ ~ i m e Y.0 Aniseqlpropenylazoxime-w-carboryc acid is obtained when the amidoxime is melted with succinic anhydride ; i t crystallises from dilute alcohol in yellowish needles melts a t 140-1141" and is readily soluble in alcohol ether and chloroform but only moderately in benzene and very sparingly in l i g h t petro- leum. Salicylonitrile (compare Spilker preceding abstract) can be pre- VOL. LVlLT. II46 ABSTRACTS OF CHEMICAL PAPERS. pared by decomposing acetylsalicylonitrile (compare Lach Abstr.1884 1134) with alcohol. A polymeride of salicylonitrile is formed in considerable quantities when salicylaldoxirne is heated with acetic anhydride. This com- pound crystallises from boiling nitrobenzene in pale yellow needles melts at 296-5399" and is sparingly soluble in boiling chloroform benzene and ether. When melted with potash it is decomposed into salicylic acid and ammonia and when heated at 200" with concen- trated salphuric acid it is decomposed into phenol ammonia and car- bonic anhydride. Ethyl salic~?~ylamid~ximecnrboxylate CloH12N20 crys tallises from dilute alcohol in colourless needles melting at 96". Salicenylpropenylazoxime-w-carboxylic acid OH*CeH4*C<:&-C *c,H** CO OH separates from a mixture of benzene and light petroleum in small well-defined crystals melts at 116-117" and is readily soluble in alcohol ether and chloroform but more sparingly in benzene.Methylsalicylonitrile prepared by treating salicylonitrile with sodium ethoxide and methyl iodide boils a t 255-256" and is volat,ile with steam; Ahrens (Abstr. 1888 266) gives 265-5366" as the boiling point of this conipound. MethylsalicenyZamidoxz??ze OMe.C,H,*C(NH,):NOH prepared by digesting the nitrile with hydroxylamine for a long time crystallises from benzene in needles melts a t 123" and is readily soluble in alcohol ether chloroform and hot water but insoluble in light petroleum. Methylsalicenylbenzenylazoxime OMe.C6HI'C<-N>CPh7 N-0 melts a t 117" and is readily soluble in chloroform alcohol ether and benzene but insoluble in light petroleum.P. S . I(. Action of Hydroxylamine on Orthocyanobenzyl Cyanide. By G. EICHELBAUM (Ber. 22 2973-2975).-H0mo-orthophthalene- alszidinaidolrime C6H,< CH,.C'NHz)>N(?)7 C(NH)-0 is most readily obtained by keeping an alcoholic solution of orthocyanobenzyl cyanide (1 mol.) and hydroxylamine (rather more than 1 mol.) for several days in a phce protected from direct sun-light; it is then filtered from the crystals which separate arid evaporated down. It crystallises from water in long needles (with 2 mols. H20) melting at 95"; the anhydrous substance melts at 158" is very readily soluble in alcohol insoluble in ether chloroform and benzene &c. It has the same percentage composition as orthocyanophenylethenylamidoxime but cannot be an amidoxime as it has only basic properties and thus resembles the compound obtained by Beidermnnn from trimethylene dicyanide and hydroxylamine (hhis vol.p. 1536j. The hydrochloride C9HSN30,HCl crystsllises in small lustrous yellow cryshls is sparingly soluble in water almost insoluble in alcohol. The picrate CgHgN,0,CsH,N30 forms reddish-yellow needles rather more readilyORGIANIC CEEMISTRT. 1 4 i solnble in alcohol than i n water and explodes slightly when t,he dry substance is heated. When the base is dissolved in dilute hydro- chloric acid and treated with sodium nitrite homo-orthophthalic acid is formed. N. H. M. Isophthalenediamidoxime. By G. GOLDBERG (Be,.. 22,2976- 2977) .-Metadicyanobenzene is prepared by dist.illing an inti mate mixture (15 to 20 gi-ams) of potassium benzeiiemctadisulphonato with pure potassium cyanide under diminished presswe.It is first resublimed and then crystallised from alcohol from which i t separates in slender needles melting at 1.58-159". Isoyhthalenediamidoxime C,H,[C(NH,):N-OHJ r= 1 31 is formed when metadicyanobenzene (I niol.) dissolved in benzene is digested with hydroxylamine (rather more then 2 mols.) in clmed flasks at 90". It crystallises from alcohol in colourless prisms melta a t 193" with decomposition dissolves readily in hot water and alcohol sparingly iu ekher and shows the characteristic properties of the amidosime?. The crystals contain water of crystallisation (probably 8 mol.) which they lose when exposed to air. HomoterephthalenediaidoHime.and its Derivatives. By E. ROSENTHAL ( B e y . 22 2977-29844 .-Hornoterep hthalened inn? itl- oxime OH*N:C(NH2)*C,H4-CR2C(NH,)N*OH [ = 4 I] prepared by keeping a mixture of liydroxylhmine hydrochloride (3 mols.) with the necessary amount of sodium carbonate and paracyanohenzyl cyanide dissolved in alcohol for some days in a closed flask crystal- lises from hot water in microscopic prisms melts a t 192" with decom- position is rather readily solubble in methyl alcohol and acetone very sparingly i n ethyl and amyl alcohols and is insoluble in ether beiizene and light petroleum. It shows all the characteristic reactions of the amidoxinies. The h?ydrochZo?ide C9H,N,0,,2HCI dissolves very readily in water but is not hygroscopic and is also soluble in alcohol and glacial acetic acid.The diacety I-derirative Cl3HI6N4o4 crystallises in groups of needles melts a t 161*5-16f is soluble in hot water alcohol ether and benzene and in acids but not in alcohol; when boiled with water for some hours i t is quantitatively converted in to ? i o m o t e r ~ h t ~ n E e l ~ e d i a z o x i ~ e ~ ~ e t h e n ! i l c M e ~ N - ~ C * C 6 H . C H 2 . C ~ - ~ ~ c M e . The latter melts a t 11 l*:ao is soluble in hot water methyl ethyl and xmyl alcohols ether aiid benzene &c. and is insoluble in mineral acids. The dibenzoyl-co?l7- pound C23H20Nb0A crystallises from hot methyl alcohol melts at 184" dissolves in acetone ethyl acetate amyl alcohol and in acids very sparingly in ethyl alcohol and is insoluble i n water benzene arid ether.When heated at 150" for four hours it is converted into hornoterephfhalenediuzoxirne dibenzeny 1 C,,H,,N,O,. This forms long white matted needles melts a t 179*5' and is soluble in alcohol ether chloroform and. benzene. CN.C6H4* C H2-C (NH,) :N* 0 H prepared by the action of hydroxylamine (1 mol.) on paracyano- benzyl cyanide (1 mol.) melts at 168". It is converted by nitrous The h y d n d i l o r i d e is crystalline. N. J3. M. N0.N N.0 Paracyanophenylet hen9 Zamidozim e I:!148 ABSTRACTS OF CHEMICAL PAPERS. acid into paracyanophenylacetamide (M. p. 19G" Melliuglioff Inaug. Diss. B e r l i n 1889). The benzoyl-derivative CIV*C,H,.CH,.C(NH,):N*OBZ forms small white needles melts at 171*5-172" dissolves in met.hjl and ethyl alcohols and glacial acetic acid less readily in benzene and cliloroform ; it is also dissolred by acids.When heated with water for six hours it is converted iiito ~aracyanol?heiiylethen ylazoxiiire- bcwzenyl CN*C6H1.CH,*C~-N~CPh which melts a t 105" and is soluble in alcohol ether benzene and chloroform. N-0 N. H. M. Hydrazines. By M. FREUND (Ber. 22 2727).-The author replies to the statements of Willgerodt (this voL p. 40). Orthonitrophenylhydrazine. By A. BISCHL~R (Rer. 22 2801- 2809 ; compare Abstr. 1889 501) .-Orttionitrophenylhydr- azine N02*C,H4*NzH3 is best prepared by dissolving orthonitraniline (1 0 grams) in warm concentrated hydrochloric acid (100 grams j adding to the well cooled solution an aqueous solution (35 grams) of sodium nitrite ( 5 grams) and keeping the mixture at the ordinary tempera ure with frequent stirring until the crystals of the nitraniline hydroohloride have disappeared ; a solution of stannous chloride (32 grams) in Concentrated hydrochloric acid (32 grams) is then gradually added care beii~g taken that the temperature does not rise much above 0" and the stannochloride which separates from the fiolution is rec~ystallised from hot water.The hydi-ochloride CGHiN3Or,HC1 obtained by decomposing the stannochloride with hydrogen sulphide crystallises in small yellow plates or in long alender needles is readily soluble in warm alcohol and warm water but only sparingly in the cold soheuts and is insoluble in ether benzene and concentrated hydrochloric acid ; it reduces Fehling's solution in hhe cold but ammoniacal silver nitrate solution only on warming.The yield of this salt is aboct 75 per cent. of tlie theordical quantity. The free base is obtained by treating a hot aqueous solution of the hydrochloride with sodium acetate ; it crystallises from benzene in long cinnabar-red needles melt's at go" and is readily soluble in warm alcohol benzene and hot water but only sparingly in ether and light petroleum. The sulphate (C,HiN,O,),,H2SQ~ crystallises in small pinkish needles and is readily soluble in h4ot alcohol warm water and dilute sulphuric acid but insoluble in ether and benzene. Benz y l i ~ i i e o r t h o n i t r o ~ h e n y 2hy d rnzine NOz* C6H4*NH-N CH Ph sepa- rates as a reddish-brown precipitate when benzaldehyde is added to an alcoholic solution of the hydrazine ; it crystallises from boiling benzene in dark-red plates melts at 186-187" and is moderately easily soluble in hot benzene but very sparingly in hot alcohol and ether.and insoluble in water. The formyl-derivative separates in long pale yellow needles when the hydrochloride isORQANIC CHEMISTRY. 149 heated at 100" with sodium formate a D d formic acid for about an hour; it crystallises from alcohol melts a t 177" and is readil soluble in hot water and boiling alcohol but only sparingly in ether and benzene. Solutions of the formyl- acetyl- arid benzoyl-derivatives give a red or bluish-violet coloration with alkalis. The ucetjyZ-dei*iv I - tive N02*C6H4*NH.NHAc prepared by heating t be hydrochloride of the hydraxine with sodium acetate and glacial acetic acid crystallises from alcohol in lemon-yellow needles melts at 140-141" and is readily soluble in hot benzene alcohol and water.The diacdyl- derivative NO2*C6H4*NAc*NHAc prepared by heating the hydro- chloride with sodium acetate and ace& anhydride crystallises from dilute alcohol in reddish prisms melts a t 57-58" and is readily soluble in hot water benzene alcohol and cold glacial scetic acid but only sparingly in hot ether. The benzoyl-derivative N02*CsH4*NH-NHBzt crystallises from alcohol in pale-yellow needles melts at 166" and is readily soluble in ether benzene and hot alcohol but insoluble in water. The opal$-derivative C202( N2H2*C6H4-NO2) prepared by heating the hydrazine with ethyl oxalate crystallises from hot aniline and nitrobenzene in small Fellow needles and is only sparingly soluble in most ordinary solvents.a-Phen&inzime C6H4<r's H is obtained together with dihydro- phenotriazine and ortho p heny lenediamine when orthoni trophenyl- hydrazine is reduced with sodium amalgam in dilute acetic acid solution care being taken that the temperature does not rise much above 30". The solution is decanted from the mercury evaporated at a moderate temperatnie the residue dissolved in water and mixed with excess of soda ; it is then treated with potassium ferricjauide in the cold until the violet colour changes tu yellowish-red mixed with a large volume st' concentrated soda and extracted three or four times with ether. When the crude product is fractionated it) is separated into a portion boiling at 235-245" and a portion boiling above 360" which consists of phenylethenylamidine.Phenotriazine crysta llises from bt nzene in deep-yellow needles melts at 65-66" boils at 235-240" and is volatile with steam. It is readily soluble in alcohol benzene warm ether and warm water but it separates from the aqueous solution on adding concentrated alkalis ; it has a peculiar alkaloid-like odour and is a feeble base the salts being readily soluble in water and alcohol. a-Phenomethyltl-iazine C6H4<T'CMe is formed together with the N.N dihydro-derivative acetamide. acetamidophenyl hydrazine and phen yl- enediamine when acet~lnitrophenylhydrazine is reduced with sodium amalgam in acetic acid solution ; the solution is filtered from small quantities of acetylamidophenyl hydrazine and the triazine is isolated a s described above.It melts at 88-90" boils at 250-2.55" with slight decomposition is readily soluble in alcohol ether and benzene and moderately easily in cold water but only sparingly in light N.N150 ABSTRACTS OF CHEMICAL PAPERS. petroleum ; its alkaliae solutions oxidise quickly on exposure to the air. Orthucefylamido~l~ereylhy~razine NH,-C,H,*NH*NHA c (see above) crjStullises from benzene in colourless needles and melts a t 162". Metmitrophenylhydrazine and Parabromorthonitrophenyl- hydrazine. By A. B~SCHLER and S. BRODSKY (Ber. 22,2809-2818). -~eta?aitrophenylhydrazine l~ydrochloride N02.C6H,.N2H3,HC1 is prepared from metanitraniline exactly as described in the case of the corresponding ortho-compound (compare preceding abstract).The yield is 50-60 per cent. of the theoretical. It mystallises in yel- lowish plates and is readily solwble in warm alcohol and water but otily sparingly in warm concentrated hydroct~loric acid ; i t reduces Fehling's solution in lthe cold and ammoniacai silver nitrate and platinic chloride on warming. The free base N02*C6H4*N2H3 crystal- lises from alcohol in slender yellow needles melts a t 93" and is readily soluble in glacial acetic acid chloroform warm benzene and alcohol but only sparingly in boiling water. The sulphate ( C,H,N,02),,H2S04 separates from hot water in yellow crystals and is readily soluble in hot water and glacial acetic acid but o d y spar- iiigly in boiling alcohol and insoluble in ether and benzene. The acetyl-derivative N02*CJ€,.NH*NHAc crystallises in golden plates melts a t 145" and is readily soluble in alcohol ether glacial acetic acid and boiling water but only moderately easily in benzene.The diacetyl-derivative N02*C6H,*NAc*NHAc forms brownish plates me1 t s at 150" and is readily soluble in the ordinary solvenks. The bentoyl- derivative N02-C6HI.NH*NHBz crystallises from dilute alcohol in yellow prismatic needles melts a t 151" and is readily soluble in alcohol ether glacial acetic acid and hot benzene b u t iiisoluble in water. The dibenzo y I- deriuat ive NO,*C&I,-NBz*N HBz c r j s t a1 lises from acetic acid in yellow plates melts at 153" and is readily soluble in hot alcohol and benzene but insoluble in water. Is 0 2*C,H4.N B z*N H Ac prepared by heating the acetyl-derivative with beneoic anhydride at 160" separates from eumene in crystalline aggregates melts a t 13i0 and is readily soluble in doohol and glacial acetic acid but insoluble in benzene.a-Benzoyl-~-aoetyl.naetanitro~~tenylhydrazine NOz-C6Hd*NAc*NHBz obtained by heating the benaoyl-derivative with acetic anhydride aud sodium acetate separates frtom cumene in yellowish crystalline aggre- gates melts a t 147" and sublimes a t 100" in small iridescent needles ; it is readily soluble in boiling benzene alcohol and glacial acetic acid and more readily in hot mmene than the preceding compound. E thy liden e m etanitropheny lhyd?*azim N02.C6H,*NH*N CHMe pre- pared by warming the hydrazine with acetaldehyde separates from alcohol in yellow crystals melts at 98" and is readily soluble in alcohol benzene and ether but only sparingly in hot water.Renzylidene,,~etanitroyhenylhyd?.azi,2e NO,*C,H,*NH*N:CHPh crjs- tallises from boiling alcoliol in small carmine-red needles melts a t 117-118" and is sparingly soluble in hot alcohol but readily in ether hot glacial acetic acid and benzene. F. S. K. a- Acet y 1 - /3- b enzo y lwet aiiitrop heny Zhy d m z i n e,ORGANIC CHEMISTRY. 151 AcetonenitrophenyEhydrazine No2*C6H,*NH*N:CMe2 crystaliises from dilute alcohol in dark-red needles melts at 112" and is readily soliible in warm alcohol ether benzene and glacial acetic acid but only sparingly in hot water. Acetophenone.rLitrophmylhydrnzine NO2*C6H4.NH*N:CMePh crystal- lises from benzene melts at 160" and is only sparingly soluble in hot alcohol but more readily in benzene arid ether.BeiizilmetarLitrophenyLhydrazine crystullises from benzene in small orange-yellow needles melts at 158" and is readily soluble in warm benzeile but only sparingly in hot alcohol and ether. Metanitrop hen y lizinedih y d roxy tartaric acid se pttrates in crystals when sodium dihydroxytartrate (1 rnol.) is treated with hydrochloric acid ( 1 mol.) and nitrophenylhydrazine hydrochloride in aqueons solution ; it melts a t 175" with decomposition. MetanitrodiphenyZ- izinedihydroxytartaric acid p.repared in like manner but employing 2 mols. of the hjdrazine is a yellow micro-crystalline powder melting at about 200". The l a 4 two compounds are only sparingly soluble in hot water alcohol benzene and glacial acetic acid.The coin pound N O,.C,H,.N H*N:CMe* CHI,-CO OE t is formed when the hydrazine is treated with ethyl acetoacetate in alcoholic solution ; it crystallises from dilute alcohol in yellowish-red plates melts a t 117" and is sparingly soluble in hot water but readily in other warm sol vents. NOz-CeH4*N H*NH C S*NHP h prepared by warming the hydrazine (1 mol. j with phenylthiocarb- imide (1 mol.) in alcoholic solution is a dark-yellow crystalline compound melts a t 146-147" and is readily soluble in hot alcohol but only sparingly in benzene and glacial acetic acid. Uiacety luniidoyhenyllzydruzine B HAc.CcH4.NH.NHAc is obtained when acetylnitrophenylhydrazine is reduced with sodium amalgam in acid alcoholic solution and the crude product boiled with glacial acetic acid; it crystallises from acetic acid in small dark-yellow needles melting a t 1.50-151".Metanitrod iphny lt hiosemicarbazide Attempts to prepare par;tnitrophenylhydrazine were unsuccessful. Purabrot~rortl~onitro~henyllz~drazi~~e N020G6H3Br-N2H3 prepared by the method described in the case of orthonitrophenylhydrazine (com- pare preceding abstract) separates from benzene in dark-red crystals melts a t 130" and is readily soluble in alcohol ether hot glacial acetic acid and benzene but only spariugly in hot water ; it reduces silver arid platinum salts. The hydrochluride C6H6BrN3O2,H CL crys- tall ises from water in small jellowish-red needles. The sulphate ( C6H6B~-N302)2,H?S04 is a reddish microcrystalline powder sparingly soluble in cold alcohol and benzene but readily in hot alcohol water and glacial acetic acid.NOz:C6H313r*NH*N Ha CHO crystallises from alcohol in slender pale yellow needles melts a t 191" and is readily soluble in hot alcohol and benzeue. The acety2- derivative N 02*C6H3Hr*NH*NHAc crystallises from glacial acetic acid in small lemon-yellow needles and is readily soluble in hot beuzene glacial acetic acid and alcohol but only sparingly iu the The formyl-derivative,152 ABSTRACTS OF CHEMICAL PAPERS. cold solvents. The benzoyl-derivative N02.C6H3Br*NH*NHBz crys- tallises from alcohol in large yellow plates melts at 185" and is readily solnble in hot alcohol ether and benzene but only sparingly in the cold solvents. The beiLx?/Zidene-derivnt.ive NOz*CGH3Br.NH.N CHPh crystallises from alcohol in red needles melting at 207".The aceto- phenoige-derivative N0,*C,H3Br.NH-N:CMePh crystallises in red needles and melts at 148". Parabrmnorthonitrod ipheny lthiosemicarbazide NO2*C,H3Br*NH*NH*C S*NHPh is a yellow microcrystalline compound melts a t about 160-164" and is readily soluble in hot alcohol and glacial acetic acid but only sparingly in ether and benzene. Parabrom-a-phenotriazine C,H,Br<y'G H is formed when forrnyl- parabromortbonitrophenylhydrazine is reduced with sodium amalgam and glacial acetic acid in well-cooled alcoholic solution ; the solution is evaporated the residue dissolved in water treated with potaosium ferricganide and the filtered solution mixed with excess of alkali. It crystallises from boiling water in slender yellow needles and is readily soluble in hot water and other ordinary Solvents but insolnble in alkalis.N*N NaCMe N*N Parabrom-a-phenomethy ltriazine CsH3Br< I I I prepared from the acetyl-derivative of the hydrazine in like manner crystallises from water in golden plates melts a t 115" and is readily soluble in ether benzene alcohol and glacial acetic acid but only sparingly in cold water. F. S. K. Formation of Phenylhydraxides. By E. FISCHER and F. PASS- MORE (Ber. 22 2728-2736).-The hydroxy-acids of the sugar- group combine very readily with phenylhy drazine in aqueous solu- tion yielding crystalline hydrazides which are only sparingly soluble in cold water can be easily purified and are readily reconverted into the acid when boiled with baryta. The hgdrazides are prepared by treating a moderately dilute (about 10 per cent.) solution of the acid or lactone with a fair excess of phenylhydmzine and an equal quantity of 50 per cent.acetic acid heating the mixture for from 30 minutes to two hours on the water-bath ; the product sometimes crystallises from the hot solution but generally the separation occurs only on cooling. The hydrazides of the monobasic hydroxy-acids are all modeiately easily soluble in hot water but the double hydrazides of the polybasic acids are only sparingly soluble. If the solution contaius free mineral acids it must previously be neutrnlised with soda or sodium carbonate and if large qua.nt,ities of hydrochloric hydrobromic or sulphuric acid are present the acid isORGANIC CHEMSTRY. 153 best removed with lead acetate or barytt otherwise rather spavingly soluble salts are formed ; if the solution contains sugar the osazotie which is also formed in the reaction can generally be separated from the hydrazide by crystallisation from hot water.The hyrlmzides are as a rule easily obtained in a pure condition and may serve as a means of determining the formula of the acid but they resemble each other so closely in physical properties that they cannot be suitably employed for purposes of identificatinn. The hydrnzidcs of gluconic acid galnctonic acid and arabinosecarboxylic acid for example cannot be distinguished with certainty ; in such cases it is necessary to reconvert the hydrazide into the acid. For this purpose the hydrazide is boiled for half-an-hour with 10 per cent.baryta-water (30 vols.) the phenylhydrazine is extracted with ether and the residual solution together with any precipitate which has been produced is heated to boiling and the barium precipitated with the requisite quantit,y of sulphuric acid; on evaporation the filtered solution yields the free acid or lactone. All the monobasic acids of the sugar-group under the conditions described above give crystalline hydrazides which are sparingly soluble in cold but moderately easily in hot watJer. Under the same conditions saccharic acid mucic acid and metasaccharic acid yield hytlrazides which are almost insoluble. Glycollic lactic and glyceric acids gave negative results and the limit of the difference in beha- viour probably lies between erythroglucic acid and arabonic acid.Formic acid succinic acid malic acid tartaric acid and mauy aromatic acids for example cinnamic acid and gallic acid yield hydrazides under the conditions described above but m alonic acid forms only an acid hydrazide. The readiness with which the hydr- azide formation takes place is evidently dependent on the electro- nrgative character of the acid ; if the latter reaches a certain limit the hydrazide formation takes place in dilute aqueous solution ah temperatures below loo" but if the acid is less negative in cha- racter the temperature must be raised ; in such cases the presence of water does not affect the reaction. If for example a dilute aqueous solution of phenylhydr~zine acetate is heated for several hours a t 130° a considerable quantity of acetylphenyllirdrazine sepa- rates from the solution on cooling.Benzoic acid glyceric acid and lactic acid are converted into the corresponding hydrazides iinder the same conditions but the product,s do not crystallise readily. At high temperatures the yield is not quantitative as the hydrazide is partially decomposed by the water. The hydrazides can be readily distinguished from the hydrazones. as they all give a reddish-violet coloration with concentrated snlphuric acid and a drop of ferric chloride a reaction first observed by Biilow (Abstr. 1887 138) ; they are moreover readily decom- posed by alkalis and baryta. They are all colourless and generally melt not quite constantly with considerable evolution of gas. G ~ u c o l ~ i c acid phenylhydrazide C6H,,O6*??&,Ph can be prepared by heating gluconic acid (1 part) on the water-bath for 45 minutes with water (10 parts) phen.ylhydrazine (1 part) and 50 per ceut.acetic acid (1 part) ; it separates from the cold solution in crystals,15-1- ABSTRACT8 OF CHEMICAL PAPERS. and if the mother liquors are heated a:ain for ihrae hours a further crop of crystals is obtained. The total yield IS 81 per cent. of the theoretical. It cryptallises in small prisms softens at about 1!)5" and melts completelv a t 200" with decomposition. It is almost insoluble in ether and only very sparingly soluble in cold water and hot alcohol but readilyin hot water. It can be easily converted into crystalline calcium gluconate by boiling it with haryta as described above and treating the acid with calcium carbonate; the yield is 85 per cent.of the theoretical. Galactorkc acid phenylhydrazide C ~ 0 6 ~ N z H P h can be obtained in like mariner from crude galactonic acid ; it crystallises in plates melts a t 200-205," when quickly heated and is moderately easily soluble in hot wa'ter but only sparingly in cold water and hot alcollol. Aratrinosecarboxylic acid pheny lhydrazide C6H,,06*NzH2Ph prepared from the free acid or the lactone in like manner melts a t 214-216" with decomposition and resembles the preceding compound. Dextrosecurboxylic acid phe.rLylhycirazide C7Hl3O7*NzHZPh obtained from the lactone crystallises in prisms melts and is slowly decom- posed a t l7l-l7Zo and is readily soluble in hot water but much more sparingly in alcohol. Mannosecarboxy lic acid phenylhydrazide C,H,,O,-N,H,Ph crystallises from hot water in small prisms; when quickly heated it melts a t 220-22.3" with decomposition and is more sparingly soluble than the other hydrazides.11)/~arnr~osecat~borcylic acid phenylhydrazide C7H,,O6*N2€IzPh crystal- lises from hot water in small hexagonal plates melting a t 210" with decomposition Succharinic acid phpriylliydrazide C,H,,O,-N,H,Ph prepared from the lactone crystdlises from hot alcohol in very slender needles melts a t 164--ltj5" with decomposition and is much more readily soluble in water and alcohol than the preceding conipounds. Formic acid seems t o be the only fatty acid which forms a hydr- azide in aqueous solution but even i i i this case the reaction does not take place quantitatively as it is accompanied by a slight evolution of gas.The hydrazides of succinic acid nialic acid and tartaric acid are forriied a t 100" in 10 per cent. aqueous solution but the reactions take place only slowly. Succinylphenylhydrazine melts a t 217-218" ; Freund and Gold- smith give 208-209" as the melting point. Malic acid diphenyl- hydieazide melts not quite constantly a t 220-22;3" with decomposi- tioil; Biilow found the melting point to be 2 1 ; 3 O . Tartaric acid diplienylhydrazide melts at about! 24U" when quickly hsated whereas Biilow gives 226" as its melting point. Allyltricarboxylic acid and citric acid yield sparingly soluble hydra- zides under the conditions described above. The phenylhydrazine salt of phenjlhydrazidemalonic acid separakes in crystals when malouic acid (I part) is heated with phenjlhydra- zine ( 3 puts) dilute acetic acid (3 parts) and water (10 parts) for two hours on the water-bath; it separates horn hot alcohol or hotOKGASIC CHEEJIISTRT.155 water in crystals melts at 141-143" with decomposition and has the composition Cl5Hl6N403. 31ulorric acid phsnylhydrazide COOH *CH2*CO*N2H2Ph is obtained when the mother liquors from the preceding compound are acidified with sulphuric a.cid and cxtracted with ether. It crptallises in colourless needles me1 ting at 154" with decomposition is moderately soluble in water and gives the hydrazide reaction; i t reduces Fehling's solution when warmed therewith and has a. strongly acid reaction co n~aloszylphenylhydrazine CH2<CO>N2HPh is formed together with water and phenylhydrazine when the phenylhydrazine salt of the preceding compound is heated at 200" for 15 minutes ; it crystal- lises from hot water in slender colourless needles melts at 128" and is readily soluble i n alcohol. Neither benzoic acid nor phenylhydroxyacetic acid yieldsa hydrazide when heated with phenglhydrazine in 10 per cent.aqueous solution ; ciririamic acid on the other hand forms the hydrazide previously described by Knorr (Abstr. 1887 665) but the yield is not par- ticularly good. Gallic acid phenylhydrazide C19HIJY204 crystallises from hot water in long prisms melts at about 187" with decomposition and is nioderately easily soluble in alcohol and hot water. Glucom'c acid anilide C,H,,O,*NHPh prepared by heating gluconic acid (5 grams) f o r four hours a t 100" with aniline ( 5 grams) water (50 grams) and acetic acid sufficient for solution separates from alcohol in crystals melts at 171° and is readily soluble in cold water.The formation of the anilides does not take place as readily as that of the hydrazides and the products are much more readily soluble in water. F. S. K. Action of Phenylhydraiine on a-Hydroxy-acids and their Ethyl Salts. By A. REISSPRT and W. KAYSER (Bey. 22 2 9 2 6 292'3).-The authors have obtained phenylhydmzidopropionic acid (hbstr. 1884 11521 by the action of phenylhydrazine on ethyl lactate and hydrolysis of the ether formed. When equal mole- cular proportions of phenylhydrazine and a-hydroxybutyric acid are h a t e d together at 150-160" pseudophenyl?) ydr~zido-a-h1/droxybut2/,.ic acid CloHlrN20z is formed.This compound is easily soluble in alcohol sparingly in ether crystallises in needles and melts a t 151-152". It dissolves in boiling acids and alkalis but is reprc- cipitated unchanged on cooling. When dissolved in concentrated sulphnric acid it gives a violet-red coloration. Boiling alkalis do not decompose it and it is very stable towards reducing agents; it is decomposed by boiling concentrated hydrochloric acid but besides phenol no decomposition-prodocts could be isolated. These charac- leristics seem to show that this compound is not a normal hydrazide. With sulphuric acid and potassium nitrite nitrosopseudohydraaiclo-r- h?ydwzybzttyric acid CIOHl3N3O is formed. This is sparingly soluble in water easily so in aqueous alkalis and156 ABSTRACTS OF CHE~IICXL PAPERS.acids ; it melts a t 96-98' and i s very unstable. Acetic anhydride is without action on the pseudohydrazide whilst concentrated sulphuric acid and phosphoric chloride and oxychloride yield resinous products. Mandelic acid yields with phenylhydrazine a pseuudophenylhydr- azidomanddic acid C,,H14Nz02 analogous to the butyric compound. It crystallises from alcohol in long white needles and melts at 182". With lactic acid only phenylhydrazine lactate was formed. L. T. T. Acetylenedicarboxylates and Phenylhy lrazine. By E. BUCHNER (Ber. 22 2929-2932). -When phenylhydrazine is added to an ethereal solution of methyl acetylenedicarboxylate methyl oxalacetate phanylhydrazone N HPh*N:C ( COOMe) *CH,*C OOMe is form6d.It is easily soluble in boiling alcohol sparingly soluble in ether crystallises in colourless glistening scales and melts a t 118". Strong sulphuric acid dissolves i t to a reddish-yellow solution which gives a violet-red coloration with ferric chloride or a soluble dichromate. When heated with alkalis or dilute acids it yields the acid Cl,H,N,O obtained by Wislicenns (Abstr. 1887 233) from the corresponding ethyl-derivative. The latter acid is spsbritigly soluble i n cold water. and forms stable salts. It is prob,zblyphe?~yl?-yrcrxololte- carboxylic acid. L. T. T. Weselsky's Resorcinol Dyes. By R. NIETZKI A. DIETZE and H. MACRLER (Ber. 22 3020-3038).-Resazui in (Weselsky's diazo- resorcinol) Cl ,H,N04 is obtained together with resxufin (diazo- resorufin) by Weselsky and Benedikt's method (Jfonatsh.1. 8S9) and can be purified by means of the sodium salts. It crystallises froin glacial acetic acid in snidl greenish prisms which do not melt with- out decomposition. The sodium salt Cl,H6N04Na crystallises in long green lustrous needles rather readily soluble ill water sparingly in aqueous sodium csrbonate and sodium chloride. In thin layers tlie solution is almost pure blue and shows. espwixlly in presencch of a little alcohol a splendid brick-red tluorcscence. The barium salt fornis brownish sparingly soluble needles the siluer salt is a volumiiious flaky precipitate. The ethyl-derivative crystallises in long dark-red needles melting a t 815". The acetyl-derivative CI2HGNOJAc prepared by heating a mixture of sodium resazurin and sodium acetate ( d r j ) with acetic anhydride (1 2-15 parts) crystdlises from alwtwl in long ruby-coloured needles melting a t 22.2" ; when heated with sodium carbonate blue resazurin i s formed.Tetrabronioresnzurin C12H,Br,N0 (Weselsky and Benedikt's " non-fluorescent blue ") was prepared by brominnting resazurin ; the sodium salt CizH2 Br4N0,Na + 2H20 crystallises from hot dilute alcohol in lustroos green needles. When the bromo-derivative is reduced tetrabromoresornfin is formed as observed by Weselsky and Benedikt ; the potassium salt has the formula they ascribed to it Cl,H,Br4N04K + 2Hz0. The substance obtained by the action of acetic chloride on resRzurin to which Brunuer and Kranier ascribed tlie formula CI2H9Cl2NO3(Abstr. 1884 1333) crystallises in golden plates ard seems to be a mixture.Resorufin CL2H,N03 was obtained from the mother liquors from the preparation of resazurin and also by heating the latter with hydrogen sodium sulphite solution. It crystallises in small brown needles. The potassiuin salt forms small brownish plates extremely soluble in water ; the ethyl salt C,?H,NO,Et crystallisw in orange-red needles melting at 225". The acetyl-compound crjstallises in loiig needles melts at 223" and has the formula given to it by Weselsky and Benedikt. Tetrabromoresorufin (" flu ore scent^ blue ") was pre- pared in a manner similar to tetrabromoresazurin ; the sodium salt C ,,H,Br,NO,Na + 2H,O crystallises in splendid lustrous green needles. Hydroresorufin the compound obtained by the action of zinc chloride on resorufin or on 1-esazurin has the formula C1,HI,N03.It cryst'allises in nearly colourless wide needles which soon become green when exposed to air. The ti-iacety I-compound CI2H6NO3Ac3 forms long colourless lustrous needles melts a t 216" and is nearly insoluble in water sparingly soluble in hot alcohol and very soluble in hot glacial acetic acid. The molecular weight of the acetgl- derivative was determined by Raoult's method. When hgdroresor- ufin is distilled with zinc-dust diphenylamine is formed. The paper concludes with remarks on the constitution of resorutin and resazurin. N. H. M. Dyes of the BenzeYn Group. By I(. HEITMANN and H. REY (Ber. 22 3001-31104) .-l'etrfLmethylrosamin~ C2,H,,N2(OH) (?) is pre- pared by the action of benzotrichloride (1 mol.) on dimethylmetamido- phenol (2 mols.) at 50-60° using sand (;r benzene as a diluent to keep <own the temperature ; the reaction is completed by heating at 60" on a water bath.The product is steam-distilled extracted with boiling water containing hydrochloric acid and precipitated with sodiuiri chloride. It is purified by dissolving in water partially pre- cipitating with sodium carbonate filtering and precipitating with sodium carbonate or ammonia. The hydrochloride C19HllMe4N,0C1 forms black-red needles with steel-hlue reflection ; the platinochloride is a dark red precipitate soluhle in water; the ozalate and nitrate form dark green and steel-blue needles respectively. The aqueous solutions of the salts have a splendid bluish-red colour with jdlowish-red fluorescence.The solution in sulphuric acid is orange-yellow the colour being changed to red by the addition of water. Silk and wool are coloured roee-colour to dark-red by a slightly acid bath of the dye. The colour on silk and jute shows a yellowish-red fluorescence which is increased by sulphuric acid. The rosamines are decolorised by zinc-dust in acid and alkaline solutions. Addition of soda does not produce an immediate precipi- tate in solutions of the dyes ; a sodium salt seems to be formed. The alkaline solutions dye unmordanted wool an intense rose-colour or even deep-red but the colour is removed by boiling soap solution or by prolonged boiling with water. Tetrethyli osamine was also prepared from diethylmetamidophenol1 58 ABSTRACTS OF CHEJIICAL PAPERS.and benzotrichloride. The salts produce a bluer colour than those of the methyl-derivatives. Diphenylrosamiiie from metahydroxydiphenylamine is a violet dye readily soluble in alcohol sparingly in water. Action of Chlorocarbonylamide (Urea Chloride) on Aro- matic Hydrocarbons in the Presence of Aluminium Chloride. By E. P . HARRIS (Clzem,. Centr. 1889 ; ii. 285-286).-The following compounds are obtained by gently warming chlorocarbonylamide with the corresponding hydrocarbons and finely-pnwdered aluminium chloride. iMetaxyhnide C6H,Me2*CO*NH forming lufitrons needles melting a t lSO" from which Fittig's xylic acid is obtained by saponi- fying with alcoholic potash. Orthoxylamide crystallising in lustrous needles and melting a t 136-137" from which Fittig's paraxylic acid is obtained by hydrolysis.p- Isoduylamide C,H,Me,*CO*NH forming lustrous plates melting at 184". Tetrameth2/Zhenxanzide C6HMe4.C0.NH2 crystallising in plates melting at 172-173". Ace- napthenecarboxylamide C,sH,,ON forming plates melting a t 198". a-EtA y In apht ha lenecar box y 1 am ide c ,oH&t*C 0.NH2 cry st allisin g in colourless needles melting at 166". All these amides are readily hydrolysed the corresponding acids being formed. Alkaline potas- sium permanganate oxidises acenaphthenecarboxylic acid to naph- thdenetricarboxjlic acid. In the case of the homolognes of benzene the amidocarbonyl group enters in the para-position unless this is already occupied in which case it assumes the meta-position.I n the case of the homologues of naphthalene only the a-derivatives react with chlorocarbonylamide. J. W. L. Behaviour of Aniline towards Substitution-derivatives of Hydroxybenzoic Acids at High Temperatures. By H. LTM PRICHT (lh-. 22 2906-2912). The author before examiniug the action of aniline on substituted hydroxybenzoic acids repeated other experi- menters work on the action of aniline (14 grams) on the hytlroxy- benzoic acids (10 grams). With the ortho-acid 1.5 grams of anilide were obtained with the para-acid 1 gram of anilide whilst with the meta-acid apparently nearly all the hydroxy-acid mas converted into the auilide. Contrary to Kupferberg's statement the author tinds that salicylanilide distils a t a high temperature without decomposition. N. H.M. L. T. T. Action of Aniline on Amidosalicylic Acid. By H. LIMPRICHT and v. RECHENRERG (Ber. 2 2908-2912) .-Amidosalicylic acid [OH COOH NH = 1 2 41 is best obtained by heating azo- benzenesalicylic acid with stannous chloride. When amidosalieylic acid is heated with aniline hydrochloride a t 160-210" for some hours i t yields phenamidophenol NHPh*CsH4.0H and diphenamidopheny- lene C6Hr(NHPh),. The former is soluble in cold alcohol the latter only in boiling alcohol. Phenamidophenol cr~stallises from water in large flat colourless prisms which turn brown on exposure to the air. It melts a t 70"' and distils almost withont decomposition. It is soluble in soda and is coloured blue by strong nitric acid. With etbyl iodide and alcohol it yields a derivative which was not however,ORQANIC C HEJIISTRY. 159 obtained in a pure state.With excess of acetic anhydride it yieltls diacetylph et/ a t ) ir Joph eiioZ 0 Ac- C6H,*NP h Ac which forms w Iiite cry st a's soluble in alcohol ether and benzene and melts a t 119". Phenamido- phenoZsuZphowic acid SO,H*CsH,(OH)*NHPh obtained by heating the phenol with strong sulphuric acid crystallises from boiling water in Small grey prisms which are still solid a t 260" It is easil7 soluble in :tlcohol sparingly so in ether and benzene. The barium salt is crystalline. Diphenamidophenylene ohtained as above forms grey 01' brownish needles easily soluble in ether chloroform acetone. bell- zene carbon bisulphide acetic acid and boiling alcohol insoluble in water and melts a t 141". Nitric acid gives first a blue and then a blood-red coloration concentrated sulphuric acid dissolves the crystals to a blue solution; hydrochloric acid has no action but if sodium nitrite is added to the mixture a n unstable nitroso-derivative is formed.Diphenamidophenylene is not formed by the action of pure aniline on phenamidophenol but only when hydrochloric acid or aniline hydro- chloride is present. Both the phenol and phenylene are para-com- pounds and they can also be similarly prepared from the [l 3 41 aruidosalicylic acid. L. T. T. (Rer. 2 2 299 1-3001) .-P hen y lprop ylene-~-thiocarbamicte Aromatic Substituted Pseudothiocarbamides. By B. PRAGER is prepared by heating aIIylphenylthiocarhamide (m. p. 95" 50 grams) with crude hydrochloric acid (100 c.c.) for two hours at 100".The product is evaporated down diluted with water and saturated with ammonia It meks at 117" and dissolves readily in chloroform alcohol ether and benzene. The picrate crystallises in yellow needles melting at 154" ; the ylutinochloride (C,oH,zN,S),,HzPtCI forms microscopic yellow crystals. Phenyl-/3-mef hyltaurocarbainic anhydiide C,oH,2N,S03 is formed when the above base is oxidised with potassium chlorate and hydro- chloric acid (Andreasch Abstr. 1883 664). It melts at 192" dis- solves in alcohol and glacial acetic acid sparingly i n hot watcr and is indifferent to acids and alkalis. When heated with hydrochloric acid at 230" for five hours it is converted into p-methyltaurine (Gabriel Abstr. 1889 848) and anilinc. Phen y lmet hy lpop y 1 ene- q- thiocarbnmide NMeP h*CGN.S-YHMe CH is obtained when a mixture of methylaniline (30 grams) and ailylthio- carbamide (30 grams) is heated for a short time then left for Some hours and finally heated with hydrochloric acid (120 c.c.) at 100" for two hours (compare Gebhnrdt Abstr. 1885 383). The base was not obtained pure by this method but salts were prepared. The base was also prepared by the action of an excess of methyl iodide on phenyl- propylenethiocarbamide. It distils at about 300" without decompo- sition. The picrute crystallises from boiling wat,er in yellow needles melting a t 125" ; the ylati~~ochlor~de separates from the dilute hydro-1 ti0 ABSTRACTS OF CHEMICAL PAPERS. chloric acid solution in orange-red crystals melting a t 183-184" with decomposition.When phenylmethylpropylenethiocarbnmide is oxidieed with potas- sium chlorate and hydrochloric acid and the product heated with hydrochloric acid at 150-160" p-methyltaurine and methylaniline are formed. dllylorthotoZyZthiocarbnncide Cl,H,,N2S is prepared by heating a mixture of orbhotoluidine (25 grams) dissolved in alcohol (20 c.c.) and allylthiocarbamide (25 grams) and evaporating the product on a water-bath. It forms lustrous crystals melt8 a t 98" dissolves readily i n glacia.1 acetic acid chloroform alcohol and benzene is less soluble in alcohol and insoluble in water. Orthotolylpropylene-jb-thiocarbamide C,H,*NH< N-CH obtained from the above compound by the action of hydrochloric-acid crystal- lises in small rhombic plates melts a t 126" dissolves readily in the usual organic solvents and in mineral acids.sparingly in hot water. The yicrate melts a t 3 75-176"; the plutinochloride forms orange-red crystals melting at 177-178". v S.7 HMe Ort hoto ly 1 met h y lprop y Zen e- 9- thiocarbamide C7H7*NMeGN. ~~ formed by the action of methyl iodide on orthotolylpropylenethio- carbamide boils a t about 295". The hydrioclide crystallises in long hexagons melting a t 165-166" ; the picrate forms yellow prisms melting a t 137-138" ; the platinochloride decomposes at above 200". When the base is oxidised and the product heated with hydrochloric acid a-methyltanrine is formed. a-Naphth ylpropyleire-~-thiocarbamide CI4Hl4N2S obtained from allgl-2-naphthylthiocarbamide (m. p. 145" not 130" ; Zinin An:)iaZen 34 :34cj) crystallises in rhombic plates melts a t 134" dissolves readily in chloroform alcohol and benzene is less soluble in ether and insoluble in light pet,roleum and water.The yicrate crystallises in long rectangular prisms melting at 192" ; the platinochboride is an orange-coloured crystalline salt which melts a t 205-206" with effer- vescence. N. H. M. Piaselenoles and Piazothioles. By 0. HINSBERG (Eev. 22 2895-2902).-Continuing his previous work (Abstr. 1689 785) the author finds that selenious anhydride or acid reacts with aromatic orthodiamines to form piaselenoles but that no similar derivatives are formed from aromatic meta- or para-diamines or from fatty diamines. Sulphurous anhydride forms a similar series of piazothioles with aromatic ort,ho-diamines but phosphorous boric and tellurous anhydrides phosphorous chloride phosphoric oxycliloride and arsenious chloride do not yield any analogous compounds.The piaselenoles and piazothioles closely resemble many of the substituted quirioxalines. Piaselmole CsH4:N2:Se prepared from orthophenylenediamine forms colourless needles easily soluble i n alcohol ether and benzene sparingly so in water ; when heated it melts a t 76" and ernits an odourORGANIC CHEMISTRY. 161 resembling that of quinoxaline. Its salts are yellow in colour and are decomposed by excess of water. Sodium yields a characteristic green periodide. EthoxypinseZenoZe OEt*C6H3:N2:Se prepared from ethoxyphenylenediamine crystallises in pale yellowish needles soluble in alcohol and melting at 103-104".With concentrated snlphuric acid it yields an intensely yellow solution ; with stannous chloride and potassium periodide i t behaves like the other piaselenoles. AmidopiuseZenoZe NH,*C6H3:N2 Se unlike the other piaselenoles is only formed when selenious acid and triamidobenzene (1 2 4) solutions are mixed in the cold ; at higher temperatures the triamidobenzene acts as a reducing agent towards the selenious acid. It crystallises in brownish-red needles soluble in alcohol benzene and ether sparingly so in water and melting at 149-150". Its salts are dark- brown and crystalline but are rather unstable. Concentrated sulph- uric acid dissolves it forming an almost colourless solution with a reddish fluorescence but it becomes intensely brown on dilution. PiazothioZe C6H4:Nz:S is formed when orthophenylenediamine is heated with concentrated aqueous sulphurous acid (or sodium hydrogen sulphite) for five or six hours at 180-200".It is also formed when a stream of sulphurous anhydride is passed into the boiling diamine but its formation is then generally accompanied by that of resinous bye-products. It forms colonrless crystals having a strong odour resembling that of quinoxaline melts at 44" boils at 206" (uncorr.) distils in a current of steam is sparingly soluble in boiling water easily so in organic solvents and is only feebly basic in character its solutions in strong mineral acids being pre- cipitated on the addition of water. Piazothiole is a very stable sub- stance and very resistent to oxidation ; strong reducing agents convert it into phenylenediamine and hydrogen sulphide.Methyl- piuzothiole C6H,Me:N2:S from metaparatoluylenediamine resembles piazothiole in character melts at 34" and boils at 233-234' (uncorr.). Determination of it8 molecular weight by Raonlt's method gave 143 the formula C7H6N2S requiring 150. Its salts are colourless and are decomposed by water. The platinochloride ( C7H6N2S)z,H2PfCls forms reddish-yellow crystals ; the periodide is also crystalline. When methylpiazothiole is dissolved in strong sulphuric acid and strong nitric acid then added in excess nitromethy~iazot7zioZe N02*CsH2Me:N2:S is obtained. It forms colourless crystals soluble in alcohol and glacial acetic acid and melting at 154-156". Rromomethy ZpiazothioZe C6H2MeBr:N3:S formed by the addition of bromine to a cold chloro- form or hot acetic acid solution of methylpiazothiole forms white needles melting at 98".It is volatile in steam and is very stable the bromine-atom not being removed by boiling with potash. Derivatives of Paranitrocinnamaldehyde. By A. EINHORN and C. GEHRENEECK ( A n n d e n 253 348-376 ; compare Abstr. 2889 396) .-Paranitrocinnamaldoxime N02*C6H4-C3H3:N *OH prepared by boiling the aldehyde with hydroxylamine hydrochloride and sodium carbonate in dilute alcoholic solution is a yellow crystalline compound melting at 178-1 79". The anilide C15H,2N202 crystallises from alcohol in yellow needles melting at 132-133". L. T. T. VOL. LVIII. m162 ABSTRACTS OF CHEMICAL PAPERS. Paranitro-a-bromocinnamaldehyde (m. p. 136") identical with the compound obtained by Zincke and Hagen (Abstr.1884 1343) by nitrating a-bromocinnamaldehyde is formed when nitrocinnamalde- hyde is treated with bromine in glacial acetic acid solution; the dibromide could not be obtained in a pure condition. Paranitrophanytbutine rnethy 1 ketone N02*C6H,*CH:CH*CH:CH.COMe is obtained together with paradinitrodiphenyldibutine ketone when paranitrocinnamaldehyde is treated with acetone in alcoholic soda solution ; the filtrate from the paradinitro-compound is poured into acidified water the precipitate digested with dilute sodium carbonate solution to free it from paranitrocinnamic acid and recrystallised. It separates from water in colourless needles melts at 132" and is readily soluble in the ordinary solvents. The hydrazone CI8H1,N3O2 separates from alcohol in ruby-red crystals melting art 209-210".Paradinitrod~pheny Zdibutine ketone CO ( CH:CH°CH:CH*C6H,*N O,) crystallises from acetic anhydride in pale yellow needles melts at 216-218" and is readily soluble in glacial acetic acid but insoluble in water ether chloroform and alcohol. Paranitrophenylbutinecarboxylic acid (compare Einhorn and Gehrenbeck Zoc. cit.) can be prepared by gradually adding an alcoholic solution of paranitrophenylbutine methyl ketone to a boil- ing concentrated s o h tion of sodium hypochlorite. The ethyl salt Cl3Hl3NO4 crystallises from alcohol in yellowish plates melting at 118". The copper salt C2?H16N,08Cu is crystalline the silver 8dt CIIH,NOIAg amorphous ; the alkaline salts are very readily soluble in water.Paranitrophenylbutine-w-dicarboxylic acid (m. p. 208") is readily soluble in alcohol hot water and glacial acetic acid but sparingly in benzene ether and chloroform. The ethyl salt C18H17N06 crystal- lises from dilute alcohol in colourless needles melting at 10&105". The copper salt C,2H7NO&u is crystalline the silver salt. C12H7N06A@ amorphous and the alkaline salts are very readily soluble in water. Paranitrophenyl-~6-dibromethyl-/3-bromacrylic acid is readily soluble in ether ethyl acetate and alcohol but only sparingly in &loroform and benzene ; when oxidised with 3 per cent. potassium permanganate it yields paranitrobenzoic acid. The ethyl salt C13H12NBr304 crystallises from alcohol in colourless plates melting at 124". The sodium salt crystallises with 2 mols.H,O. F. S. K. Constitution of Filicic Acid. By H. SCHIFF (Annulen 253 336-342) .-The author discusses the results obtained by Grabowski (Annulen 143 279) Luck (Abstr. 1889 276) and Daccomo (&id. 54) in their investigations of filicic acid and comes to the conclusion that filicic acid is a butyrophloroglucyl ally1 ketone of the constitution I (oH):CH*$*o*CH2'CHMe2 The criticisms of paterno CHIC( OH) *C*C0.CH2*CH:CH2' (Abstr. 1889 615) on the experimental results of Daccomo (Zoc. cit.)ORGANIC CHEMISTRY. 163 would seem according to the author to be to a great extent un- grounded. F. S. K. Carbothionylic Acids of Resorcinol and Pyrogallol. By E. LIPPMANN (Monatsh. 10 617-623 ; compare Abstr. 1888 1092).- Dihydroxydithiobenxoic ucid c6&( OHL*CSSH is obtained in 60 per cent.of the theoretiad yield by heating in a closed flask €or 12 hours a t 100" a mixture of resorcinol (50 grams) and potassium xanthate (80 grams). On heating the acid (50 grams) at 130-140" with potash (250 grams) dissolved in a little water it is converted into P-resorcylic acid and consequently must be regarded as a metacarbo- thionylic acid. PyroguZloZcarboth~ortyZic acid C,H,(OH),*CSSH + H20 is pre- pared in a manner precisely similar to that used in the case of dihydroxydithiobenzoic acid. It crystallises unchanged from dilute alcohol in the form of beautiful glistening golden scales which become anhydrous at 70" and melt at 154". On heating it with five times its weight of potash and a little water at 120-130" it gives the pgrogallolcarboxylic acid of Senhofer and Brunner and consequently has the constitution CSSH (OH) = 1 2 3 4.G. T. M. Action of Orthonitrocinnamaldehyde on Malonic Acid. By A. EINHORN and C . GEHRENBECK (Annalen 253 374-376) .-Ortho- nitrophenylbutine-w-dicurboxylic acid C12H9N06 prepared by heating orthonitrocinnamaldehyde with malonic acid for six hours in glacial acetic acid solution crystallises from glacial acetic acid in yellowish needles melts at 212-21 3" and is sparingly soluble in benzene ether and chloroform but readily in alcohol and hot water. The silver salt C12H7NOsAg2 crystallises in yellowish plates ; the copper salt CI2H7NO6Cu is a yellowish-green crystalline compound. Ort honitrophen y lbutene-a-hy droxy - w-dicarbox y 1 ic acid NO2.C6H4*cH CH*CH (OH) cH( co 0 El) is the first product of the action of malonic acid on orthonitrocinnam- aldehyde ; it crystallises from alcohol in which it is only sparingly soluble in colourless needles melts at 269" explodes when heated strongly and is insoluble ir- benzene and light petroleum and only sparingly soluble in ether chloroform and glacial acetic acid but; readily in hot water.F. S. I(. Benzoyltannin. By C. BOTTJNGER (Ber. 22 2706-2709).- Benzoyltannin can be obtained by shaking an aqueous solution of tannin with soda and benzoic chloride ; the dirty-white precipitate which is produced is boiled with ether to free it from benzoic acid and the residue is warmed to expel the ether washed with water and dried. It is a pale yellow crystalline powder insoluble in boiling water and almost insoluble in boiling alcohol.It is not acted on by ammonia and it is only very slowly dissolved and decomposed by cold dilute soda.. When heated with water at 150° it liquefies com- nb 2164 ABSTRACTS OF CHEMICAL PAPERS. pletely but it is only partially decomposed even a,fter heating for two hours at 165". It dissolves in hot aniline with formation of benz- anilide and is soluble in hot dimethylaniline. It is decomposed by warm concentrated sulphuric acid or when heated alone. It dissolves in warm pbenylhydrazine with slight evolution of gas yielding a yellow substance and a crystalline compound which is soluble in ether and in boiling soda. Other naturally occurring tarinic acids give simiIar benzoyl- derivatives.Tannin dissolves in warm concentrated sulphuric acid and is thereby converted into gallic acid. The benzoyl-derivative of tanriic acid (from oak bark) dissolves in warm phenylhydrazine with evolution of gas yielding a yellowish- brown substance which is soluble in soda. F. 8. K. Tannins. By C. ETTI (Monatsh. 10 647-664) .-Investigation of the tannins of the formulat! C1,H,609 and C20H2009 (compare Abstr. 1881 277; 1883 994) has proved that they are not glucosides but are to be regarded as derivatives of a ketonic acid C6&( OH),*CO0C6H( OH),*COOH. The author has now isolated a new tannin which resembles those above mentioned in its general chemical and physical properties appearing from its behaviour with phenylhydrnzine and hydroxyl- amine to be also a ketonic compound.It has the formula C16H1409 and is obtained as a red powder from the diluted extract of the wood of the common Slavonian oak by careful precipitation with hydro- chloric acid (excess of acid must be avoided as it diminishes the yield). The precipitate is allowed to remain for several days then collected well washed with water air dried and lastly fractionally dissolved by alcoholic solutions of different strengths and precipitated with water. The pure substance whic!i is brownish-red is made up of microscopic warty spherical masses (recrystallised from alcohol) insoluble in wat,er and ether butl readily soluble in acetone and has been shown by Fuchs (Monatsh. 9,1132-1142) to be a monobasic acid. With phenylhydrazine it gives a yellow amorphous compound C22H20N20s forms a brown amorphous oxime C16H15N09 and when heated with dilute snlphuric acid (1 10) for six hours in a sealed tube at 120-130" yislds together with an insoluble anhydride a red solution from which by extraction with ether a red crystalline mass may be obtained.On pressing this and recrystallising from water it becomes colourless and is identical with gallic acid (m. p. 238-240'). On treatment with magnesia the tannin C16H1409 gives the following salts :-( C16H1309)2Mg a brownish-yellow amorphous mass ; (C16Hlo0,)zMg~ and (C14 H1109)2Mg3 both bright-yellow powders scarcely soluble in water ; (c16H1309)nMg + 2Cl6H1409 of a brownish- yellow colour and very soluble in water. In all probability the extract furnishing the tannin contains it as a soluble normal mag- nesium salt.The tannin C,6H& when heated alone at 130-135" or in closedORGANIC CHENISTRY. 165 tubes with water at loo" loses water forming anhydrides from which the acid cannot be again regenerated and which yield methyl iodide on boiling with hydriodic acid. On boiling the tannin with dilute sulphuric acid in an open vessel an acid of the formula C32H24016 = 2C16H1409 - 2H20 is formed as a reddish insoluble mass whilst on heating in a closed tube two anhydrides are formed of which one CnH2,01a of a dark-red colour is soluble in 95 per cent. alcohol and according to Fuchs (Zoc. cit.) is of an acid nature whilst the other C32H18013 which is blackish is insoluble and shows no acid reaction. The tannin CI6Hl4O9 on long heating with hydrochloric acid at loo" loses a methoxyl-group and is converted into an acid CI5HI2O9 of a yellow colour which still contains a methoxyl-group ; so that the tannin itself contains two methoxyl-groups.G. T. M. Dibromosulphanilic Acid and its Derivatives. By 0. HEINKHEN (Annulen 253 267-288) .-Dibromosulphanilic acid can be conveniently prepared by gradually adding a freshly prepared solution of bromine (10 c.c.) and soda (16 grams) in water (150 c.c.) to a hot aqueous (500 c.c.) solution of sulphanilic acid (17.3 grams) and 35 per cent. hydrochloric acid (21 grams); the yield of the barium salt is 39.9 grams or 95 per cent. of the theoretical. It can also be prepared by gradually adding a solution of potassium bromate (11.1 grams) in water (250 c.c.) to a hot aqueous solution (500 c.c.) of sulphanilic acid (17.3 grams) and 43 per cent.hydro- bromic acid (37.6 grams) ; the yield of the barium salt is 38 grams or 90 pel9 cent. of the theoretical and no tribromaniline is formed in the reaction. Sulphanilic acid is converted into aniline but only very slowly when it is heated at 200-220" with dilute sulphuric acid (b. p. 160') in a current of steam. Dibromosulphanilic acid at a temperature of about 170-178" other conditions remaining the same is readily converted into dibromaniline (m. p. 83-84"); the yield is 83 per cent. of the theoretical. Dibromaniline [Br NH = 1 3 21 crystallises from hot dilute alcohol in long colourlesa needles melts at 83-84" sublimes at 262-264" and is readily soluble in alcohol ether benzene and chloroform.The hydrochloride prepared by passing hydrogen chloride into a benzene solution of the base melts at 126" and is decomposed by alcohol and by water or by exposure to the air. ThepZatinochZo+Ze (C6H,Br,.NH2)z,H2PtCl~ crystallises in golden plates and is decom- posed by water. Diazodibromobenzene sulphate C6H3Br,N,,HSOa prepared by treat- ing dibromaniline with sulphuric acid and ethyl nitrite in well-cooled alcoholic solution crystallises in colourless needles and is relatively very stable ; when boiled with water under reduced pressure i t yields an oil probably metadibromobenzene but when heated with snl- phnric acid (b. p. l50") it i s converted into dibromophenol (m. p. Metadibromoguinone [02 Br = 1 4 2 61 is obtained when di- bromosulphanilic acid is oxidised with potassium chromate alid 55-56").166 ABSTRAOTS OF CHEMICAL PAPERS.sulphuric acid in the cold. It crystallises from hot alcohol in golden iridescent plates melts at 131" and is readily soluble in alcohol ether chloroform and benzene but only very sparingly in cold water. The same compound is obtained by oxidising dibromoparaniidophenol ; this quinone is probably identical with the dibromoquinone obtained by Levy and Schultz (Abstr. 1882 509) by oxidising tribromophenol with fuming nitric acid. F. S. K. Tin Tetraphenyl. By A. POLIS (Ber. 22 2915-2918).-500 grams of a tin-sodium alloy (25 per cent. of sodium and 75 per cent. of tin) 600 grams of bromobenzene and 25 C.C. of ethyl acetate were heated together at incipient boiling for about 30 hours.The product was a syrupy brown mass the solution of which in boiling benzene deposited crystals of tin tetraplzenyl SnPhd on cooling. This sub- stance when pure forms thin colourless prisms belonging to the tetragonal system a c = 1 0.3893 ; 111 110 = 70" 35'. It is thus isomorphous with silicon tetraphenyl and lead tetraphenyl the axial ratios following the order corresponding with the positions of the metals in the periodic system. It melts at 225-226" volatilises unchanged and boils above 420". It resembles the corresponding silicon and lead compounds in soh- bility dissolving readily in boiling benzene glacial acetic acid chloro- form and carbon bisulphide ; very sparingly in alcohol and ether. It inflames spontaneously when exposed to air. When treated with bromine (2 mols.) bromobenzene and tin diphenyl dibromide are formed. The author finds that under 42 mm.pressure the latter compound distils at 230" without decomposition. Chlorine is similar in its action t o bromine whilst iodine is without action. L. T. T. Derivatives of Diphenyline. By J. REULAND (Ber. 22,3011- 3019) .-UibenzyZidenediphenyZine CIPHP( KCHPh) is prepared by heating a mixture of diphenyline (1 mol.) and benzaldehyde (2 mols.) on a water-bath for several hours until clear dissolving the product in ether and precipitating with light petroleum. It crystallises from alcohol and benzene in lustrous yellow plates melts at 232-233" and is sparingly soluble in alcohol and ether. Dinzetaizitrobenzy lidenedipheny line C12H8(N:CH* C6H4*N02) prepared by heating diphenyline (1 mol.) dissolved in a little alcohol with metanitrobenzaldehyde (2 mols.) for some time on a water-bath crys- tallises from a mixture of benzene and alcohol as a fine yellow crystalline powder.It melts at 184-185" and is readily soluble in benzene less so in alcohol. The dipuranitro-cleri?;ative C2SH18N404 is a yellowish-red powder melting at 208". Diorthohydroxybenzylidinediphen yline Cl2H8(N:CH*C,H,*0H) pre- pared from diphenyline and salicylaldehyde crystallises from alcohol in yellow plates melting at 145". Difurfiwaldiphenyline CuH8(N:C5H40) is formed when furfuralde- hyde (3 grams) is added to a solution of diphenyline (3 grams) in absoluto alcohol (100 grams) and kept for 24 hours. It crystallises in It was not analysed.ORGANIC CHXMISTRY. 167 lustrous yellow plates and melts at 137".When the alcoholic solution is treated with mineral acids splendid red compounds are formed. PhthaZodiphenyZine C J & ( N:C<06->CO)2 c H4 obtained by heating diphenyline with phthalic anhydride (2 mols.) for two hours at 115-120" crystallises from glacial acetic acid in lustrous white plates melting at 25.5-257". is prepared by heating di- phenyline (5 grams) with absolute alcohol (15 grams) and carbon bisulphide (15 grams) for 18-20 honrs in a reflux apparatus on a water-bath distilling off tLhe alcohol and carbon bisulphide and ex- tracting the residue several times with hot alcohol and ether. It melts at 238" and does not give an odour of thiocarbimide when heated with strong hydrochloric acid.Diphenylenebisazo-P-naphthol C12Ha(N:N*C10H6*OH)2 is obtained when diphenyline is dissolved in hydrochloric acid (4 mols.) well cooled and treated wit,h the calculated amount of sodium nitrite. The tetrazo-compound is filtered and added to a filtered solution of @-naphthol in just sufficient potash. It is crystallised from benzene. It melts a t 243-245" and dissolves in strong sulphuric acid with red colour. DiphenylenebisazoresorcinoZ C12Ha(N:N*C6Hb02)2 prepared in a manner similar to the above compound is a reddish-brown powder. Dt$henylenebisazodimethylaniline C12Ha(N:N*C,H4*NMe2)2 is formed as a red precipitate of a metadlic lustre by the action of the tetrazo- compound of diphenyline on methylaniline. Tetramethyldiphenyline NMwC,H4* CsH4.NMe2 is obtained by heat- ing dry diphenyline hydrochloride (1 mol.) with methyl alcohol (4 mols.) at 180" for two hours. The product is poured into hydro- chloric acid treated with potash and extracted with ether ; the ether is distilled off the residue boiled with acetic anhydride and fraction- ally distilled.The oil which distils over at 333-345" solidifies in a short time. It crystallises from absolute alcohol in monoclinic prisms which are phosphorescent when rubbed together ; it melts at 51-52". It gives a blue coloration with chloranil. The picrate crptallises from alcohol in long red needles resembling chromic acid melts at 199-200" and decomposes at 208". The methiodide forms slightly rose-coloured needles melts at 184" and is readily soluble in alcohol and water almost insoluble in ether.The dimethiodide melts at 196" and is readily soluble in water and alcohol. Diphenylorthoparadicyanide C,,H,(CN) [= 2 4'1 is prepared by Sandmeger's method for displacing amido-groups by cyanogen follow- ing exactly the instructions given for benzonitrile (Abstr. 1885,149). It crystallises in slightly yellowish plates and melts at 152-153". Diphenylortho~aradicarboxylic acid CI,H,(COOH) [ = 2 4'1 ob- tained by the hydrolysis of the above dicyanide crystallises in colour- less plates melting at 251-225". The silver salt is a white powder melting at 235-237" readily soluble in ammonia ; the copper saZt is a sparingly soluble bluish-green crystalline powder NH*$l6Hj s < ~ ~ o ~ ~ Thiocarbodipheny line N. H. M.168 ABSTRACTS OF CHEMICAL PAPERS.Oxidation of Triphenylmethane. By &I. HANRIOT and 0. SALNT-PIERRE (Bull. Roc. Chim. [3] 1 773-774) .-Triphenylmethane suspected by the authors to contain a higher homologue derived from toluene was oxidised with chromic mixture; in addition to triphenylcarbinol (20 per cent.) and benzophenone (40 per cent.) small quantities of orthobenzoylbenzoic acid and of anthraquinone resulting from the dehydration of this acid were obtained. Pure triphenylmethane yielded neither of the latter substances on oxida- tion. T. G. N. Paramethylbenzil and Benzilparacarboxylic Acid. By E. BUCHER (Ber. 22 2819-2820).-Paramethyldeoxybenzo~n yields the following bromo-substitution-products :- CHPhBr.CO*C6H4]lfe CBr2Ph*CObC6H4Me CBr2Ph*CO*C6H,*CHBr2 and CBr2Ph*CO*C6H4-CBr3 from which paramethylbenzil dibromo- deox y benzoznparacarboxy lic acid CBrJ? h*C 0- C6H1* CO OH and b e n d - paracarboxylic acid can be obtained.Paramethylbenzil COPh*CO*C6HaMe is formed when dibromo- deoxybenzoin is heated with water at 180" ; it is a yellowish oil. Benzilparucarboxylic acid COPh*CO-C,H,.COOH is obtained by heating the pentabromide with water at 160"; i t crystallises in colonrless plates and decomposes at 280-300" without melting. The acid CBr2Ph*COG6H4*COOH is formed when methyldeoxy- benzoin is heated with bromine (5 mols.) at 160° or when dibromo- paramethyldeoxybenzoin is heated with bromine (3 mols.) and water at 160" ; it crystallises in yellow needles melts at 218" and is partially converted into benzilcarboxylic acid when heated with magnesia a t 190".F. S. I(. 1.4'-Iodonaphthalenesulphonic Acid. By R. MAUZELIUS (Ber. 22 2820-2823) .-1.4'- Iodonaphthalenesulphonic acid CloH,I*S 03H can be prepared by treating a-diazonaphthalenesulphonic acid with warm 40 per cent. hydriodic acid ; it is purified by converting it into the chloride (see below) and decomposing the latter with water at 150". It crystallises in almost colourless plates with 2 mols. H20 melts at 129" and is readily soluble in water. ammonium salt sodium salt with 1 mol. H20 silver salt copper salt with 2H20 and a number of other salts were prepared; they are mostly crystalline and sparingly soluble in water. The methyl-salt C,oH61*S03Me crystallises from alcohol in prisms melts at 59-60' and is readily soluble in chloroform and ether but only sparingly in cold alcohol.The ethyl-salt crystallises from alcohol in hexagonal plates melts at 74" and is readily soluble in chloroform ether and benzene. The normal propyl salt crystallises in plates and melts a t 67" the isopropyl salt in long pi-isms melting at 90". The chloride C,oHJ-S02CI crystallises from chloroform in large monoclinic prisms melts at 114" and is readily soluble in hot glacial acetic acid chloroform and benzene but only sparingly in light petroleum. The bromide crystallises from benzene and chloroform in short prisms Thepotassium salt C~OH~I'SO~K + H20,ORGANIC CHEMISTRY. 169 melting a t 153". The amide C1,,HGT-SO2-NH2 crystallises from alcohol in smull scales melting at 239". F. S. K. Specific Volumes of Camphor and Borneol.By M. KUHARA (Chem. News 60 114).-The camphor employed melted at 177.7" (corr.) and boiled at 205.3" (corr.) the borneol boiled at 209.7" (corr.). Numerous determinations of the specific gravities of these two sub- stances were made by filling small glass cylinders with them a t their reclpective boiling points and weighing when cold. The sp. gr. of the camphor was found to be 0.8110 at 205-3" and its sp. vol. 187.42; whilst the mean sp. gr. of the borneol is 0.8083 at 209.7" and its sp. vol. 190.5. D. A. L. An Isomeride of Camphor. By 0. WALLACH and A. OTTO (An- nalen 253 249-267; compare this Jour. 1889 1069 1071 and 1072) .-In preparing pinene nitrosochloride by the method already described (Abstr. 1888 1098) oily bye-products are formed in con- siderable quantity and can be isolated by distilling them with steam in small quantities at a time.The same oily compounds are obtained when ethyl nitrite is used in the place of amyl nitrite ; experiments showed that under certain conditions the former can be advantage- ously employed instead of amyl nitrite in the preparation of nitroso- chlorides. The crude bye-product distils completely between 160 and 190" the principal portion boiling a t 182-186"; it is most probably a mixture of cymene and a compound of the composition CIoH160 which the author names pinoZe as will be shown below. PinoZe dibromide CloH,OBrz is obtained in crystals when the fraction boiling at 182-188" is treated with bromine in glacial acetic solution until a permanent coloration is produced and the solu- tion then allowed to evaporate slowly.The mother-liquors from the dibromide contain cyrnene which can be isolated by distillation with steam. The dibromide separates from ethyl acetate or alcoholic ether in rhombic crystals a b c = 0.57 1 1.5553 melts at 94" boils at 143-144" (11 mm.) and is moderately easily volatile with fitearn. It is insoliible in water but readily soluble in alcohol ether chloroform and ethyl acetate. When boiled with alcoholic potash it is decomposed yielding an oil which is readily volatile with steam and very easily soluble in dilute alcohol. This oil can be separated into two principal fractions boiling at 183-184" and at about 210" respectively. The fraction boiling a t 183-184" consists of almost pure pinole CloH160.It has an odour hardly distinguishable from that of cineole a sp. gr. of 0.953 at 20° and a refractive power [aJD = 1.46949 at 20". It combines energetically with bromine yielding a dibromide (m. p. 94") also with halogen acids and with nitrosyl chloride but i t does not react with acid chlorides hydroxylamine phenylhy- drazine or hydrogen sulphide. It is readily oxidised by warm dilute potassium permanganate solution yielding carbonic anhydride oxalic acid and terebic acid (m. p. 173-176") ; nitric acid (1 1) converts i t into terebic acid and resinous products. The dibromide gives the170 ABSTRACTS OF CHEMICAL PAPERS. same oxidation-products as ginole itself but it is only very slowly acted on by both the reagents. The constitutional formula /CHP@*CHz\ CH-0- CH 'CH = CMe' is in accordance with the observed properties of pinole.The fraction boiling at about 210" consists of impurepinoleglycot ethy2 ether C10H160( OEt),. This compound can be obtained in colourless compact needles by fractionating under reduced pressure cooling the portion boiling at 110-120" (14 mm.) in a freezing mixture and spreading the crystals on well-cooled porous plates; it is then dissolved in a little glacial acetic acid the solution poured into water and the precipitated oil brought into contact with a crystal of the sub- stance. Pinole nitrosochloride C,oH,60,NOCI is a relatively very stable compound melting at 103" ; it is readily converted into nitrolamines which generally crystallise well and thus serve as a means of dis- tinguishing this compound from other nitrosochlorides.Pinolenitrolaniine hydrochloride NOH:CloH150-NH2,HCl separates after some time in crystals when the nitrosochloride is treated with excess of alcoholic ammonia ; i t crystallises well from water and dilute alcohol. The alcoholic mother-liquors from the hydrochloride con- tain the free base which can be isolated by evaporating under reduced pressure extracting the residue with chloroform and distilling the extract under reduced pressure; it is a yellowish liquid boiling at about 129-130" (14 mm.) with slight decomposition. Pinolenitrolpi~eridine NOH:CIoH,,0*C5NHlo separates from alcohol in crystals melts at 154" and is insoluble in water. The hydro- chloride c,,Hz6O,N,,HC1 is a colourless crystalline powder very readily soluble in water.Pinolenitrolbenzylamine NOH:C10H150*NH*C7H7 is best obtained in a pure state by decomposing the hydrochloride as it seems to crystallise from alcohol with I mol. of alcohol. It crystallises from ether in transparent prisms melts at 135-136" and soon becomes opaque on keeping but without change in melting point or composition. The hydrochloride Cl7HZ,O2N,,HC1 is crystalline and readily soluble in water. Pinolenitrolaniline NOH:C,,H,,O*NHPh crystallises in yellowish plates melts at 174-I75" and is readily soluble in alcohol and ether. The hydrochloride C16H22N202 HCl is crystalline and decomposes on exposure to the air. PinolenitroZ-P-naphthylamine NOH:C,oH,50*NH*CloH7 crystallises from alcoholic ether melts at 194-195" and is insoluble in water and only sparingly soluble in alcohol ; solutions of the base and its salts are highly fluorescent.This compound is isomeric with camphor. F. S. K. Preparation of Aloin. Ry T. WOODRUFF (Pharm. J . Trans. [ S ] 19 773-775).-The aloes are exhausted with amyl alcohol a t the temperature of a water-bath when most of the resinous mattersORGANIC CEERIISTRY. 171 remain in the residue. The liquid is filtered and evaporated and the aloin is obtained as a crystalline mass contaminated however with a small deposit of resinous matters. This product is then exhausted with cold water the solution is filtered and the filtrate allowed to evaporate spontaneously when the crystals are obtained quite pure. R. R. Cephalanthin a Bitter By E. CLAASEN (Chem. Centr. 1889 ; ii 258 from Pharm.Zeit. 34 384).-The bark of Cephalanthus occidentalis (" button bush " or " swamp dogwood") a bush belonging t o the Cinchoneae contains a saponin-like substance having a bitter taste and tanning properties. For its separation the bark is digested with lime the filtrate treated with carbonic anhydride and the cephalanthin precipitated from the solution by hydrochloric acid and purified by treatment with alcohol and ether. It is amorphous sparingly soluble in cold and hot water readily soluble in alcohol and ether and has the properties of an acid. When warmed with nitric acid i t gives a yellow coloration and with concentrated sulphuric acid an orange coloration changing to reddish- brown. Dilute sulphuric acid seems to split up cephalanthin with formation of sugar.J. W. L. Digitalin and Tanghinin. By ABNAUD (Compt. rend. 109 701-703).-1f digitalin is heated in sealed tubes at 180" with water and barium hydroxide it yields a crystalline compound which is in- soluble in hot water but somewhat soluble in boiling alcohol. It melts at 395-310" with rapid decomposition. It has the composi- tion ( C,lH,101,)2Ba and is the barium-derivative of a compound C31H52011 formed from digitalin by the assimilation of water. It follows that the molecule of digitalin is represented by the formula Tanghinin under similar conditions yields a barium-derivative of the compound Cj27H44O10 which is formed by the assimilation of 2 mols. H20 by the tanghinin. The molecule of tanghinin is therefore re- presented by the formula Cz,H400s.(Comp. Abstr. 1889 900 and this vol. p. 65.) C31H60010. C. H. B. Colouring Matters of Chlorophyll. By A. HANSEN (Amz. AgrorLom. 15,428-429 ; from But. Centr. 38,632).-The author pre- pares the yellow and the green constituents of chlorophyll in what he believes to be a pure condition by the following process :-Some leaves of grass are boiled in water for 15-30 minutes then washed many times with water and dried in the dark. The dry matter is extracted with boiling alcohol and the solution saponified by boiling three hours with a slight excess of aqueous soda ; a current of carbonic anhydride is then passed through the solution which is afterwards evaporated to dryness on the water-bath. Ether extracts from this soap the yellow colouring matter only which is purified by evaporating down and crystallising from a mixture of equal parts of ether and light petroleum.The soap after extraction with ether is extracted with a mixture of alcohol and ether which dissolves only traces of the combination of the green colouring matter with soda. On adding172 ABSTRACTS OF CHEMICAL PAPERS. another quantity of alcohol-ether and also phosphoric acid the green matter is liberated and passes at once into solution from which it is obtained by evaporation in the form of a brilliant fragile greenish- black solid insoluble in water benzene and carbon bisulphide sparingly soluble in pure ether very soluble in alcohol with strong red fluores- cence. The crystals of yellow colouring matter form orange-red plates insoluble in water soluble in alcohol ether chloroform and benzene to a deep-yellow colour and in carbon bisulphide to a brick- red.These crystals are transformed in the light into cholesterin. The author considers this yellow substance to be identical with the yellow colouring matter of flowers and fruits in general including that of the carrot. J. M. H. M. Dibromoquinolines. By 9. CLAUS and C. GEISLER (J.pr. Chem. [a] 40,375-362).-1 4-Dibromoquinoline has been obtained by Metzger (Abstr. 1884 757) who asserts that it is identical with La Coste's dibromoquinoline (Abstr. 1881 74 ; 1882 980). When oxidised by potassium permanganate it yields only pyridinedicarboxylic acid which is converted into nicotinic acid (m. p. 229') at 180". It yields no methiodide and only one nitro-compound.Nitro-1 4-dibromoquinoZine obtained by nitrating the above com- pound with a cold mixture of two parts of nitric acid (sp. gr. 1.52) and four parts of water forms colourless silky needles melting at 155" (uncorr.) and sparingly soluble in water and cold alcohol but freely in other solvents. The hydrochloride forms small yellowish crystals melting at 228" (uncorr.) when sharply heated. The PZatinochloride is described. Amido-1 4-dibromopuinoline C9NH4BrZ*NH2 formed by reducing the nitro-compound with stancous chloride and hydrochloric acid in alcohol distils with steam as small colourless needles melting at 165" (uncorr.). Bromine converts it into a tribromoquinoline melting at 174" (uncorr.) perhaps identical with Lubavin's (m. p. 173-175'). By directly brominating 1 4-dibromoquinoline a tribromide of melting point 115" (uncorr.) and another substance are obtained.1 3-~ibromoquinoline (La Coste Abstr. 1882 978) forms no methiodide and only one nitro-compound. 4-1Viitro-l 3-diEibromoquinoline crystallises in lustrous leaflets which have a greenish shimmer and melt at 162' (uncorr.) ; it forms well- crystallised unstable salts. 4-Amido-1 3-dibronzoquinoline crystallises in needles melting at 184" (uncorr.). 2 4-DibromoquinoZine obtained from symmetrical dibromaniline crystallises in beautiful white lustrous needles melting at 110" (uncorr.) and freely soluble in the usual solvents except water. The hydrochloride forms small colourless needles melting at 158". The plaatiraochloride is described. When 2 3-dibromaniline is quinolised two dibromoquinolines are produced and are separated by crystallising from ether and sorting the crystals.2 3-Dibromoquinoline forms prisms which melt a t 95" uncorr. ; its hydrochloride melts at 144" (uncorr.). The platinochloride is described.ORQANIC CHEMISTRY. 173 3 4-Dibromoquinoline crystallises in slender needles melting at 124' (uncorr.) ; its hydrochloride and platinochloride are described. 1 2-Dibromoquinoline and Derivatives of 2-Bromoquino- line and 4-Bromoquinoline. By A. CLAUS and G. N. VIS (J.pr. O h m . [2] 40 382-387).-l-Nitro-2-bromoquinoline and 1-amido- 2-bromquinoZine have been already described as a-nitrometabromo- quinoline and a-amidometabromoquinoline respectively ( Abstr. 1889 281). The 1 2 :-amidobromoquinoline platinochloride is here de- scribed.1 2- Dibromopziinoline obtained by diazotising 1-amidobromoqnino- line and treating the diazo-compound with cuprous bromide crystallises in beautiful white needles melting at 112" (uncorr.). 4-Bromoquinoline melts at 52" not 48" (loc. a't.) ; it is best obtained as follows :-The mixture of bromoquinolines prepared from meta- bromaniline (70 grams) is dissolved in warm dilute nitric acid (1 litre) when 2-bromoquinoline nitrate separates ; the mother-liquor is mixed with potash the precipitatcd oil dissolved in alcohol (100 c.c.) and a solution of oxalic acid (15 grams) in alcohol (25 c.c.) added ; 4-bromo- quinoline oxalate (m. p. 143' uncorr.) crystallises out and is saponified with ammonia to obtain the pure base. The nitro-4-bromoquinoline melting a t 146" (Abstr.1889 281) is 3 4-nitrobromoquinoline; its basic properties are very feeble so that it is only soluble in concentrated acids and forms no methiodide. 3 4-AmicZobromopuinoline forms small yellowish crystals melting a t 103" (uncorr.) sparingly soluble in water and dissolving in dilute acids with an intensely red colour ; it gives the carbylamine reaction with alcoholic potash. ItsplatinochZoride is described. A. G. B. Bromine-derivatives of Quinoline. By A. CLAUS and A. WELTER ( J . pr. Chem. [2]? 40 387-395).-The authors point out that La Coste's bromoquinoline (Abstr. 1881 741) is not 3-bromo- quinoline but 4'-bromoquinoline and that the dibromoquinoline ob- tained from it is not identical with 1 4-dibrornoquinoline already described (above abstract) ; the former dibromoquinoline can also be obtained by brominating 4'-bromoquinoline and is therefore 3 4'- bromoquinoline.A tribromopuinoline melting at 169" (uncorr.) is obtained at the same time. 3 4'-DibrornopuinoZine crystallises from alcohol in lustrous silky needles melting at 130" (uncorr.). The hydrochloyide forms colour- less four-sided prisms melting a t 185" and easily decomposed by water alcohol or dilute acids. The nitrate forms colourless needles and prisms which melt at 158". The platinochZoride and the meth- iodide are described. Generally speaking whenever a bromoquinoline with the bromine in the benzene-ring is brominated the new bromine-atom enters into the 4'-position ; this is the case with anabromoquinoline the 4 4'- dibromoquinoline previously described by Claw and Decker (Abstr.1889 7259 being obtained. 4 4'-Dibromoquinoline hydrochloride €orms lustrous rhombic tables melting at 183" (uncorr.) and decom- posed by water ; the nitrate crystallises in colourless four-sided tables A. G. B.174 ABSTRACTS OF CHEMICAL PAPERS. melting at 147" (uncorr.). The sulphate the r/tethiodide and the methochloride and its platinochloride are described 2 4'-Dibromoquinoline obtained by heating metabromoquinoline dibromide hydrobromide crystallises from alcohol in beautiful thick colourless rhombohedra which are strongly refractive whilst immersed in the liquid. The hydrochloride is very sparingly soluble ; the nitrate forms colourless prisms melting a t 178" ; the platinochloride is described ; the methiodide forms micro- scopic needles melting at 271" (uncorr.).1 4'-bromoquinoline has been described by Claus and Tornier (Abstr. 1888 164). It melts at 126-127" (uncorr.). A. G. B. Kynurin. By Z. H. SKRAUP (Nonatsh. 10 726-73l).-Kynurin an oxidation-product of cinchonine and of cinchonidine but not of quinine is obtained to the extent of about 10 per cent. of the weight of the cinchonic acid taken when the latter (50 grams) is oxidised with a mixture of chromic acid (20 grams) and snlphnric acid (30 grams) dissolved in water (200 grams). The kynurin (hydr- oxyquinoline) thus prepared melts a t 'LOl" and has all the propert.ies of the compound obtained by the direct oxidation of cinchonine. On heating at 100-110" with 1$ times its weight of phosphorus pentachloride it is converted into a chloroquinoline which melts a t 34" and is reconverted into kynurin by heating with acidified watei- at 120" ; consequently it cannot be a-chloroquinoline since that com- pound melts a t 38" and is converted into carbostyril on heating with water.G . T. M. Alkyl-derivatives of 1-Hydroxyquinoline. By E. LIPPMAKN alid F. FLEISSNER (Monatsh. 10 665 67'L).-A molecular cornpound of methoxyquinoline hydriodide and hydroxyquinoline methiodide CgNH6*OMe,HI + CgNH6*OH,MeI + 2H2O [OH = 1 ; OMe = 11 is obtained by heating together in sealed tubes at 100" for several hours a mixture of 1-hydroxyquinoline and methyl iodide in mole- cular proportion with methyl alcohol. It is insoluble in ether but soluble in alcohol and water crystallising from the former in yellow triclinic plates decomposes a t 143" gives a hydrochloride C9NH6Me0,HC1 + CgNH,O,MeC1 4- 5H20 forming miuute red'crys- tals easily soluble in water and a platinochloride C,oH,,N,02,H2PtCI + 2H20 crystallising in orange-red prisms which decompose a t 248".Methoxyquinoline-hydroxyguinoline methiodide C20H,gN2021 may Ice prepared by treating the above compound with ammonia or soda. It crystallises from hot alcohol in orange-red needles and combines with methyl iodide to form the compound C21Hz2N20J2 + 2H,O which crystallises in yellow needles and is converted by silver Gxide into the deliquescent compound GOH,,N,O3. The iodide C20H,gN20,1 on reduction with tin and hydrochloric acid was expected to yield kairin and tetrahydroxymethoxyquinoline but only the formation of tlle former of these compounds could be ascertained.The ethyl-compound C22H,3N2021 is prepared by a method similar to that used in the case of the methyl-compound above described. It crystallises i n redORGANIC CHEMISTRY. 175 needles which melt at 202" and furnishes a platinochloride which crystallises with 2 mols. HzO. Quinolineparamethenylaslidoxime and its Derivatives. By J. BIEDERMANN (Ber. 22 2761-2767).-&uinolincparamethenylan~id- oxime CgNH6*C(NH,):NOH is formed when paracyanoquinoline (m. p. 135") prepared from paraquinolinesulphonic acid by Fischer and Willmack's method (Abstr. 1884 1051) is treated with hydr- oxylamine hydrochloride aud sodium carbonate in dilute alcoholic solution. It crystallises from boiling alcohol in yellowish needles melts at 105" and is readily soluble in alcohol and ether more sparingly in benzene chloroform and hot water and almost insoluble in light petroleum.It dissolves freely in acids but is only sparingly soluble in alkalis ; it gives a greyish-green precipitate with Fehling's solution and a deep-red coloration with ferric chloride. In aqueous solutions silver nitrate produces a colourless crystalline precipitate which darkens after some time with separation of silver. The hydro- chloride CloH9N30,HCI crystallises in colourless needles and is readily soluble in alcohol and water but insoluble in ether benzene light petroleum and chloroform. (CloHgN30) 2 HzPtCl6 crystallises in well-defined prisms. The ethyl-derivative ClzHI3N30 crystallises from dilute alcohol in colourless needles melts at 85" and is readily soluble in alcohol ether chloroform benzene and hot water but almost insoluble in cold water.The ncetyl-derivative Cl2HllN3O2 prepared by treating the amidoxime with acetic chloride in ethercal aolution crystnllises from hot benzene in colourless needles melts at 115" and is sparingly soluble in alcohol ether chloroform and benzene and almost insoluble in cold water. G. T. M. The platin,ochloride f&?uinolineparamethenylethenylazo~nae c,NH,*c<?$&Me pre- pared by dissolving the amidoxime in hot acetic anhydride or by digesting the acetyl-derivative with alkalis or water crystallises from dilute alcohol in slender needles melts at 175" and is soluble in alcohol ether benzene and chloroform but almost insoluble in water.It gives with ferric chloride a bluish-violet coloration and mercuric chloride and auric chloride produce precipitates in a hydrochloric acid solution. E t hy 1 puinolinep arameth en y 1 amidoxiin ecarbolc y late CgNH6.C (NHZ) :NO.C 0 OE t is formed when the amidoxime is treated with ethyl chlorocarbonate in chloroform solution. It crystallises from boiling alcohol in colour- less needles melts a t 97" and is soluble in ether chloroform benzene and acids but almost insoluble in light petroleum and cold water and insoluble in alkalis. Quinolineparamethenylcarbon ylamidoxirne CgNH6*C<NH N-0 > co pre- pared by boiling the preceding compound with alkalis or by digesting the amidoxime with excess of ethyl chlorocarbonate crystallises from176 ABSTRACTS OF CHEMICAL PAPERS.boiling benzene in colourless needles melts at 155" and is soluble in alcohol ether chloroform and alkalis but almost insoluble in cold water. In aqueous solutions of the ammonium-derivative copper sulphate produces a green lead acetate and silver nitrate a colourless crystalline precipitate. CgNH6- C (NOH)*NH*C ONH2 separates in colourless ci-ystals when a concentrated aqueous solution of the amidoxime hydrochloride is treated with potassium cyanate ; i t crystallises from boiling water in small coiourless needles melts at 164-5" and is only sparingly soluble in cold water and acids but more readily in hot water alcohol ether benzene light petroleum and alkalis. Quinolinepuramet heny lurainidoxinz e Quinolineparametheny 1 b enzen y 1 azoximeparacarbox y lic acid prepared by melting the amidoxime with phthalic anhydride crystal- lises from hot alcohol in colourless needles melts at 203" and is soluble in ether and chloroform but only sparingly in benzene and water and almost insoluble in light petroleum.F. S. K. a-Cinnamenylcinchonic Acid and 2 4-Quinolinedicarboxylic Acid. By 0. DOEBNER and J. PETERS (Ber. 22 3006-3011)- a- Cinnamelz y lcinchoizic acid C HP h CH. C < N-y6& is prepared by gradncllly adding from a dropping funnel an alcoholic soh- tion of aniline (52 grams) to a. solution of cinnamaldehyde (75 grams) and pyruvic acid (50 grams) in absolute alcohol. The whole is boiled in a reflux apparatus on a water-bath for four to five hours; the liquid is then concentrated and the crystals which separate washed with ether and crystallised from hot alcohol.The yield is 10 grams. The acid crystallises in yellow needles melts at 295" wit,h evolu- tion of carbonic anhydride is insoluble in water sparingly soluble in ether benzene and chloroform more soluble in hot alcohol especially if a few drops of hydrochloric acid are added. The acid solution has a green fluorescencc. The potassium sodium and ammonium salts are readily soluble ; the magnesimn salt (CleH,zN02)2Mg crystallises in concentrically-grouped lustrous yellow needles; the silcer salt is a flaky precipitate; the nickel and copper salts are yellowish-green and the zinc and lead salts yellow. When the acid is distilled it decomposes into benzylidenequinaldine (Jacobsen and Reimen Abstr.1884 335) and carbonic anhydride. Cinnamenylcinchonic acid is also formed by heating =-methyl- cinchonic acid with benzaldehyde and zinc chloride and by the action of aniline on pyruvic acid and cinnamaldehyde at the ordinary temperature. In the latter case an indifferent compound of the formula C2rHzoNz0 is obtained which crystallises from glacial acetic acid in yellowish needles melting at 194". 2 4-Quinoliitedicarboxylic acid CgNH,( COOH)2 is obtained by adding a solution of potassiam permanganate (7-5 grams) in water (500 c.c.) to a solution of a-cinnamenylcinchonic acid in CH C C 0 OH'ORGANIC CHEMISTRY. 177 soda diluted to 500 C.C. After 24 hours i t is filtered evaporated down to one-third of its bulk treated with dilute hydrochloric acid and allowed to cool.The acid separates in slender needles and is crystallised from water. It melts at 246' with decomposition is sparingly soluble in cold water alcohol and ether insoluble in henzene and chloroform. The calcium salt C,,H,NO,Ca crystallises iu slender white lustrous needles ; the barium salt forms gronps of long needles ; the copper salt (with 1 mol. H,O) is a sparingly soluble hluish-green precipitate ; the silver salt is a very gelatinous white precipitate other salts were prepared. When the acid is heated above its melting point i t partly sublimes and is partly decomposed into quinoline and carbonic anhydride. Hydroquinoline-derivatives. By 0. SRPEK (Monatsh. 10 701-729).-A solution of the hydrochloride of quinic acid (20 grams) in concentrated hydrochloric acid (100 grams) was mixed with stan- nous chloride (10 grams) and then heated with metallic tin (28 grams).When the metal had dissolved the solution was saturated with hydrogen sulphide to precipitate the tin filtered and concentrated i n an atmosphere of carbonic anhydride whereby the hydrochloride of tetrahydmquininic acid CllHI3NO3,H C1 crystdlising in small needles melting at 205-206" (uncorr.) separated out. The acid has probably all four but certairily two hydrogen-atoms attached to the yyridine nucleus since it gives an acetyl-derivative Cl1Hl2AcNO melting at 240-241" (uncorr.) and therefore contains an imidogen- group. On treatment with bromine the acid furnishes what is probably an additive product which has a red colour and on treating this w i t h hot hydrochloric acid washing with water boiling with sodium hydrogen sulphite and recrystallising from xylene it gives tribromo- quinanisoil C10H6Br3N0 a substaitce which crystallises in white needles melts a t 233" and is identical with the compound obtained by Skraup from thalline ; on heating it with concentrated hydrocliloric acid first a t 150" and afterwards at 170"-1~0" it gives a tdromhcydr- oxyquinoZine.This tribromhydroxyquinoline crystallises from acetic acid in needles melting at 818" (uncorr.) and is also produced together with tribromoquinanisoil on bromination of thalline hydro- chloride. Tribromoquinanisoil is oxidised by boiling concentrated nitric acid to a bromop~ridinecarboa~Zic acid which melts at 182" (uncorr.) and proves to be identical with the bromonicotinic acid obtained by Clans and Collishonn (Abstr.1887 158). Tribromohydroxjquinoline is converted by potassium perrnangmate into a bromoquinolinic acid C,H2Br(COOH)2 + H20 which appears to be identical with the acid obtained by Claus and Collishonn (Zoc. cit.) and decomposes at 165" into carbonic anhydride and the above-mentioned bromoiiicotinic acid. On fusion with potash these bromonicotinic acids furnish an acid free from bromine and 4'-hydroxypyridine. The tribromo-compounds must consequently be regarded as having one bromine-atom in the 4'-position of the pyridine nucleus and the other two atoms in the benzene niicleus. Tetrah y drobroinhy d w x yq uinoline hydrochloride C,N H,Br 0 H HCl VOL.LVIIL. n N. H. M .t 78 ABSTRACTS OF CHEMICAL PAPERS. which crystallises in needles melting at 238" is obtained on rediicing tribromohydroxyquinoline with tin and hydrochloric acid. G. T. M. Formation of Azines from Orthodiamines and Polyamines. By R. NIETZRI (Ber. 22 3039-3040).-A discussion of the bearing of recent work on this subject. Derivatives of Ortharnidobensyl Alcohol. By H. G. S~DER- BAUX and 0. WIDMAN (Ber. 22 2933-2942).-The platinochloride of the benzophenyldihydroketometadiazine previously described (Ahstr. 1889 973) forms prismatic crystals melting with decomposi- tion a t 199" ; the awochloride yellow needles melting at 170-172". - I CHz.NMe Phenometh~ldihydrothiometadiazl:ne C6&<NH As is formed by heating orthamidobenzyl alcohol with methyl thiocynnate in benzene solution.Hydroxytolylmethylthioc.arbamide is first formed as a brown oil which becomes thick on cooling b u t does not crystallise and if this is heated with hydrochloric acid it is converted into the diazine which crystallises from methyl alcohol in long glistening needles and melts at 139". The platinochloride crystallises in four-sided plates melting with decomposition a t 195" ; the aurochloride forms yellow microscopic needles melting a t 1.51-153". w-Hydroxytolyl~thylthiocarbamide formed like its methyl analogue is also an oil and with hydrochloric acid yields phenethyldihy drothiometadi- CHz'yEt which crystallises from alcohol in long needles NH* CS azine C6Ha< melting a t 103". The platinochloride is a pale-yellow powder melting at 208" ; the aurochloride forms crystals melting at 118".When the methylthiocarbamide is heated with mercuric oxide it This is yields phenomethzJldih2/droketometadiazine C6H4< easily solublc i n organic solvents sparingly SO in waker. The platino- chloride ( C,H,~,0),,H,PtC16 crystallises in needles or plates melting at 202-203" the aurochloride ( C9HloN20),HAuC14 in yellow glisten- ing prisms melting a t 185". The ethylthiocarbamide in like manner yields phenethyldihydroketometadiazine which crys tallises from alcohol in flat colourless needles and melts at 94-56". The platinochloride crystallises in yellow needles melting with decomposition at 205" ; the aurochloride forms golden-yellow scales melting a t 116-118". C Hz*T Me NH*CO * Phenallyldihydroketometadiazine C6H4<NH.CHz*T*C,H co prepared from the allylthiocarbamide is very soluble in alcohol crysfallises in microscopic prisms and melts a t 77-78". The platinochloride crystal- lises in needles and melts at 169-171'. CH,*rPh prepared from NH-CO Benzophenodihydroketometadiazine CsHa< the benzothiocarbamide crystallises from alcohol in needles or prisms melting at 145-146". It forms a crystalline platinochloride and auro- chloride. All attempts to obtain phenodihydrothiodiazine provedORGANIC CHEMISTRY. 179 futile. The author points out the regularity of the melting points in these thio- and oxy-series. When oxidised with chromic acid in acetic acid solution phenodi- CO.S;IH hydroketometadiazine yields benzoylencarbamide C6H4<NH co 9 described by Griess and by Abt.The formation of these two groups of compounds appears at first sight to be analogous to that of the pseudo-carbamides lately described by Gabriel (Abstr. 1889 848). But after a careful examination of the evidence the author concludes that the formula ascribed by him to the diazine is correct and that his and Gabriel's compounds are not strictly analogous. Codeine Methiodide. By Z. H. SKRAUP and D. WIEGMANN (Monatsh. 10 732-733). It has been previously shown (Abstr. 1889 1018) that in all probability the nitrogen-atom in morphine has both a methyl- and an ethyl-poup directly attached to it. If this view is a correct one codeine methiodide which on heating with alkalis is converted into methylmorphemethine should give rise to ethyldimethylamine when treated with alcoholic potash and not to dimethylamine (the product said to be obtained by Knorr Abstr.1889. 417). On repeating Knorr's experiments the authors find that ethyldimethylamine together with a small quantity of trimethylamine is really produced and furnishes a characteristic platinochloride which is sparingly soluble with alcohol and crystallises from water in octahedra melting at 193". G. T. MI. Oxidation-products of Quinoidine. By H. STRACHE (Monatsh. 10 642-646 ; compare Abstr. 1889 1016).-When quinoidine (800 grams) is oxidised by boiling with commercial nitric acid (about 26 kilos.) added a little at a time until the solution is no longer rendered turbid by ammonia a mixture of a-pyridinetricarboxylic acid (73 grams) cinchorneronic acid (48 grams of the hydrochloride) aud cinchonic acid (34 grams) is obtained.At the sa.me time a hydro- chloride of a nitroquinolinecarhoxylic acid is formed which on snblimation gives a ni troquinoline crystallising in needles melting at 153-154". The properties of this base agree with those of La Coste's 4-nitroquinoline. G. T. M. L. T. T. Action of Potash on Alkyl Halogen-derivatives of Papa- verine. By G. GOLDSCHMIEDT (Monntsh. 10,673-69l).-The author defends the views of Stransky (Abstr. 1889 166) against those of Clans and Edinger (ibid. 415) and has made the following observa- tions on repeating Stransky's experiments. According to Claus the bases obtained on treating the alkyl halogen additive products of papaverine with silver oxide and with potash respectively differ con- siderably for whereas the hydrochloride a11d alkyl chlorides of the former give a platinochloride which is crystalline anhydrous and may be crystallised from hot water the hydrochloride of the latter gives a platinochloride containing water of crystallisation and which readily decomposes when attempts are made to recrystallise it from n 2180 ABSTRACTS Ol!' CHEMICAL PAPERS.boiling water. Clam and Edinger obtained from the methyl base an uncrystalJisable platinochloride containing 1 mol. H20 and Hutlein found that the ethvl base gave a crystalline platinochloride also con- taining 1 mol. H20. The author shows that the platinochloride of ethylpapaverinium oxide ( CmH21N04Et,)2PtC16 + 3$H20 prepared by means of potash and the corresponding methyl-compound similarly prepa.mil are both stable in presence of boiling water whilst the methyl-compound obtained by means of silver oxide is an anhydrous salt.On the other hand the liydrobromide obtained by Stransky from ethylpapaverinium oxide and hydrobroinic acid is crystallographically identical with the papaverine ethyl bromide pre- viously described by the author. Of these apparently coiitradictory facts no explanation can at present be offered. Claus and Hutlein have expressed the opinion that during the action of potash on the alkyl halogen-derivatives of papaverine the alkyl- groups swing from the nitrogen- to a carbon-atom ; the author how- ever finds that ethylamine is formed by boiling pspaverine ethyl bromide with potash ; at the same time a compound melting at 240" and also one melting at 186-187" cryatallising from alcohol in white needles having the formula CIgH,o05 or ClgHl& and containing four methoxyl-groups are formed.Papaverinic and Pyropapaverinic Acids. By G. GOLDSCHMIEDT and H. STRACHE (Monatsh. 10 692-700; compare Abstr. 1888 302) .-Correcting a previous communication (Abstr. 1886 4 i 9 ) the authors state that papaverinic acid (Abstr. 1885 lOSO) C,,H13N0 crystallises with 1 mol. H20 and furnishes a ketoxime C16H14NZ0 which crystallises from alcohol in small needles melting at 154-157". Ammonium pyropapaverinate gives precipitates with many metallic salts and may be used to prepare the undermentioned compounds Calcium pyropapaverinate ( C15H,2N0,)2Ca + 4 H20 crystallises in groups of needles ; barium pyropapaverinate ( C15EI12N05)2Ba + 4H20 in plates ; the hydrochloride C1,H,sN05,HC1 + H,O crystallises in oisange-red needles ; the phenylhy drazone C15H,,N04:N2HPh crystal- lises from alcohol in yellow prisms softens and turns red a t 210° melts with decomposition a t 223" and forms a hydrochloride G.T. M. C l,H13NOa:N,HPh HC 1 a vermilion-coloured powder. The ketoxime of pyropapaverinic acid C15H14N205 crystallises from alcohol in needles melting ah 266" its hydrochloride C15H14N205,HC1 + H20 crystallises in lemon-yellow needles which lose HC1 and HZO when heated at 105" and are slowly decomposed on boiling with water. G. T. M. Ulexine. By A. W. GERRARD and W. H. SYMONS (Pharm. J. Trans. [ 3 3 19 1029-1030).-Ulexine C11H,4N20 the alkaloid previously obtained by the authors from the seeds of the common furze Ulex Europceus (Abstr.1886 1048) forms colourless odourless deli- quescent crystals freely soluble in chloroform but insoluble inORQANlC CHEMISTRY. 181 absolute ether. The. substance fuses at 151" and begins to char a t 175". It is a strong base for it precipitates quinine coca'ine and strychnine and also liberates ammonia from its compounds. It cannot be sublimed without decomposition. The platinochloride (C,lH,,N,o)2,H2PtC1 forms lustrous crystalline plates ; the aurochloride CllH,,N,O,HAuC1 was also analysed. When ulexine is treated with alkaline permanganate it gives off two-thirds of its nitrogen as ammonia. Ulexine has a powerful physiological action and ane-tenth of a grain has been found to pro- duce toxic effects.It raises arterial tension produces diuresis and acts as a nerve and muscle poison affecting the respiratory organs especially. A second base seems also to occur in the seeds but has not yet been obtained in quantity sufficient for examination. R. R. Bile-Pigments. By J. B. HAYCRAFT and H. SCOFIELD (Zeit. physiol. Chem. 14 I7;<-181).-When bilirubin is oxidised biliverdin is formed ; if the oxidation be carried further as by nitric acid a blue pigment bilicyanin is formed then a violet (perhaps a mixture of the blue and red) then a red and lastly a yellow pigment (chaletelin) are formed. There have been however very few experiments recorded in which by means of reducing agents the lower terms of the series have been obtained from the higher.Lauder Brunton (Hudb. of Physiot. Lab. p. 498) alone mentions that sulphuric acid colours an alkaline solution of bilirerdin yellow and that if this pellow solution is then treated with nitric acid a solution of bilirubin is obtained. In the present research it was noticed that ox bile on being allowed to remain for some hours changed in colour fram green to orange- brown. This is regarded as reduction for it' nitric acid be added to it bilirubinis first obtained and then the usual' series of green blue violet red and yellow pigments. It was also noticed that the bile in the gall-bladder was yellowish where it came in contact with the wall of that viscus ; this is an instance of reduction brought about by living tissues Another instance of reduction is the presence of gall- stones coloured by bilirubin in the bile of the ox of which the natural pigment is biliverdin.Experiments were then carefully performed in which bile was observed under different conditions in the air in closed sterilised tubes mixed with pieces of mucous membrane and so forth from which the following conclusions are drawn :-That biliverdin parts with its oxygen as easily as oxyhaemoglobin ; in steriliscd vessels the reduction stops at bilirubin ; the reduction is hastened by exposure to light putrefaction and admixture with mucus or mucous membrane but hindered by darkness and drying the bile. When putrefaction occurs reduction goes on to the formation of a brownish pigment which gives no play of colours with Gmelin's test but which differs from hydrobilirubin by being insoluble in ether and easily soluble in alcohol.It moreover shows no absorption-bands. Copeman and Winston (Abstr. 1889 792) have observed that human bile is olive-182 ABsTRACTS OF CHEMICAL PAPERS. green ; probably this undergoes reduction after death ; hence the pigment usually described in human bile is bilirubin. The play of colours can be obtained at the positive pole of a battery (4 Grove cells) placed in the bile indicating successive stages of oxidation ; if the negative pole be then placed in the bile the series is reversed indicating reduction. Preparation of Crystalline Egg-albumin. By F. HOFME~STER (Zeit. physiol. Chem. 14 165-172).-Fresh white of egg freed from membranes was mixed with an equal volume of saturated solution of ammonium sulphate to precipitate the globuliu and the filtrate allowed to evaporate in flat dishes at the ordinary tem- perature.In a few days st deposit of granules or scaly aggregations of g r a d e s was observed and later needles or stellate collections of needles were mixed with these. Whether these are pure egg-albumin or a compound of egg-albumin with ammonium sulphate and whether other animal prote'icls act similarly are questions which have still to be investigated. Remarks on the differences between colloids and crystalloids and the necessity of modifying our ideas concerning this difference conclude the paper. Peptone and Similar Substances. By J. SERELIEN ( B i d Centr. 1889 71 7-718).-Pure milk csse'in was digested with peptone and hydrochloric acid the nuclein filtered off all albumoses sepa- rated by ammonium sulphate and the resulting filtrate mixed with tannin.The precipitate thus obtained was decomposed by baryta- water and then the barium removed. A solution of pure peptone was thus obtained and was only precipitated by alcohol phospho- tungstic acid and tannin and was redissolved by excess of the latter. Optical estimation of the amount of peptone present indicated a percentage of only 1.2-2-7 per cent. which was obviously too low ; hence it was concluded that the compound was almost or even quite inactive. E. W. P. W. D. H. W. D. H.I lli ABSTRACTS OF CHEMICAL PAPERS.Organic Chemistry.Purification of Amy1 Iodide. By H. MALBOT (Bull. SOC. Chim.[33 1 604).-Amy1 iodide may be completely freed from the alcoholwhich distils over in its preparation by treatment with an equalvolume of concentrated hydrochloric acid which dissolves this im-purity ; the alcohol may be recovered by subsequently diluting the11 y drochloric solution.Carbonylhydroferrocyanic Acid and Carbon ylferrocyanides.By J.A. MULLER (Ann. Claim. Phys. [GI 17 93-102).-The authorhas previously described a new class of ferrocyanides and ferri-cyanides in which the group CO is substituted for KCN ( A bstr. 1887,649). The crude violet precipitate (Znc. cit.) which still containsferrocyanide is treated with a warm solution of potassium carbonate,the liquid filtered and when cold slightly acidified with acetic acid andmixed with excess of lead acetate.After remaining for a day the liquidis again filtered the filtrate mixed with a slight excem of potassiumrubonate and boiled. The traces of lead which remain in thefiltrate from the lead carbonate are removed by means of hydrogensnlphide after slightly acidifying with acetic acid.Carbo?ryZh?ldroferrocyania acid HaeCO( CN) is obtained by theaction of hydrogen sulphide on the copper salt and when the solu-T. G. NORGANIC CEEMISTRP. 117tion is evaporated over potassium hydroxide in the dark the acidseparates in colourless platy crystals with an acid taste and anastringent after-taste. It is acid to litmus and decomposes alkalinecarbonates. When the aqueous solution is boiled the acid decom-poses with formation of a violet-blue precipitate and evolution of alarge quantity of hydrocyanic acid but no ca.rbonic anhydride isevolved and neither formic acid nor ferrocyanide is formed.The sodiunz salt is obtained in the same manner as the potassiumsalt (Zoc.cit.) and crystallises with 6 mols. H,O in very pale-yellow,monoclinic needles which become anhydrous at 110". The insolublecarbonylferrocyanides are obtained from the alkaline salts by doubledecomposition.The silver salt precipitated by excess of silver nitrate in presenceof a small quantity of acetic acid forms a white curdy precipitatewhich rapidly becomes black even in the dark. After being washedwith water it contains no potassium. It is slightly soluble in dilutemineral acids with evolution of hydrocyanic acid but is practicallyinsoluble even in boiling acetic acid.Potassium hydroxide convertsit into potassium carbonylferrocyanide and silver oxide. It retainswater after being dried in a vacuum and at 100" to 110" i t slowlydecomposes still retaining a small quantity of water. At a dull redheat decomposition is rapid cyanogen and hydrogen cyanide beingevolved. If in the preparation of the salt the alkaline carbonyl-ferrocyanide is in excess the precipitate only becomes slightly grey,but it retains potassium nitrate and possibly some silver nitrate.The .uranium salt (U02)3(FeCOCy5)2 + 5H,O from uraniumnitrate and the potassium salt is an orange-yellow gelatinous sub-stance which retains no potassium and is only slightly soluble inwater b u t somewhat more boluble in dilute acetic acid.At 70" i tforms a ruby-red granular solid which re-acquires the yellow colourwhen powdered ; at 110" it becomes black and partially decomposes,but still retains a small quantity of water.The cobult sult forms a lilac precipitate which contains 3.5 mols.H20 and retains potassium even after prolonged washing its compo-sition being represented by the formula (Co,.,,K,,.,,)FeCO(CN),. I t isslightly soluble in water and is decomposed by cold dilute nitric acid.I n a dry vacuum or when gently heated i t is partizlly dehydratedand becomes deep-blue. This change takes place even in boilingwater but the salt is rehydrated on cooling. It retains a smallquantity of water even at 110".The copper salt forms a yello wish-green gelatinous precipitateinsoluble in dilute nitric or sulphuric acid.I t retains no potassium,becomes dehydrated with change of colour when gently heated andat 110" forms a somewhat hygroscopic dark-brown powder whichundergoes slight decomposition at this temperature but still retains asmall quantity of water.The ferric salt is obtained from the potassium salt and ferricchloride as a violet precipitate which is free from potassium andwhen dried at a moderate temperature forms a very friable resinousmass with a brilliant conchoidal fracture of very high metallic lustre.It alters even below looo and undergoes profound change a t 100" t 118 ABSTHACTS OF CEEMICAL PAPERS.110". After being dried in a vacuum it retains 12 to 13 per cent. ofwater.The violet precipitate dissolves in an aqueous solution ofoxalic acid forming a solution with a magnificent violet colour but i tis not soluble in acetic lactic succinic tartaric or citric acid. Itdissolves however in solutions of the normal aalts of these acidswen in presence of a small quantity of free acid. The solutions arealmost colourless or have only a slight violet tinge but on the additiono t sulphuric acid carbonylferrocyanide is again formed and isprecipitated or remains in solution according to the nature of theacid present. The violet precipitate of the ferric salt is not solublein solutions of poibassiurn chloride or nitrate or in very dilutephosphoric or sulphuric acid but is distinctly soluble in solu-tions of sodium hydrogen phosphate.It is slightly decomposed bypotassium sulphate and the liquid becomes acid ; it decomposespotassium hydrogen carbonate even a t 25") carbonic anhydride beingen)lved. Analysis of the salt shows that it contains more ferriciron than is required by the formula a result probably due t o thepresence of ferric oxide which was contained in the ferric chloridesolution used in the preparation of the salt and cannot be removedby washing. Precipitation of t h e alkaline salt with ferric chloridesolution of known strength followed by a determination of the ironin the filtrate also showed that the amount of iron precipitated wasgreater than the calculated quantity.All these results poink to the existence of a trivalent acidic radicleof the formula FeCO( CN),.The insoluble carbonylferrocyanidesresemble the insoluble ferrocyanides in retaining small quantities ofwater which cannot be expelled without decomposing the salt.C. H. B.Note hy A:bsimctor.-It is interesting to compare the properties offerric carbonylferrocymide with those of soluble Prussian-blue(Guignet AbsDr. 1889 475).Vinyl Alcohol a Constant Constituent of Ethyl Ether. ByT. PQLECK and K. TH~MMEL (Ber. 22 2863-2880).-When a soh-tian of mercury oxychloride in pure sodium or potassium carbonate isshaken for 10-20 minutes with ether from the most varied sources ayellowish-white amorphous precipitate is always produced in smallquantities varying from 0939-6.64 per cent. The samples employedhad generally a neutral reaction liberated iodine from a solution ofpotassium iodide gave a brown coloration with potash and were freefrom acetaldehyde; after having been shaken with the mercurysolution the ether gave no coloration with potash.The white precipitate has the composition CH,:CH*OHg*O*Hg,Cl,,and may be named vinyl oxymercurochloride. It turns yellow a t loo",becoming colourless again on cooling and a t about 170" it swells up,like mercury thiocyanate with evolution of a gas which burns with ablue flame.It is insoluble in water alcohol and ether ; when freshlyprecipitated it dissolves freely in hydrochloric acid nitric acid and11 ydrocyanic acid but when dry it dissolves completely only on boilingeven in concentrated hydrochloric acid.When boiled for a long timewith potash it is converted into a greenish-black powder which is in-C. H. BORGANIC CHEMISTRY. 119soluble in potash and the alkaline solution contains a colourlesscompound which is precipitated on adding nitric acid.The greenish-black compound has the compositionCHiC.Hg,(OH),,Hg,!OH)2,and is named '' acetylenemercurg." It dissolves in concentrated aceticacid forming a crystalline acetate arid i t is soluble in nitric acid andin aqua regia but insoluble in hydrochloric acid. It explodes veryviolently when heated (at about 157") but not by percussion. Theacetate CHiC.Hg.,(OAc),,Hg(OAc) is obtained when the blackpowder is dissolved in concentrated acetic acid and the filtered solu-tion evaporated. It decomposes at loo" or when boiled with water,and it is insoluble in ether and acids except acetic acid ; if the aceticacid solution is diluted a colourless compound is precipitated andmercury remains in solution.When hydrogen sulphide is passedinto the acetic acid solution a yellowish or colourless precipitate isproduced and the precipitate turns greenish-black after some days.The acetate is decomposed by warm potash being reconverted into theblack explosive compound.The colourless compound which is precipitated on adding nitric acidfo the alkaline solution of vinyl oxymercurochloride (see above) has thecomposition CHiC*HgO,HgCI and is named acetyler~ernerciiry ozy-chloride. It is an amorphous powder iiisoluble in hydrochloric acid,nitric acid ammonia aud alkaline carbonates but readily soluble inpotash jielding a solution which is coloured yellow by hydrogen sul-phide; it is not explosive and when heated it volatilises leaving acarbonaceous residue.When ether is distilled with phenylhydrazine the distillate gives nocoloration with potash and no precipitate with the mercury solution ;the residue contains ethylidene phenylhydrazine.Vinyl oxynierciirochloride (see above) is decomposed by bromine,yielding bromal hydrate or bromoform and formic acid according tothe length of time during which the reaction takes place. Whentreated with a solution of iodine in potassium iodide this vinyl-corn-pound gives iodoform and when triturated with dry potassium iodidean energetic reaction takes place the dark-coloured explosive substancebeing formed.If vinyl oxymercurochloride is suspended in water andtreated with potassium iodide the mixture turns yellow or greyish-green and the solution becomes strongly alkaline ; on adding hydro-chloric acid a reddish-brown powder is precipitated. When excessof hydrogen sulphide is passed into water containing the vinyl-compound in suspeusion r-trithioacetaldchyde (m. p. 75-76"),identical with the compound obtained by Marckwald (Abstr. 1888,127) is formed ; a small quantity of a very volatile unpleasant smell-ing oil probably thioacetaldehyde (compare Marckwald Zoc. &.) isalso produced. Vinyl oxymercurochloride is decomposed by ammoniumsulphide with separation of mercuric sulphide yielding acetamideand probably also traces of thioacetamide.It is only slowly osidisedby chromic acid and potassium permanganate yielding acetic acid,carbonic anhydride and small quantities of formic acid.When a large quantity of ether is repeatedly submitted to fractiona120 ABSTRACTS OF CHEMICAL PAPERS.distillation two liquids boiling a t 30-:31" and 37-38' respectively,are obtained ; both these liquids give a copious precipitate with themercury solutioii but they are generally obtained in small quantitiesonly owing t o polymerisation taking place during the distillation.The lower boiling liquid has an ethereal odour and a neutral reaction,b u t it soon becomes acid owing to the formation of acetic acid; itdoes not liberate iodine from pot<assium iodide until it has undergoneoxidation a fact which indicates the formation of hydrogen peroxide.The higher boiling liquid has a slight ethereal odour does not alteron keeping has a neutral reaction and unlike the lower boiling liquid,is not oxidised by potassium permanganate.An ammoniacal solu-tion of silver nitrate is not reduced by either of the two liquids butboth give a brown coloration with potash ; the lower boiling liquidonly reduces alkaline copper solutions and yields iodoform withpotassium iodide.Vinyl ethyl ether gives a precipitate with the mercury solutionreferred to above but the precipitate differs from vinyl oxymercuro-chloride in composition and in not forming an explosive compoundwhen treated with potash.Vinyl chloride and vinyl iodide in alcoholic solution give pre-cipitates from which explosive substances are obtained by treatmentwith potash.The above experiments show that the substance which is presentin ether and which is precipitated by the merciiry solution is vinylalco ho 1.When air containing ozone is passed for a long time through pureether or when pure et,her is shaken for a long time with hydrogen per-oxide it yields subsequently a precipitate of vinyl oxymercurochloride.A violent reaction occurs when pure ether is added drop by drop toanhydrous chromic acid a liquid distilling which if the operation iscarefully conducted smells only slightly of ether but has on theother hand a peculiar aldehyde-like odour.When the distillate isfractionated a liquid boiling a t 3 3 O probably a polymeride of vinylalcohol is obtained.It has a neutral reaction does not liberateiodine from potassium iodide and does not give a brown colorationwith potash but it yields a copious precipitate with the mercurysolution ; it resembles the liquid boiling a t 37-38" (see above) in itsot h er proper ties.Vinyl alcohol and hydrogen peroxide are formed when pure ether isexposed to direct sunlight either alone or in contact with water ; thepresence of hydrogen peroxide can be recognised by the chromic acidrea c tio n.Commercial ether gives only a slight blue coloration with dilutechromic wid solution but on agitating with air an intense blue colora-tion is produced. The formation of hydrogen peroxide i n this wayaccounts for the explosions which sometimes occur when ether whichhas been kept for a long time is distilled.Synthesis of some Glycerols by means of Hypochlorous Acid.By S.REFORMATZKY (J. pr. Cliem. [2] 40 3 9 6 4 1 9 ; compare Abstr.,1885 882).-A chlorhydrin C6Hl3O2C1 is obtained on adding byF. S . I(ORGANIC CHENISTRT. 121degrees a solution of hypochlorous acid free from chlorine to allyl di-methyl carbinol(20 grams) and some ice-water in a retort cooled by ice(compare Orloff Abstr. 1886 138 681). When the odour of hypo-chlorous acid has nearly disappeared a little sodium thiosulphate isadded to destroy the last traces of it the liquid is filtered and thenshaken with ether which extracts the chlorhydrin (23 grams) ; it is athick liquid.To obtain t'he corresponding gZyceroZ C6H1403 potassium hydroxide(25 grams) is added to the residue in the retort without previouslyextracting the chlorhydrin and the mixture is distilled until t wo-thirdshave passed over ; the residue is nearly all evaporated in a dish theexcess of potassium hydroxide neutralised with sulphnric acid and theexcess of the latter with dry sodium carbonate ; evaporation is thencontinued to dryness and the residue extracted with 95 per cent.alcohol ; the solution is mixed with ether which throws down foreignmatters and then evaporated to obtain the glycerol (80 per cent.oftheory). It distils atlabout 198" at a pressure of 60-65 mm. and is acolourless sweet thick liquid soluble in water and alcohol but not inether.The acetate C6H1,(OAc)3 is obtained by heating the glycerol(3 grams) with acetic anhydride (9 grams) at 100" in a tube for 10hours and evaporating off the excess of the latter; it is a mobileliquid insoluble in water soluble in alcohol and ether.When oxidised by nitric acid the glycerol yields a triatomic mono-basic acid containing 6 atcms of carbon. Potassium permanganateoxidises the glycerol to hydroxjvaleric acid.A c,L?orhydrin C8H12C102 is prepared from allyl diethyl carhinol inthe same way as from allyl dimethyl carbiiiol and from this the cor-responding glycerol C8H,,(OH) is obtained ; it is a colourless thick,bitter liquid soluble in water alcohol and ether and boiling at2OP-207" under 55-60 mm. pressure. An acetyl-derivative,C8Hl5O3Ac3 was obtained.Ally1 methyl pmpyl carbinol yields a chlorhydrin C,Hl,(OH)2Cl asa somewhat thick colourless liquid.The corresponding glycerol,C8H15(OH)3 is a thick colourless liquid easily soluble in water andalcohol sparingly in ether and boiling at 210" under 60 mm. pressure.An acetyl-derivative was obtained.Unsuccessful attempts were made to prepare a glycerol from allyldipropyl carbinol and a glycerol by the hydrolysirj of diallyl carbinolby cold sulphuric acid.A chlorhydrin C,HlI(OH)3C1 was obtained from diallpl carbinolby the action of hypochlorous acid but it gave no glycerol;A. G. B. -Identity of Brain Sugar with Galactose. By H. THIERFELGER(Zeit. physiol. Chem. 14 209-216 ; compare Brown and Morris,Trans. 1890,57,57j.-Bayer and Liebrich (Virchow's Arch.39,183)first described a carbohydrate in the brain which they obtainedfrom protagon. Since then Otto (ibid. 41 272) Geoghegan(Zed. physiol. Ghem. 3 337) and Thudichum (Abstr. 1882 537)obtained one by treating cerebrin with hydrochloric acid. The last-named observer prepared it in a crystalline form and termed itcerebrose. I n the present research the sugar wits prepared fro122 ABSTRACTS OF OHEMICAL PAPERS.cerebrin by the action of 2 per cent. sulphuric acid. It reducesFehling's solution yields mucic acid on oxidation with nitric acid,and thus resembles galactose which is the only glucose that yieldsmncic acid on this treatment. In its melting point specific rotation,fermentation and phenylhydrazine-compound its properties are alsothe same as those of galactose.The mother substance of this sugarin the brain has yet to be isolated.By MAQUENNE (Ann. Chim. Phys. [6] 17,495-500).-Eucalyptus honey is secreted by a peculiar species ofblack bee which constructs enormous hives on the summits of thegigantic Eucalypti of Australia. Some of these hives furnish as muchas 5000 kilos. of crude honey each. It is a thick syrup similar inappearance to ordinary honey but containing a somewhat smallerproportion of crystals and i t has a strong aromatic odour. It consistsessentially of levulose and dextrose in practically the same proportionsat^ in invert sugar with a small quantity of aromatic substances andtraces of gum insoluble in alcohol. No peculiar sugar could be detected.The Precipitation of Colloid Carbohydrates by Salts.ByJ. POHL ( Z e d . physiol. C'hem. 14 151-164).-'l'he neutral saltsused in the separation of prote'ids can also be employed for the sepa-ration of plant mucilages and other colloid carbohydrates. Thoseexamined in the present research can be grouped as follows :-A. Those not precipitable by saturation with neutral salts :-Gumarabic and sodium arabinate.B. Those precipitable by saturation with ammonium snlphate :-The mucilages of tragacanth althea linseed and cydonia. Gumtragacanth is also distinguishable from gum arabic by its lessersolubilities. Cydonia mucilage is a mixture of cellulose and a car-bohydrate very like gum tragacauth.C. Those precipitable by saturation with ammonium snlphate am-monium phosphate and potassium acetate :-Carragheen mucilage.D.Those precipitable by saturation with sodium snlphate mag-nesium sulphate ammonium sulphate and ammonium phosphate :-Soluble starch lichen starch dextrin salep mucilage and pectin.These forms of carbohydrates are further distinguished by the per-centage of salt necessary for the commencement of precipitation ;thus tragacanth requires complete saturation with ammoniumsulphate for its precipitation that is 53.5 grams of salt to everylo0 C.C. of solution. Salep mucilage begins to be precipitated by40.4 grams and soluble starch by 24.1 grams of the same salt per100 C.C. of solution. Further by fractional precipitation with mag-nesium sulp hate salep mucilage can be differentiated into twovarieties named a and B.These two varieties further differ in theW. D. H.Eucalyptus Honey.C. H. B.inel ting-points of their phenyl hydrazine-compounds.W. D. H.Oxalenediamidoxime and Oxaleneanilidoximamidoxime.By W. ZINKEISEN (Ber. 22 2946-2957.)-Vxalenediamidozime,OH*N:C (NH,)*C( NH,) :NOOH is prepared by gradually adding cyan-aniline (LOO parts) to a solution of hydroxylamine hydrochloridORQ ANIC OHEMISTRY. 123(50 parts) in 90 per cent. alcohol (500 parts). The amount of sodiumcarbonate necessary to liberate the hydroxylamine is then added andthe whole filtered from the sodium chloride. The filtrate is evapo-rat.ed down a little well shaken when cold and left for some hours ;the diamidoxime which separates is dissolved in boiling water andboiled with animal cha,rcoal.It crystallises in dazzling white con-centrically-grouped lanceolate crystals melts at 196" (uncorr.) withevolution of gas is sparingly soluble in alcohol insoluble in ether,chloroform benzene and light petroleum readily soluble in hotwater ; it dissolves in acids and bases. The aqueous solution withcopper sulphate ferric chloride and Fehling's solution gives a grass-green flaky precipitate a deep brownish-red coloration and a dirtyprecipitate respectively. The hydrochloride forms slender colourlessprisms insoluble in absolute alcohol and ether. The dibenzoyl-derivative Cl6€II4N4O4 obtained by gradually adding the finely-powdered dioxime to hot benzoic chloride crystallises in slender,slightly-yellow plates melts at 217" is insoluble in water ether,benzene and light petroleum readily soluble in chloroform sparinglyin alcohol.It is insoluble in hydrochloric acid and in alkali butdissolves unchanged in acetic and in cold strong sulphuric acids.TIT -n7Ozalenediazoximedibenzy 1 C P h < ~ ~ > C * C < A ~ ~ >CPh is formedwhen oxalenediamidoxime is heated for a long time with an excess ofbenzoic chloride. It crystallises from chloroform in slender whiteneedles melts at 246" is soluble in benzene insoluble in water,alcohol ether and in strong hydrochloric acid and alkalis ; but readilysoluble in strong sulphuric and acetic acids. When heated aboveits melting point it sublimes without decomposition.Diacetyloxalenediamidoxime CBH10N401 prepared by graduallyadding the powdered diamidoxime to boiling acetic anhydride crys-stallises in needles melts at 184-187" dissolves readily in alcohol,sparingly in benzene and is insoluble in chloroform ether and lightpetroleum.Acids and bases readily decompose it. When heated for along time with acet'ic anhydride oxalenediazoximedietlieny I C,H,N,O,,is obtained. This ci-ystallises in colourless needles melts a t 164-165",dissolves in alcohol and chloroform less readily in hot water andbenzene ; and is insoluble in ether and light petroleum. It sublimesin long slender needles.Oxalenediamidoziine diethy1 ether OEt.N:C (NH,)*C(NH,):N*OEt,is prepared by boiling an alcoholic solution of oxalenediamidoxime(1 mol.) with ethyl iodide (2 mols.) and the calculated amount ofsodium ethoxide for three hours in a reflux apparatus evaporatingthe whole to half its original bulk treating with water and filtering.It is washed several times with water dissolved in boiling alcohol,and sufficient water added to produce a slight turbidity.It crystal-lises in slender colourless matted needles melts at 114-115' dis-solves readily in alcohol ether chloroform and benzene sparinglyin hot water. The hydrochloride crystallises well.Ozalenediazoximedipropenyldicarboxylic acid124 ABSTRACTS OF CHEMICAL PAPERS.is obtained by heating an intimate mixture of oxalenedismidoxime(1 mol.) and succinic anhydride (2 mols.) at 140-150" dissolvingthe product in hot dilute aqueous soda and precipitating withhydrochloric acid.It crystallises from boiling water in almostcolourless needles melts at 200" dissolves sparingly in hot water,readily in alcohol and chloroform and is insoluble in ether andbenzene. The alkali salts are readily soluble in water,Oxalenediurarnidoxitn e,0HnN:C (NK*CO*NH,)*C (NH*C 0-NH,) :N*OH,prepared by adding a saturated solution of potassium cyanide(2 mols.) t o a hydrochloric acid solution of oxalenediamidoxime(1 mol.) crystallises from very dilute alcohol in slender whiteneedles melts at 191-192" with decomposition dissolves sparinglyin hot water readily in alcohol and is insoluble in ether benzene,and chloroform.Et h y 1 oxalenediamidorirne d icarbonat e C8 H,,N Os is formed whenfinely powdered dry oxnlenediamidoxime (1 rnol.) is slightly heatedo n a water-bath with ethyl chlorocarbonate for 20 minutes.It crys-tallises from water in long thin needles melting at 168"; i t issparingly soluble in hot water and soluble in alcohol ether and inacids and bases.Oxaleneanilidoximamidoxime OH-N C (NHPh)*C (NHPh)jN*O H isformed as bye-product in the action of cyananiline on hydroxylamine,and is best prepared by gradually adding solid cyananiline t o analcoholic solution of hydroxylamine hydrochloride (2 rnols.) filteringfrom the ammonium chloride and evaporating down until crystalsseparate. When cold it is again filtered from the oxalenediamidoxime,and evaporated almost to dryness. The crystals which separate affera long time are crystallised from boiling water.It forms colourless,hexagonal plates melts at 180° and has almost exactly the same pro-perties as oxalenediamidoxime except that it dissolves more readilyin alcohol and seems to be less stable. The precipitate with coppersulphate has a less pure colour than that which the diamidoximegives. The hydrochloride crystallises in slender colourless needles,which become green when exposed to air. The dibenzoyl-derivative,CozH,,N,04 prepared by heating oxaleneanilidoximamidoxime (1 mol.)with benzoic chloride (2 mols.) on a water-bath crystallises fromdilute alcohol in slender slightly-yellow matted needles melts at189" is insoluble in water arid light petroleum soluble in alcohol,benzene and chloroform.When boiled with alkalis i t is graduallydecomposed but does not change when boiled for a short time withhydrochloric acid.Both acids and bases dissolve it readily.Oxaleneani2idoximazoxime ethenyl OH*N:C(NHPh)*C<FO>CMe Nis obtained by dissolving oxaleneanilidoximamidoxime in hot aceticanhydride filtering when cold washing repeatedly with cold water,and dissolving in boiling water containing a little alcohol. It crys-tallises in slender colourless needles melts at 172" dissolves in alcohol,ether and benzene rather sparingly in hot water. It is dissolved byboth acids and bases and is less stable than the double nzoximeo bt ained from oxalenediamidoxime. N. H. MORQANlC OHEJIJSTRY. 125Succinenediamidoxime.296 7) .-Succinenediamidoxime,By F.SEMBRITZKI (Bey. 22 2958-0H.N C ( NHz) CHz* CH,*C (NH,):N* 0 H,is prepared by adding a strong solution of hydroxylamine hydro-chloride (2 mols.) and sodium carbonate (1 mol.) to an alcoholicsolution of ethylene dicyanide (1 mol.) and keeping the mixture forthree or four days in a well-closed vessel. It is then filtered from thecrystals of the diamidoxime and! sodium chloride and left to evaporatein a warm place. The sodium chloride is dissolved in cold water andthe remaining diamidoxime recrystallised from hot water. It formstransparent monoclinic crystals a b c = 1.2'744 1 0.9269 ; /j =79" .50' melts at 188" with evolution of ammonia and is sparinglysoluble in hot alcohol insoluble in cold water ether acetone benzene,and chloroform.It yields salts with acids and with bases; thehydrochdoride is white and dissolves in absolut,e alcohol ; the coppersalt is bright-green; the silver salt is white but a t once becomesdark when exposed to light and is completely reduced when heated,with formation of a silver mirror. The dihenzoyl-derivative,Cl9HI8N4O4 crystallises from amyl alcohol in small white needles,melts a t 192" is insoluble in water alcohol ether chloroform andbenzene &c. and does not unite with acids and alkalis.Succin enediazoximedibewzeny 1,is obtained when the above dibenzoyl-derivative is heated with waterfor five hours at 150-160". It crystallises in needles melts a t158-159" is soluble in benzene and hot alcohol sparingly soluble inether insoluble in water light petroleum and chloroform.Diacet y Esuccinenediamidoxime CsH1aN4O4 crystal1 i ses from absolnt ertlcohol in white monoclinic scales a b c = 2.2998 1 0.9105 ; p= 82" 58'; i t melts at 167-168O is soluble in hot water and inacids insoluble in ether benzene and in alkalis.The diethyl sa.lt,OEt.N:C(NH,).CEI,*CH,*C(NHz):N*OEt prepared by digesting theequivalent amounts of succinenediamidoxime sodium ethoxide andethyl iodide for some hours crystallises in colourless needles nielts at,119" dissolves readily in water alcohol ether and chloroform isinsoluble in light petroleum and is soluble in acids but not ina1 kalia.S u c c i n e n e a ~ u r a m i t l ~ i m e C,&,NsO4 is readiJy obtained by mixingconcentrated aqueous solutions of the hydrochloride of the diamid-oxirne and potassium cyanate.It crystallises with 2 mols. H,O inneedles which soften a t 100-105"; the anhydrous salt melts a t163.5 wit.h decomposition is soluble in hot water insoluble in coldwater alcohol ether and benzene &c. unites readily with acids butis sparingly soluble in cold alkalis.Succineneimidodioxime I >NH is formed in small quan-tity in the preparation of succinenediamidoxime but is obtainedalone when the mixture is digested for several dayq at 60-70". It,C H,-C (N.0 H)CH2.C (N*OH126 ABSTRACTS OF CHEMICAL PAPERS.crystallises with 2 mols. H20 and resembles the diamidoxime in itsproperties and solubility. When dissolved in aqueous potash thesolution becomes first blue then green.With ferric chloride adark-violet coloration is produced. The copper salt is dirty green ;the silver salt C4H5N30zAq2 forms small lustrous plates whichdetonate when heated leaving a residue of silver. The dibenzoyl-derivative CI,H,,N,O melts at 187-189" with previous blackening issoluble in benzene and hot alcohol insoluble in water ether andchloroform does not unite with acids but dissolves in hot alkaliswith decomposition. The diacetyl-derivative C8HllN3O4 is a white,crystalline powder melts a t 170 -171" dissolves in water alcohol,ether and chloroform sparingly in benzene and is insoluble in lightpetroleum. N. H. M.Glutarenediamidoxime and its Derivatives. By J. BIEDERMANN(Ber. 22 2967-2973).-Trimethylene cyanide is conveniently pre-pal-ed by digesting trimethylene bromide dissolved in 96 per cent.alcohol ( 5 parts) with a slight excess of finely ppwdered pgtassiumcyanide for eight hours on a water-bath filtering and distilling offfive-sixths of the nlcohol.The residue is treated with an equalvolume of ether. The ethereal alcoholic layer is separated from theaqueous evaporated down and the resulting yellowish oil distilledunder diminished pressure.Glutarenediamidoxiwe CHz[ CH2*C(NH2):N*OH J2 is obtained to-gether with glutarenimidodioxime when equivalent amounts ofhydroxylamice hydrochloride sodium carbonate and trimethylenedicyanide dissolved in aqueous alcohol are digested for 10 hours at60-70". A part of the diamidoxime separates on cooling. Themother liquor is evaporated to dryness extracted with boiling water,the solution allowed to cool filtered and again evaporated to dry-ness.The residue now consists of sodium chloride glutarenimido-dioxime and a small amount of the dinmidoxime. Glutarenediamid-oxime crystallises from water in well-formed lustrous prisms (with1 mol. H20) dissolves readily in hot water and alcohol less in etherand chloroform and is dissolved by acids and bases. It gives a red-dish-brown coloration with ferric chloride. The diacefyl-derivative,C9H,6Nb04 crystallises in microscopic slender colourless needles meltsat 115" and is readily soluble in hot water and alcohol insoluble i nether chloroform benzene &c.Glutarenediuzoximsdiethenyl CH2( CH2*C<N>CMe) N*O is preparedby boiling a solution of glutarenediamidoxime in acetic anhydride,evaporating down dissolving the crystals which separate in benzene,and precipitating with light petroleum.It forms slender colourlessneedles melting at 138-139"..-,H,>CH is obtained byextracting the residue from the preparation of the diamidoxime withhot absolute alcohol; the solution is evaporated and the residuedissolved in chloroform and precipitated with light pet.roleum. Itmelts at 193" without decomposition is very sparingly soluble inC(N*OH)*CH GEutnrenimidodioxime NHORQANIC CHEMISTRY. 127alcohol ether and chloroform insoluble in benzene and light petro-leum soluble in both acids and alkalis and gives a red-violet colora-tion with ferric chloride.The picrute crystallises from alcohol insplendid yellow needles melting at 175" with decomposition ; thehydrochloride forms white needles. The diczcetyl-compound C,H13N,01,is a white crystalline powder melts at 127" is readily soluble in water,alcohol ether? and chloroform sparingly in benzene and is readilydissolved by acids and alkalis. The benzoyl-compound C,,H,,N,O,,crystallises in stellate groups of needles melts at 179-180" is solublein hot alcohol and benzene almost insoluble in water ether andchloroform.When trimethylene dicyanide is treated with hydroxylamine(1 mol.) at the ordinary femperature. a compound having the formula,C5H,N,0 (which is the formula of y-cyanobutenylam.doxime) isobtained. It crystallises in colourless needles melts at 103" is readilysoluble in hot water and alcohol very sparingly in ether chloroform,and benzene.With ferric chloride it gives a red coloration butneither Pehling's solution silver nitrate nor lend acetate gives a pre-cipitate. It h& only basic properties being insoluble in dkalis. -N. H. M.Hydroxamic Acids of the Fatty Series. By C. HOFFMANN(Ber. 22 29562856) .-Acetohydroa*mic acid OH*CMe:NOH andnot ethenylamidoxime as previously stated (compare Abstr. 1887,911) is formed when acetamide (1 mol.) is treated with hydroxylaminehydrochloride (1 mol.) in cold concentrated aqueous solution. Themixture is kept until i t no longer reduces Fehling's solution thenacidified with acetic acid and mixed witb excess of copper acetate ;the precipitated copper salt is washed suspended in alcohol decom-posed with hydrogen sulphide and the filtrate evaporated. It sepa-rates from dilute alcohol and hot water in crystals containing 4 mol.H,O melts at about 58-59" and is very readily soluble in water andalcohol but insoluble in ether.It loses its water over sulphuric acidunder rediiced pressure and then melts a.t 87-88'. It has a neutralreaction gives a dark cherry-red coloration with ferric chloride andreduces ammoniacal silver nitrate solution in the cold.Formamide seems to react with hydroxylamine and sodoacetanilideand benzamide but only at ft higher temperature and even then veryslowly ; benzhydroxamic acid wag obtained in rhombic plates melt-ing at 124-125".Intramolecular Change of Allylcarbamides into IsomericBases. By S.GABRIEL (Ber. 22 2984-2991).-PropyEene-~-thio-carbamide CHMe<Fi!,:g)> is formed when allylthiocarbamide(m. p. 74" ; 1 gram) is heated with fuming hydrochloric acid (sp. gr.= 1.1 7 ; 3 c.c.) at 100" for an hour and the clear liquid evaporatedon a water-bath. The syrup is treated with 33 per cent. aqueouspotash and extracted with benzene. It has an unpleasant distinctlybasic odour and when distilled decomposes with formation of hydro-gen sulphide and ammonia. It is soluble in water. The p l a t i ~ ~ o -F. s. K128 ABSTRACTS OF CHEMICAL PAPERS.chloride (CaH,N2S),,H2PtC1 forms orange-yellow crystals ; thetrurochloride crystallises in yellow indented needles ; the picrate meltsat 198-200" and is sparingly soluble.When the base is oxidised bymeans of hydrobromic acid and bromine-water (Abatr. 1889 848),P-methyltaurocarbamic acid S0,H*CHMeCH2-NH*CO*NH2 is formed ;this crystallises in colourless crusts readily soluble in hot water.~ - M e t k y l t a w i n e SOaIT*CHMe*CH2*NH is obtained by heating theacid (5 grams) with crystdlised baryta (20 grams) and water(20 c.c.) for five hours at 140-150". It crystallises in rhombic plates,which swell up when heated.Propyle?iethiocarbarrLide m ethiodide CaH6N2S,MeI prepared by evapo-rating a mixture of the base dissolved in methyl alcohol and methyliodide melts a t 171-172".p-Dzwtethyltaurine SO,H*CHMee CH2*NHMe is obtained by treatingthe above methiodide with strong potash and extracting the basewith benzene.The base (15 grams) is then dissolved in water(300 c.c.) neutralised with hydrobromic acid treated with bromine-water (2 litres) and heated on a water-bath until the oil which sepa-rates is redissolved. The whole is evaporated to dryness dissolved inhot water (15 c.c.) and allowed to cool. Crystals of dimethyltaurocarb-amic acid SO,H*CHMe*CH,.N Me*C0.NH2 (about 3 grams) separate ;these melt at 230-240". The filtrate from these crystals is evapo-rated down and heated with water (15 c.c.) and baryta (30 grams)a t 150-160" for three hours. The product is freed from barium,evaporated to dryness and dissolved i n absolute alcohol (40 c.c.). Itis then further piirified from the potassium bromide still remainingby means of platinic chloride.It crystallises from 96 per cent.alcohol in flattened prisms melts a t 220-223" and is extremelysoluble in water.P~opylenecnrbamide CHMe< CH,,NH > is formed by the oxida-The picrate crystallises in long lust'rousO*C( NH)tion of allylcarbamide.needles melting at 185-186'. N. H. M.Ethylenelactic Acid. By M. STEGFRIED (Ber. 22 2711-2717 j.-The mother liquors from the crystalline zinc paralactate preparedfrom (horse) flesh contain as has been previously shown byWislicenus (Annulen 167 302) small quantities of a zinc salt whichdoes not crystallise. The author finds that this amorphous zinc saltis a salt of acetyllactic acid. When it is dissolved in alcohol andreprecipitated with ether i t is prtrtially converted into a basic salt,from which acetyllactic acid can be obtained in colourless needles,melting a t 166-167".This formation of zinc acetyllactate is ex-plained by the facts that flesh extract always contains traces ofacetic acid and that acetyllactic acid is produced in small quantitieswhen an aqueous solution of zinc paralactate is boiled with zincacetate.,4cetytZactic acid OAc*CHMe*COOH is also formed in small quan-tities when paralactic acid is repeatedly evaporated with 30 per cent.acetic acid. It can be obtained in somewhat larger quantities bygradually adding finely divided zinc paralactate (1 part) to anhydrouORGXSIC CHEMISTRY. 129zinc acetate (4 parts) heated to its melting point and keeping themixture in a liquid condition until it forms a homogeneous paste.The melt is digested with hot water the cold solution treated withdilute sulphuric acid and quickly extracted with pure ether; theresulting syrup dissolved in water the filtered solution evaporatedwith glacial acetic acid (+ vd.) and the crystals which separate arespread on a porous plate.Acetyllactic acid can also be prepared byheating paralactic acid (1 part) with glacial acetic acid (1 part) andsodium acetate (1% parts) at 180" for four hours ; it is isolated asalready described.The acid prepared by these methods has the same melting pointand the same crystalline form as that obtained from flesh extract.It is readily soluble in alcohol and most ordinary solvents but whenkept it becomes insoluble in alcohol does not melt below 300° anddecomposes at a higher temperature but without melting ; t h i s inso-luble modification is only slowly hydrolysed by alkalis whereas theoriginal acid (m.p. 166-167') is readily decomposed even by water.The acid prepared synthetically and that obta.ined from flesh do notrotate the plane of polarisation.When acetyllnctic acid prepared from paralactic acid is boiledwith soda it is decomposed into acetic acid and optically inactivelactic acid ; the occurrence of the latter in flesh extract a fact whichhas been observed by Heintx may be due to the previous formationof acetyllactic acid.Lactic acid yields an acetyl-derivative identical with the compounddescribed above in crystalline form in melting point and in itshehaviour with solvents ; the same acetyl-derivative can also beobtained in small quantities by carefully decomposing ethyl rtcetyl-lactate with cold water.F. S. K.Conversion of Pentamethylene-derivatives into Benzene-,Pyridine- and Thiophen-derivatives. By A. HANTZSCH ( Ber. 22,2827-2843).-A compound of the composition C ti,CI,BrO is formedwhen trichloropenteiiediliydroxycarboxylic acid (1 part) is heated fora few minutes a t 100" witsh bromine (5 parts) and water (5 parts)(compare Abstr. 1889 853). It cryat,allises in well-defined quadraticprisms melts a t 8T0 and is readily solulde in alcohol and ether butrather sparingly in water. I t quickly loses 1 mol. H,O when keptover sulphuric acid a second molecule of water being very slowlygiven off under the same conditions.The anhydrous compound canalso be obtained by recrystallising the hydrate from hot chloroform,from which it separates in hexagonal prisms melting at 136". Chluro-bromanilic acid is formed when the hydrate is warnted with excess ofalkali but a portion is completely decomposed; this reaction takesplace quantitatively when the hydrate is boiled with a concentratedsolution of sodium carbonate the cliaracteristic red crystals of thesodium salt of chlorobromanilic acid separating From the hot solution.The hydrate does not combine with phenylhpdrazine it gives the sariiedecomposition-products as trichloropentened i hy droxyca rhoxylic acidwhen heated at l:W" with excess of bromine and water and it isreconverted into the original acid when reduced with a small quantityVOL.LVIII. 130 ABSTRACTS OF CHEMICAL PAPERS.of sodium amalgam in alcoholic solution. These facts seem to showthgt this bromo-compound is a pentene-derivative of constitiitionanalogous to that of trichloropentenedihydroxTcarboxylic acid but. thefollowing experiments point to a totally different constitution. It i snot acted on by concentrated sulphuric acid with formation of anopen-chain ketone acid as is the case with the pentenecarboxylic acid.It has no well-defined acid properties only a feeble acid reaction rinddissolves in sodium carbonate without evolution of carbonic anhy-dride and not more readily than in water. Tt can be extracted fromslightly alkaline solutions with ether and it cannot be accuratelytitraked with barjta and phenolpbthdeyn.Its electrical conductivitywas examined b i Ostwaid and found to be seventythat of the original acid a fact b-hich shows beyondtwo compounds are analogously constituted. Thethis bromo-compound is therefore most probablytimes less thakdoubt that theconstitution ofp-Chloropyridine is formed when n fiolution of l.2-chlorodi keto-pentamethglene is boiled with ammonia or when a solution of thesodium-derivative is boiled with any ammonium salt. The reactionis hest cai~ied out by adding ammonium acetate to a warm s:ituratedsolution of the sodium-derivative and heating the mixture to boiling,when chloropyridine distils with the steam. This pyridine-deri-vntive is identical with the /3-chloropyridine obtained by Ciamicianfrom chlorcform and potassium-pyrroline.@-Chloropyridiwe picrate crystallises in slender yellow needles melt-ing at 135" with previous softening.The ?r,ercvrochZo?-ide crystallisesin fimall colourless needles melting a t about 180". The aurochlorideforms moss-like needles and deromposes at about 200".a Thioplrenaldehyde is produced when 1.2-chlorodiketopenta-methylene is treated with hydrogen sulphide at a temperature below loo" and the reaction Cakes place almost quantitatively whenhydrogen snlphide is passed into a solution of the sodium-derivativeheated to 30-40" and finally to boiling; the aldehyde distils withthe steam. and only small quantities of resinous products remain.The thiophenaldehyde thus obtained gives all the characteristic colourreactions for this compound and it is converted into tohe corrcspond-ingacid on exposure to the air.It combines with hydroxplamine,yielding the aldoxime (m. p. 12SJ) and with phenylhydrazine formingthe hydrazone which melts a t 134.5".Decompcsition-products of Chloranilic Acid. By A . HAXTZSCH(Ber. 2 2 2841-2833) -Tetrac?i 1o.l.oketotl.ihydroz~penturn ethy Zenecarb-oxylic acid I >C(OH)*COOH is produced when chlor-anilic acid (8 mol.) or t~ichlorodiketopentamethylenehydroxycarb-nxylic acid (1 mol.) is treated with sodiiim hypochlorite but theformation takes place slowly and only in neutral solutions (compareAbstr. 1888 1190). It is best prepared by dropping a solutionof sodium hSpochlorite into a cold aqueous solution of pureF.S. K.co - CCl,C(OH),.CCIORQANIC CHEhlISTRY. 131potassium chloranilate until the colour disappears then adding avolume of the hypochlorite solution equal to or rather larger thin Chatalready employed and keeping the mixture for 24 hours ; it is thentreated with concentrated hydrochloric acid extracted at least foiirtimes with ether and the crude product spread on a porous plate. Itcrystallises in small colourless needles melts and is completely de?composed a t 216" and is very readily soluble in water and alcohol ;it genemlly crystallises with 2 mola H20 both of which it losesslowly when kept over sulphuric acid. It resembles the originaltrichlorinated acid in appearance and is like the lattw completelydecomposed by aPkalis yielding oxalic acid.It does not combine withorthotoluylenediamine or with phenylhydrazine and it is very stabletowards oxidising agents ; it isnot acted on by boiling bromine-water,only very slowly by potassium chloi-ate and hydrochloric acid and i tcrystallises unchanged from hot concentrated nitric acid. It is notacted on by hot sulphuric acid in which it is only very sparinglyfioluble. It is a bibasic acid and measuremenfs of its electrical con-ductivity show that it is a simple chloro-substitution derivative of thetrichlorinated mid. The ammom'um salt. C6H2C1406(NH4)2 + H20,crystallises in short prisms melting at 147-148" with decomposition,when an alcoholic solution of the acid is saturated with ammonia aridallowed to evaporate in the air; The barium salt crystallises well andis very readily soluble in acetic acid and moderately easily in water.The lead sil'uer and mercuric salts are amorphous and sparinglysoluble but the mercurous salt crystallises well.The acid gives a redcoloration witrh ferric chloiide. When the acid is heated with excessof bromine and water at 130" it is decomposed into carbonic anby-dride oxalic acid and tetrachlorodibromacetone.Chlorod~ketoyentameChyleneh~droxycarboxylic acid,~O'cHcl> C(OK)COOH,CO-CH,is obtained when a well-cooled nmmonical solution of the correspond-ing triclilol-o-derivative i s treated with zinc-dust in small portions a t a!time until there is no further development of heat ; the solution is thenfiltered acidified extracted with ether and the crudeacid purified byconverting i b ivt,o the ammonium salt It crjs-tallises from ether in colourless microscGpic needles melbs at 147"with decomposition and behaves with solvents like the other acids ofthis class.The ammonium salt CBIE,C14(NH4) L crystallises fromwater in whkb i t is readily soluble in short thick prisms and de-composes at ahout 140° but has no well-defined melting point.Solutions of lead silver and mercurous salts produce precipitates inneutral solutions of the ammonium salt ; when orbhotoluglenediaminehydrochloride is added to a warm concentrated solution of tlieammonium salt a yellowish-green azine is precipitated and pheriyl-hydrazine acet.ate precipitates an oily hydrazone which graduallysolidities.When the acid is treated with concentrated sulphuric acid,i t yields a syrupy acid probably chlorodiacetylglyoxplic acid andwhen warmed with excess of bromine it is decoriiposed i n t o chloro-The yield is small.k t 132 ABSTHAOTs OF CHk MlCAL PAPERS.pentahmmacetone (m. p. 91-92?') carbonic anhydride and oxalicacid.Dichlorodik~to~~en~ameth~leneh~droxycarboxylic acid can be obtainedin like manner from the curroesponding tetrachloro-derivative but theyield is very small ; it is a syrup and is decomposed by concentratedsoda in the cold yielding large quantities of oxalic acid.Te fra ch lo rodiacrty Zg l p x y Zic acid C 0 0 H*C (0 H)2.C C12-C 0.C 0.C H CI,,is obtained when triclilorodiacetyl~lyoxylic acid (1 mol.) is treatedwith sodium hypochlorite (1 mol.) as described above.It cyystal-lises in sniall colourless needles melts at 146-147" with decomposi-tion and is very readily soluble in all ordinary solvents. It formsan aziiie a.nd a crystalline hydra.zone and it is readily decomposedby sodium hypochlorite.Dichlorc~pyruriic acid C H C12-CO*COOH is obtained when tetra-chlorodiacetylglyoxylic acid (1 mol.) is treated with sodium hypo-chlorite (1 mol.) in neutral aqueous sohition. It crystallises inneedles with 6 mol. H20 melts at :8-79" and loses its waterover sulphnrie acid i t is very readily soluble in water but isreprecipitated on adding concentrated hydrochloric acid. Itcombi ties with phenylhydrazine forming a hydrazone which containschlorine.Zromodiehloropyruvic acid CBrCl,*CO*COOH can be prepared byheating the preceding compound with bromine and water at 120" ; i tsoparates from water with 3 niols.H 2 0 in colourless crystals loses itswater over sulphuric acid and is immediately decomposed into bromo-dichlorosnethane and oxalic acid when treated with cold alkalis.F. S. K.Two Isomeric Syrnmetrical Dimethylglutaric Acids. By N. ZELINSKY (Bey. 22 'L82Y-2827) .-Ethyl dimeth!/ldicyar~oglutarate,CH2[ CMe( CN)-COOEt] is formed when ethyl sodocyano-a-pro-pionate ( 2 mols.) is treated with methylene iodide ( 1 mol.) inalcoholic solution ; the yield of the crude product is about 50 percent. of the theoretical quantity. It boils a t 282-288" with otllyslight decomposition (at 165-170" under 10-12 mm.) but couldnot be obtained pure.When boiled for 10-12 hours with moderatelycoricentrated hydrochloric acid it yields two isomeric symmetricaldimethylglutaric acids CH2(CHMe.COOH) which can be separatedby fractional crystallisation. The one melts a t 202-104" the otherat 128"; the silver salts C,Hl,Ag,04 of both acids are moderatelyRtable and undergo no change when heated a t 100".Dipher! ylglutaric acid (symmetrical) has been prepared by theauthor and Feldmann and is a t present under investigation.Dimethyladipic acid (symmetrical) seems to exist in two isomericm odifimtions. I?. S. K.Dicarboxylic Acids C,H,,O,. By I(. AUWERS and V. MEPER(Bey. 22 3005). -Of the two acids obtained by the action of silver onethyl a-bromisobutyrate (Abstr.1889 1143). the volat,ile acid istetvamethylsuccinic acid whilst the non-volatile acid is symmetricaldimetbyladipic acid C,H4((;HMe*COOH)2 (compare Zelinsky preORGANIC CHEMISTRY. 133ceding abstract). According to Hell (Ber. 10 2229) a portinn of tliea-bromisobutgric acid decomposes into hydrogen bromide and methyl-acrylic acid which unite according to Fittig and Engelhorn(Annalen 200 65)) to form p-bromisobutyric acid. The normalproduct of the action of silver on the lattar would be the abovedimethyladipic acid. I n order to test the correctness of this view,the authors are studying /3-bromisobutyric acid and especially itsbehaviour towards silver. N. H-. M.Allylethylsuccinic Acids. By E. HJELT (Ber. 22 2906).-Allylbutenyltricarboxylic acid was heated until the evolution ofcarbonic anhydride ceased and the residue was crystallised fromboiling water.Two isomeric nllylethy lsuccinic acids C,H,,O,,were obtained. The pnm-acid crystallises in small rhombic scales,sparingly solable (1 110) i n water and melts a t 1.;5-156"; theanti-acid crystallises in srnall plates more readily soluble (1 37) inwater and melts at 110-115". L. T. T'.Action of Bromine on Ethyl Oxalacetate.(Ber. 22 2912-2915) .-EtlhyZ ddbrornozalacetate,COOEt*CO.CBr,*COOEt,is formed by b a t i n g a solution of the acetate in an indifferentsolvent with a slight excesq of bromine. It forms a colourless oilyliquid which boils at 165 -168" under '20 mm. pressure; it is in-soluble in water and gives no coloration with ferric chloride. It iseasily decomposed! by bases the resolution taking place between thoketone- and dibromo-groups.Ammonia for instance yields oxamide,dibromacetamide and alcohol ; whilst phenylhydrazine yields oxalicdiphenylhydrazide (CO-N,H,Ph),.Etli y l monobromoxalacetafe COO E t*CO*CHBr.COOE t is obtainedby the action of ex:tctly the theoretical quantity of bromine on pureethyl oxslacetate in carbon bisulphide solntion ; its purification ispossible by fractional distillation in a vacuum but is most easilyeffected by the cryst:tllisation of the sodium-derivative. It is an oilboiling a t 144-147" under 8-12 mm. pressure. Its alcoholic solu-tion is coloured intensely red by ferric chloride. Attempts to isolat,ethe acid COOH*CO*CH( OH)*COOH by substituting hydroxyl for thebromine proved futile although this acid seems to be formed butimmediately decomposed again.By W.WISLICENUSL. T. T.Tricarballylic Acid. By W. 0. EMERY (Be?.. 22 2920-2924).-Tricarballylic chloride C6H6C1303 prepared by the action of phos-phoric chloride on the acid forms a thick pale-yellow oil boiling,with slight decomposition at 140" under 14 mm. pressure. Tricct7-6-allylanilide C,H,(COWHPh) obtained by the action of aniline onthe chloride crystallises in very thin white needles melting a t 252".Trimethyl tricarballylate C,H,(COOMe)J is a colonrless liquid boilingat 150" under 13 mm. pressure ; sp. gr. = 1.18281 a t 20J (water at4" = 1). With concentrated aqueous ammonia it yields tricabally 1134 ABSTRACTS OF CHEMICAL PAPERS.am;& C3H5(OON R?) which crystallises in long prisms easily solublein water very sparingly .in alcohol ether chloroform &c.and melt-i n g with decompositian at 205-203" t o a black liquid.L. T. T.Phenylthiophen. By A. RGNARD (Compt. rend. 109,699-700). -When a mixture of the vaponrv of toluene and sulphur in equal propor-tions by weight is passed through an iron 6ube heated to dull redness,thc products are hxdrogen sulphide carbon bkulphide and a blackish.substance which solidifies on cooling. If the latter is distilled i tyields some carbon bisnlphide and unaltered toluene and a yellow,solid substance which is purified .by repeat,ed crystallisation fromalcohol. A portion of the product is only very slightly soluble inalcohol and consists of another thiophen-derivative.PhenyZthiophen CISH3Ph forms brilliant white plates which meltat 170" sublime easily and boil a t about 30U".It is only slightlysoluble in cold alcohol more soluble in boiling alcohol very solublein benzene light petroleum chloroform arid carbon bisulphide butle<s soluble in ether. With isatin and sulphuric acid it gives ablue coloration and with phenanthraquinone and sulphuric acid agreen coloration. Chromic acid in presence of acetic acid convertsit into benzoic acid.~)ibro1)7ophenlllthiop~n CJ&I3rC4SHar is obtained by the actionof excess of bromine and forms vexy small white crystals whichmelt at 195" and are almost insvluble i n all ordinary solvents butdissolve to some extent in carbon bisulphide. It gives a greencoloration with phenan;tbraqninone and sulphuric acid and whenoxidised yields parabrmbenzoic acid melting at 251".D1:,/itro~l/e~yZthio~hen C,H4N02*C4SH2*N0 is obtained by thegradual addition of phenylthiophen to fuming nitric acid.It formsa. yellow non-crystallisable powder which melts a t 1789 is almostinsoluble in all ordinary solvents and whm oxidised yields para-aitroberizoic acid melting a t 2332.PhenllLth~o~hendisulpl~onic acid is formed'by heating phenylthiophenwith ordinary sulphuric acid at a temperature of 50" to 60"; i t yieldsa barium salt which is very soluble in water and very difficult tocrystal lise.Phe122/tthio~~e~te~rasZLlpkonic acid is obtained by the action of Nord-hausen acid on phenylthiophen; its barium salt is veiy soluble inwater.C. H. B.Derivatives of Ethylbenzene. By W. SUTDA (Ber. 22,2919-2920).-With regard to Sempohwski's work (this vo!. p. 5!),the author points out that oi*thethylphenol and its sulphonic acidhave already been described by Suida and Plohn (Abstr. 1881 268)and others. 11. 1'. T.Xylylene Sulphides. By E. HJmfr (Rer. 22 2904-2905).-Ortho-xylylene sulphide described by Leser (Abstr. 1884 1313),crystallises a t O" but is very unstable changing quickly into a blacORGAN10 CHEMISTRY. 135resin. The ~nercuroc7~Zoride ( CsH6S)2,HgC12 crystallises in soft longneedles. A platinochloride and a bromide were also obtained Ortho-xyl y 1 methy lsulphine iodide S c6H &I forms yellowish crystalsmelting a t 154-155".When this iodide is treated with water andsilver oxide a strongly basic sulphonium hydroxide is formed.When mets- and para-xylylene sulphides are treated with potas-sium sulphide insoluble white amorphous compounds are formed.The author has not yet obtained them quite pure btit analysesleave little doubt but that they are the corieaponding rneta- aild para-xcy ly lene sulp hides.Ethereal Oil of Betel-leaves. By J. F. EFKMAN (Be)-. 22,2736-2754. Compare Bertram and Gildemeister Abstr. 1889,863).-The leaves of CImiica BsfEe Mip. when distilled with water,yield a small quantity of a yellowish-green oil which has a burningtaste a peculiar pleasant smell and is feebly laevorotatorg.Wheushaken with concentrated potash it is partially dissolved and onadding sulphuric acid to the solution a phenol (chavicol) is pre-cipitated. The portion insoluble in aikali can be separitted byfractioiial distillation into two principal portions boiling at 175 -190"and 255-265" respectively.Chavicol C9Hlo0 is a colourless liquid boils at about 237" atid issoluble in alcohol ether chloroform and light petroleum in allproportions but only sparingly in water and ammonia. With ferricchloride the aqueous solution gives a blue coloration which disap-pears on adding alcohol. Molecular- weight determinat,ions by Raoult'srnet,hod vapour-density determinations carried out in an atmosphereof hydrogen under reduced pressure a n d an examination of its re-fractive properties showed that the molecular formula of this phenolis CgHl,O.It is a powerful antiseptic its action on bacteria beingfive times as strong as that of phenol and about twice as strong asthat of eugeiiol. The ethyl-derivative CgH,*OEt prepared by Iieatingchnvicol with potash and ethyl iodide in alcoholic solution is acolourless liquid boiling at about 232" ; when oxidised with chromicacid i t yields parethoxyhenzoic acid (m. p. 195"). Its molecularformula was found to be C11H140 by the same methods a s thoseemployed in the case of chavicol. The methy1-derivative CgHg.OMe,prepared in like manner is a colourless liquid boiling a t about 226 ;its molecular weight determined optically was found to be 151.When oxidised with potassium permangannte it yields anisic acidand an acid of lower melting point probably pammethoxyphenyl-acetic acid.The fraction boiling a t 115-190" and insoluble in alkali (seeabovc) probably contains several terpenes perhaps also cymeue andcineole but i t is free from pinene; no pure compound could beisolated from the mixture.The fraction boiling a t 255-265" contains a colourless sesqui-terpene C1,HZ4 boiling at about 260".GLiavicol has most probably the constitution OH*C,H,-CH,*CR:CH,[= 1 :.4] as is shown by its chemical properties aud also by its lowrefractive power.L.T. T136 ABSTRACTS OF CHEMICAL PAPERS.An optical examination of isosafrole and isoeugenol showed thatboth compounds probably contain the propenyl-gr&p-CH:CHMe.F.S. K- ~- -. __Safrole. By T. POLECK (Bet-. 22 2861-2863).-When safrole isoxidised with potassium permanganate i t yields piperonal piperonylicacid formic acid acetic acid oxalic acid and carbonic anhydride butno propionic acid is formed as stated by Scliiff (Abstr. 1884 1338) ;this result is in accordance with the view that safrole is the methyleneether of an allyldihydroxybenxene.Phloroglucinol. By Z. H. SKRAUP (Molzatsh. 10 721-725) .-The author has previously described the actio2 of benzoic chlorideon phloroglucinol in presence of elkalis (Abstr. 1889 1152) and hasnow by careful fractional crystallisation of the product from benzene,succeeded in obtaining the following compounds in a state of purity.DireswcinyZ tetra benzoate Cl2H6O4Bzd is readily soluble in hot benzene,and crystallises from i t on cooling in prisms melting at 199".PhZo?-o-glucinyl tribenzoate C,H,O,Bz is insoluble in water only slightlysoluble in alcohol and crystallises from benzene in plates or scalesmelting a t 173-174".Commercial phloroglucinol may best be purified by first convertingit by means of potassium hydrogen carbonate into phloroglucinol-carboxylic acid (which may be obtained free from other compounds bytaking advantage of the fact that it is soluble with difficulty in asolution of potassium carbonate and alcohol) and afterwards repro-ducing the phloroglucinol by boiling t'he pure carboxylic acid withwater (compare Will Abstr. 1885 906).F. S. K.G. T. M.Action of Alkalis and Ammonia on Halogen-substitutedQuinones.By F. KEHRMANN (J. pr. Chem. [2] 40 365-375).-Paradiethoxydichloroquinone (Abstr. 1889 707) melts a t 97-98" ; ithas the same formula as Stenhouse's ethyl chloranilate obtained bythe action of ethyl iodide on silver chloranilate but is not identicalwith it. The author distinguishes the former as the P-compound,and the latter as the a-compound. Both are obtained by the actionof potassium ethoxide on clrloranil but the /%compound largely pre-dominates when the solutirrn is weak and the temperature low. Ifthe reaction for preparing the ,!3-compound (Zoc. cit.) is allowed toproceed near the boiling point of alcohol a considerable quantity of thea-compound crystallises wi t,h the P-compound and may be separatedfrom i t by fractional crystallisation from hot alcohol in which thea-compound is more soluble as small red needles melting at104-105".The a-compound cannot be changed into the /3-compound,or vice vers6 by crystallisation.The p- and a-methyl-compounds are also both produced by theaction of potassium methoxide on chloranil the /%compound pre-dominating when the temperature is lower. By crystallisation frombenzene the dimethoxydichloroquinone (/I-compcjund) is separated a tfirst either as grains or needles melting a t 157-158" not 130'(loc. cit.). The methill chloranilate (a-compound) separates from themother liquor of the p-compoilnd in leafy crystals melting aORGANIC CHEMISTRY. 137141-142" and identical with those obtained by t h e action of methyliodide on silver chloranilate.By acting on the z-ethyl-compound with ammonia and with aniline,chloranilamide and chloranilanilide are obtained respectively ; theyare identical with the amide and anilide produced by the action ofammonia and aniline on chloranil and are therefore paradiamido-paradichloroquinone [O C1 (NHE,) = 1 4 2 5 3 61 and para-dianilidoparadichloroquinone [02 C1 (NHPh) = 1 4 2 5 3 ti]respectively.When the /3-ethyl-compound is heated with excess of aniline inalcohol for some time it becomes dark-green and dark-green crystalswith a violet iridescence separate.With ammonia instead of auiline,a deep-violet colour is produced and by diluting the alcoholic solutionwith water dark violet needles are obtained.When the p-compoundis heated with excess of aqueous potash most of it is converted intopotassium chloranilate ; but i f dilute potash is added drop by drop inslight excess to a cold alcoholic solution the liquid becomes suc-cessively violet yellow-red and colourless ; if now heated it becomespermanently violet and a violet potassium salt may be crystallisedout.When the i3-compoand is shaken with stannous chloride in etherealsolution the ,3-quinol only is obtained but if an acetic acid soluti*onis so treated both the /3-quinol and a - q u i d are obtained. Thea-compound yields only the r-quinol.a- Uiethoxydichloroquinol melts a t 151-152" not 148-150" (Zoc.p- Diethoxydichloroquinol forms lustrous colourless leaves or needlesmelting a t 108-109"; in water they melt a t 70" the greater partdissolving and separating again on cooling.a- Diwet hox ydichloroguino l forms short colourless prisms melting a t195-196" soluble in the ordinary solvetits except water.p- Din7 ethoxydichZoropuintZ forms colourless prisms melting at156- 157".A. G. 13.These matters are still under investigation.cit.) .Paratoluidine Oxalate. By E. BORYEMANN (Bm. 22 2710) .-Paratoluidine oxalate C,H,KH2,C,0sH2 crystallises with + mol. ofwater. F. S. K.Action of Bromine on Paratoluidine in the Presence ofConcentrated Sulphuric Acid. By R. HAFNER (Ber. 22,2902-2904 ; compare this vol. p. 37).-125 grams of bromine wasadded to a solution of 30 grams of paratoliiidine in 400 grams ofsulphuric acid and the whole allowed t l ) remain for 10 days.A gooddeal of paratoluidine remained unchanged whilst metabromopara-t,oluidine and orthobromoparatoluidine were formed. Sulphuric acid,therefore seems to have a tendency to promote the formation of Bmeta-derivative as was noticed (Zoc. cit.) with chlorine-derivatives.L. T. T.Action of Aluminium Chloride on Dirnsthylaniline. By H.GIKAUD (Hull. SOC. Chim. [ 31 1 691-69~3).-81uminium chloride anddimethylaniline combine with developmznt of heat and yield a138 ABSTRACTS OF CHNMICBL PAPFRS.substance which crystallises in long prisms melting at 88" ; no reac-tion however obtains when the original compounds are heated insealed tubes a t 250' for 10 hours.Dimethylaniline when heated with excess of aluminium chloride inpresence of air yields a base which crystallises from alcohol in small,felted needles melting a t 195" and colowed green by oxidising agents ;it is a tetramethylbenzidine N~~ez*C6H,*C68,*NMe2.From dimethylaniline containing dimethyltoluidine by similartreatment a base melting a t 90" coloured blue-violet by oxidisingagents and which appears to be tetraniethyldi~midophenylmethane,is obtained.The author is continuing the research. T. G. N.Condensation of Phenylenediamines with Butaldehydes. ByLASSAR-COHN (Bey. 22 2724-2i%).-A compound CIOHI4N2 isformed when orthophenylenediamine (10.8 grams) is mixed with ayuantity of alcohol insuflicient f o r corriplete solution and then treatedwith isobutaldehyde (7*6 grams) ; the mixture is boiled for a shorttime and the crystalline compound which separates on cooling ispurified by pouring its a.lcoholic solntivn into warm water.It sub-limes in cvlourless needles melts at 233" and is very readily solublein alcohol but almost insoluble in ether. The hydrochloride,CloH,,N,,HC1 crystallises from water and alcohol melts a t 184",has not poisonous properties and forms a golden PZatinochloride,An isomeric compound is obtained in like manner from isobutalde-hyde and metnphenylenediamine ; it melts a t 216" and separatesfrom benzene and chlo~of~nm in crusts. The yZutirLochEoride has thecomposition ( CIOHIINz)~,HZ PtCI6.Isobutaldehyde and paraphenylenediamine yield an oily base theplatinochloride of which has the composition (C,HL4N2),,H,PtC16 butneither the base nor the hydrochloride could be obtained in crystals.Normal butaldehyde does not react with orthophenylenedismint! insolution in absolute alcohol.F. S. K.(Cia H,,N,),,H,PtCI,.Fluorescent Derivatives of Aromatic Metadiamines. By H.SCHIFF and A. VANNI (A7~9mZen 253 319-335; compare Schiff,ArLtraZe,i 140 97 and 159 64) .-Mettttoluylenedinmine combineswit 11 oenanthaldshyde yielding a compound of the compositionC,H6N,(C,HI4),; if the reaction takes place in the cold the alcoholicsolution of t9he product is only slightly fluorescent until after theadditmion of a few drops of hydrochloric acid When metatoluylene-diamiue is warmed for a few hours with a slight excess of oensnth-aldehyde an orange vitreous mass is obtained the alcoholic solutionof which is highly fluorescent.This product consists of a portionreadily soluble in cold ;ilcohol probably methyltetrahydrodibutyl-phenanthroline and a portion which is only sparingly soluble ; theyboth resemble the original product are very stable and are not de-composed by warm hydrochloric acid.A red compound probably dibut8yloctohyclrophenanthroline isformed when cmianthaldehyde is added to a warm alcoliolic solutionof metapheiiy!enediamine hydrocliloride and the solution shows 8ORGAKIC CHEMISTRY. 139green fluorescence ; a thick oil remains on evaporation readily solublein benzene but more sparingly in ether and insoluble in water. Theylutinochloride seems to have the composition ( C&32N2)2,H,PtC16.Acetaldehyde or paraldehpde combines with metaphenylenedia-mine hydrochloride in alcoholic solution forming a red semi-solid com-pound the solutions of which are deep-orange and especially whendilute show a green fluorescence.On adding ammonia to an aqueoussolution of the crude product the free base probably dimethyltetra-hydrophenanthroline is precipitated in the form of a reddish- brown,unstable powder. The p-lntinoclcloride ( C14HlsNz),,&PtC~ is anorange amorphous compound which dissolves sparingly in alcohol,yieldiiig a highly fluorescent solution. When the base is oxidisedwith potassium perrnauganate it jields an acid and this like thebase itself gives considerable quantities of pyridine-derivatives ondistillation.Metaphenylenediamine and metatoluylenediamine hydrochloridesgive analogous compounds (alkyl hydrophenanthroline salts) withother aldehydes of' the fatty series.Sal ;c y 1 olmetap hmylen sd itrmiiAe hydrocldoride,C 6H4 (N :C H.C 6H4' OH) 2 H C1,prepared by treating phenylenediamine hydrochloride with salicylicaldehyde in alcoholic solution is an orange crystalline compound.The free base is a yellow flocculent substance soluble in alcohol andhydrochloric acid ; it4 is decomposed by acids or by prolonged boilingwith water. The plutinochloiide (CzoHls0,N2),B2PtC16 is a cinnabar-red powder.SalicyloZ?netatoZuylenediamine C7H,@:CHC6H4*OM) crystallisesfrom a mixture of alcohol and benzene in long yellow needles and isreadily soluble in ether and benzene but only sparingly in alcohol.It has only feeble basic properties is soluble in moderately concen-trated potash aud is converted into a low-melting acetyl-derivativeby acetic acid.Cuminoliiietatoluylenediamivae C7H6(N:CH*C6H4Pr) is a yellow,crystalline powder melts at about 99" with decomposition and isvery readily soluble in benzene and ether ; it has no basic propertiesand its soiutions do not fluoresce.Ciitnamaldehyde combines with metaphenylenedinmine hydro-chloride i n warm alcoliolic solution yielding an orange unstablepowder most probably tetrahydrodiphenylphenanthroline hydro-chloride.Cinnamaldehyde and metaloluyienediamine hydrochloride,under the same conditions give a red microcrystalhe salt the verydilute solutions of which show a feeble fluorescence; the platino-chlovide is a yellowish-red crystalline powder soluble in alcohol.Cinnamolmt.tntoluylenedinmine C7H6 (N 1CH.C kl :CHPh) is pre-cipitated BS an orange powder when cinnamaldehyde is treatrdwith metatolulenediamine in dilute alcoholic solution ; it melted atabout 380" but could not be obtained in a pure condition. It com-bines with bromine ('2 mols.) yielding a red unstable powder.Amidophenyleneoxamic acid combines with fatty aldehydes inalcoholic hydrochloric acid solution yielding compounds which sho140 ABSTRACTS OF OHEMICAL PAPERS.a slight green fluorescence.When fhe ammonium salt of this acidis treated with a mixture of furfuraldehyde and aniline hydrochloride,a red dye is formed.Para phen y 1en ediamine and or t ho tc 11 u ylened i amine do not givefluorescent condensation-products with aldehydes of the fatty series.F. S.K.Azotoluenes and Azoxytoluenes. By J. V. JANOVSKY (Monatsh.,10 535-601 ; compare Abstr. this vol. p. 392 and 865). Mononitro-parazotoluene is best obtained by heating a t 30" a mixture of azotol-uene with one-fifth of its weight of nitric acid of sp. gr. 1-43. It maybe recrystallised from alcohol melts at 80" and has the formula-3 1 4 1NO,*CsH,Me*N,*CsH,Me,since on reduction with tin and hydrochloric acid it yields a mixtureof paratoluidine and P-toluylendiamine [Me (NH,) = 1 3 41 melt-ing a t 88".If in the above mentioned operation the temperature is allowe6 torise above 30" or if it stronger acid is used dinitroamtoluene[Me (NO,) N = 1,l 3,3 4,4] melting at 114" is formed.On re-duct>ion with alcoholic stannous chloride this yields P-toluylendi-amine and must consequently be regarded as the symmetrical com-pound Tha two trinitroszotoluenes previously described (Zoc. cit.)which melt a t 1:B" and 139" respectively are both converted onreduction into 6-toluylendiamine and the sa,me triarnidotoluene[Me (NH,) = 1 2 3 41 the hydrochloride of which crystallises inscales which become coloured on exposure to the air; they must con-sequently be regarded as physical isomerides having respectively theformulE-G. T. M.Amidoximes and Azoximes. By F. TIEMBNN (Ber. 22 294%-2946).-This paper gives a sliort r4sume' of the work previously doneon the subject of diamidoximes and diazoximes by the author and hiscollaborators.The oxaleneamidoximes snccineneamidoximes glutnreneamid-oximes isoplitlialeneamidoximes and hometerep h thalet~eamidoximesare soluble in boiling water and alcohol very sparingly so in ether.Their aqueous solutions show very strongly the characteristic arliid-oxime reactions.The hydrochlorides of the diamidoximes coil tain'L mols. of hydrogen chloride and are highly crystalline but easily losea part of the hydrogen chloride. The replacement of the two hydro-gens of the twc; oximide-groups takes place in a normal way buthitherto all attempts to displace only one of these atoms have provedunavailing. The acid derivatives of the diamidoximes,NO( COR) :C (NH,)*R"*C(NH) :NO*COR,pass less easily into the azoximes than the corresponding derivativeORGAN [C CHEJIISI'RY.141of monamidoximes. The diazoximes so formed have the generalformula <CR:N>C*R'"C<N.CR>. The diamidoximes of such 0 -N N - 0dicarboxylic acids as easily forin irnides decompose very readily intoimido-dioximes of the f o r m u l ethiis forming compounds with 5- and 6-atom closed rings whichare soluble in water are sometimes basic sometimes acid in character,and usually yield stable silver-derivatives.When hydroxylamine (1 niol.) acts on such dinitriles as yieldimidodioximes ( 1 mol.) basic derivatives are formed isomeric withcyano-amidoximes. The constitution of these compounds is not yetfu Ily provcd but as an example that obtained from orthocyanobenzylcyanide is probably represented h-j the formula-L. T.T.Formation of Benzaldoxime. By B. LACHOWICZ (Bey. 22,2H87 -2888) .-Benzaldoxime is best prepared by triturating hydro-berizamide (1 mol.) with hydroxylamine hydrochloride ; the reactionis at an end in 10 to 1.5 minutes and on adding water the benzald-oxime is precipitated as an oil.Amidoximes and Azoximes. By F. TIEMANN (Bey. 22 2758-276l).-The author makes a few general remarks on the papers ofBiedermann (this vol. p. 175) Spilkcr (next abstract) and Miller(this vol. p. 144).Nitrogen-derivatives of Salicylic Acid. By A. SPILRER (Beg..,22 2767-2790).-Salicylamide is best prepared by heating ethylsalicylate a t 100" w i t h concentrated ammonia; it melts at 138".Dibi.omosaZ;cyZamide OH.C6H,Br,*CONH prepared by treating awarm concentrated aqueous solution of the amide with excess ofbromine-water crystallises from dilute alcohol in colourless needles,mdts at 183" with decomposition and is readily soluble in alcohol,ether and alkalis more sparingly in benzene and chloroform.I naqueous alcoholic solutions ferric chloride produces a reddish-violetcoloration.Salicy Zothiamide OH.CsH4-C SNH2 is obtained together with severalother compounds when the amide is melted with phosphorous penta-sulphide. It cr~stallises from hot water in colourless needles melts at117-118" and is readily soluble in alcohol ether chloroform benzene,bof water and alkalis. It is slowly converted into the amide whenboiled with water or alkalis.Ferric chloride in dilute aqueous solu-tions produces a violet coloration and a brownish- black precipitate isformed on heating. Lead acetate copper sulphate and silver nitratealso produce precipitates in the cold or on warming ; these compoundsdarken in colour wit,h separation of the metal.Salicylonitrile OH.C,H,.CN is best prepared by distilling theF. S. K.F. S. I(142 ABSTRACTS OF CHEMfCAL PAPERS.thiamide under reduced pressure ; it crystallises in colourlees needles,melts at 98" boils a t 195" (I80 mm.) and is readily soluble in alcohol,ether benzene and chloroform but only spayingly in cold water.With ferric chloride aqueous solutions give a violet coloration and withbromine-water a colourless crystallirle precipikate.The compound(m. p. 195") obtained by Grimaux (Bull. SOC. Chirn. 13 26) by heat-ing salicylamide with phosphoric anhydride and also by Ahrens(Ahstr. 1588 266) from orthamidophenol by Sandmeyer's reaction,is not salicylonitrile although the latter can be obtained by both theseme tlh od s .Dihromosali~~yZt~iamids OH*C6H2Brz*CS-NH2 is obtained when thethiamide is treated with excess of bromine i n dilute alcoholic solution ;if a solution containing salicylthinmide and salicylamide is gradnallytreated with bromine-water monobmmosalicyl thiamide is precipitatedfirst the nmide remaining in solution. Dibromosalicylthinmidecrystallises from alcohol in dark-violet microscopic needles melts at,about 230" with previous softening and is moderahely easily solublein alcohol ether benzene and chloroform.yielding violet solutions,but is insoluble in water ; it dissolves unchanged in alkalis forming adark-violet solution. In alcoholic solutions silver nitrate coppersulphate and lead acetate produce dark-red precipitates.Xalicenylamidoxime OH*C,H,*C (NH?):NOH prepared by boilingtlie thiamide with hydroxylamine hydrochloride alrd sodium carbonatein dilute alcoholic solubion crystallises from water and benzene in thick,colourless needles melts a t 98-99" and is readily soluble in alcohol,ether chloroform acids and alkalis ; in aqueous solutions ferricchloride p~*odrtces an intense violet coloration Fehling's solution andcopper sulphate a greenish precipitate and silver nitrate on warming,a metallic mirror.The hydrochloride C7H6NzOz,HC1 melts at 175"and is very madily soluble in water. The platiizochloride,forms small ill-defined crystals and is readily soluble in water andalcohol. The sodiwm-derivative C7H6N2O2Na3 is precipitated as Rcolourless hygroscopic powder when the amidoxime is treated withsodium ethmide in alcoholic solution and a large volume of ether thenadded. The compound C7H7N202Na is obtained in like manner whensodium ethoxide (1 mol.) is employed i t is a colourless crystal-linesubstance and is very hygroscopic. The copper-compound has thecomposition CI4HI4N4OJC~.preparedfrom dibromosalicenylthiamide in like manner crystallises fromdilute alcohol in colourless plates melts a t 180" and is readilysoluble in alcohol ether acids and alkalis but more sparingly inchloroform benzene and light petroleum and very sparingly inwater.In alcoholic solutions copper sulphate produces a gi-eenishprecipitate ferric chloride a reddish-violet coloration ; alkalinesolntions reduce silver nitrate and give a green precipitate withFc hl in g ' s s ol u ti o n . The c y ~ p er - derivative ( C H ,N 0 B r 2) C u i ssparingly soluble in watei. an0 alcohol.Snlicenylamidozimesul~hunic acid So3H*C6H3( OH)-C(NH,) :NOH isDih-0 mosa lice n y lam id oxhe 0 H*C6H?B rz*C (NIX2) :NOHORQANlC CHEMISTRY. 143obtained when the aniidoxime is heated with concentrated sulplturicacid a t ahnut 150"; it separates from boiling water iii colourlesclcrystals does not melt below 250" and is insoluble in alcohol ether,chloroform and benzene and only very sparingly soluble in coldwater.The salts of the alkalis and alkdine earths are readilysoluble in water. The barium salt (C7H7N2S05)2Ba separates fromhot water in colourless ill-defined cr~stnls.B c n z n y lsa7'icea y lamidoaime OH*C6H,*C (NH,) KOBz crydallisesfrom dilute alcohol in needles melts a t 173" and is readily soluble inether alcohol chloroform and benzene sparingly in alkalis andinsoluble in water and acids. J t gives a reddish-violet colorationwith ferric chloride and a precipitate with bromine-water. Theacetyl-derivative OH*C,H,~C(NH2):NOAc crystallises from warmwater in colourless plates melts a t 117" and is reRdily soluble inalcohol ether alkalis and acids but only sparingly in chloroform,benzene and water ; in dilute alcoholic solutions ferric chlorideproduces a reddish-viol& coloration and bromine-water a colourlessprecipitate,rralicen~lbenzen~taxox~~e OH*CsH4*C<- N>CPh prepared byboiling the benzoyl-derivative for a long time with water or heatingit alone a t 180".separates hom hot dilute alcohol in crystals melts at128" and i s readily soluble in alcohol ether chloroform and benzene,but insoluble in water. I n dilute alcohol~c solutions copper sulphateproduces a green bromine-water a colourless precipitate and ferricchloride a violet coloration which quickly disappears. The eth,enyZ-azozime C9H,N,O2 prepared by heating the acctyl-derivative a t 125"or by boiling i t with water or acetic anhydride crystallises fromdilute alcohol in colourless needles melts at 77" and is readilysoluble in alcohol ether chloroform benzene and alkalis but onlysparingly in water.It gives the usual reactions with ferric chloride,copper sulphate and bromine-water.Dibenzoy ZsaZiceny lamidoxime OBz*C,H,*C( NH,) :NORz i 8 obtained,together with d h y l benzoate when the amidoxime is treated withbenzoic chloride and sodium ethoxide in alcoholic. ethereal solution,It separates from dilute alcohol in coIourless ill-defined crystalfi,melts at 127" and is readily soluble in alcohol ether benzene andchloroform but insoluble in water and acids ; i t gii-es H colourlessprecipitate mith bromine-water and i t is decomposed by alkalis.N - 0 The corresponding azoxime OBz*C,HI*C<-N>CPh can be pre-pared by boiling the dibenzoyl-derivative with water or by heating itabove 150" ; also by treating salicenylbenzenylazoxime with benzoicchloride and sodium ethoxide in alcoholic solution.It crystfilliscsfrom alcohol in colourless needles melts at 120". and is readilysoluble in benzene ether and chloroform but insoluble in watc.1. andacids; it is decomposed by warm alkalis and it gives a colourlessprecipitate with bromine-water.DiacrtylsaZicenyZamidoxirme OAc*C,H,.C(NH,):NOAc is formed,together with the corresponding azoxime when the amidoxime istreated with sodium ethoxide and acetic chloride in ice-cold etherealN144 ABSTRACTS OF CHEMICAL PAPERS.solution but it cannot be obtained in a pure state.The azoxime,C,,H,,,N,O is best prepared by treating sodosalicenylethenylazoximewith acetic chloride in alcoholic ethereal solution. It crystallisesfrom dilute alcohol in colourless needles melts at 74' and is veryreadily soluble in alcohol ether chloroform and light petroleum butonly sparingly in water; i t gives a colourless precipitate withbromine-water and it is quickly decomposed by alkalis.Sa licen y Zet hy lamidoxime OH* C6H,* C (NH,) :NO E t is formed,together with its ethyl-derivative when the amidoxime is heated withsodinm ethoxide and ethyl iodide in alcoholic solution. I t is a colourlessoil boils at 278" (at 220' under 150 mm.) and is readily soluble inacids and alkalis but insoluble in waher.and only sparingly soluble inlight petroleum. In dilute alcoholic solutions ferric chloride pro-duces a violet coloration and bromine-water a colourless precipitate.The ethylderivative OEt*C,jH*-C(NH,):NOEt is a colourless oil,boils a t 195" (180 miu.) and is readily soluble in acids but insolublein water and alkalis.SaZiceny7etl~yZamidozime chZoride OH.C6H4*CC1:NOEt prepared bywarming the preceding compound with sodium nitrite in dilutehydfochloric acid solution is a colourless oil boils at 233-234" (at178 under about 'LO mm.),and is readily soluble in alkalis but insolublein water and dilute acids ; it gives a reddish-violet coloration withferric chloride and a colourless precipitate with bromiiie-water.Salicenylphenyluramidoxime OH*CsH,.C (NOH)*NH*CO.KHPh pre-pared by triturating tlie arnidoxime with phenylcarbimide crystal-lises from dilute alcohol in colourless plates melts at 119" with de-composition when heated quickly and is readily solnble in alcohol,ether and alkalis moderately easily in benzene chloroform andacids and insoluble in water ; it gives the usual reactions with ferricchloride and bromine-water.Salicenylethylamidoxime and its ethyl-derivative combine withphenylthiocarbimide yielding compounds which are insoluble inwater and do not crystallise well.Salicenylamidoxime combinesenergetically with phenylthiocarbimide forming the thiouramidoximeand diphenylthiocarbamide.SaZicen~lu~amidoxime OH.CGH4.C (NOH) -NH*CONH2 crystallisesfrom dilute alcohol in colourless plates melts at 148" with decomposi-tion and is readily soluble in alcohol benzene acids and alkalis,moderately easily in ctiloroform and ether and sparingly in water ; itgives a reddish-violet or reddish- brown coloration with ferric chloride.F.S. K.Anisenyl-. Salicenyl- and Methylsalicenyl-amidoxime. RyJ. A. MILrAEii (Be,.. 22 2790-2801).-Anisaldoxime melts at 64" ;Westenberger (Abstr. 1884 581) gives 45' as the melting point ofthis compound. AniRonitrile melts at 61-62' ; Henry (Ber. 2 6 6 i )found tlie melting point to be 56-57'.Aiaisenylamidoxi?ne OMe*CsH4*C( N H,):NOH is prepared by heat-ing anisonitrile for 6-8 hours at about 90' with hydroxylaminehydrochL )ride and sodium carbonate i n dilute alcoholic s o h tion ; theyield is 81 per cent.of the theoretical quantity. It crystallises froORG.QNIC CHEMISTRY. 145benzene in scales and from hot water in needles melts at 122-123",and is readily soluble in alcohol ether chloroform acids and alkalis,sparingly in hot benzene and hot water and almost insoluble in lightpetroleum. The hydrochzoride C8H,oN202,HCI is crystalline melts at168" with decomposition and is soluble in alcohol but insoluble inether. The ethyl-derivative Cl,oHIIN20? crystalliscs from dilutealcohol in prisms melts a t 51-52" and is readily soluble in alcohol,ether benzene and chloroform but insoluble i n light petroleum.The acetyl-derivative. CI0Hl2N2O3 crystallises from dilute alcohol inprisms melts at 106" and is readily soluble in alcohol and chloroform but.only sparingly i n benzene and ether. The nzoxime,O&fe*C6HI*cN>CMe N-0 prepared by heating the acetyl-derivativealone or with water or with acetic anhydride crystnllises in colour-less needles melts a t 68" and is readily soluble in alcohol ether,benzene and chloroform but more sparingly in light petroleum.OMe.C6H4*C<NH > CHMe is ob-tained by dissolving the amidoxime in aqueous acetaldehyde ; it crys-tallises from alcohol in colourless needles melts a t l27*So and i areadily soluble in alcohol ether benzene and cliloroform but onlysparingly in light petroleum.Ethyl anisenyZainidoximecarbo.~ylate OMe*CGH4*C (NH,) :NO.COOEf,,prepared by treating the amidoxime with ethyl chlorocarbonate incold chloroform solution crystallises from dilute alcohol in colourlessplates melts at 119-120" and is readily soluble in alcohol but moresparingly in ether and benzene.Aniseny lcarbonylamidoxime OMe*C6H4gC<~r-r > CO crystallisesfrom dilute alcohol in colourless scales melts a t 208" and is readilysoluble in alcohol ether and chloroform but only sparingly inbenzene and light petroleum.BenzoylaiLisen?/la?nic2oxi~e C,5H,4N203 separates from dilutealcohol in crystals melts at 148' and is readily soluble in alcohol,ether chloroform and benzene but insoluble in light petroleum.Anisenylbenzsnylazoxime OMe-C6H4*C<KH>CPh No0 prepared byheating the preceding cornpourid alone or with water or by dissolv-ing i t in concentrated sulphuric acid crystallises in colourless plates,melts a t 1025 and is readily soluble in alcohol ether chlorofoym,and benzene.No0 Etkylideneaniseny Z a m i ~ ~ i m e ,Y.0Aniseqlpropenylazoxime-w-carboryc acid,is obtained when the amidoxime is melted with succinic anhydride ;i t crystallises from dilute alcohol in yellowish needles melts a t140-1141" and is readily soluble in alcohol ether and chloroform,but only moderately in benzene and very sparingly in l i g h t petro-leum.Salicylonitrile (compare Spilker preceding abstract) can be pre-VOL. LVlLT.I46 ABSTRACTS OF CHEMICAL PAPERS.pared by decomposing acetylsalicylonitrile (compare Lach Abstr.,1884 1134) with alcohol.A polymeride of salicylonitrile is formed in considerable quantitieswhen salicylaldoxirne is heated with acetic anhydride.This com-pound crystallises from boiling nitrobenzene in pale yellow needles,melts at 296-5399" and is sparingly soluble in boiling chloroform,benzene and ether. When melted with potash it is decomposed intosalicylic acid and ammonia and when heated at 200" with concen-trated salphuric acid it is decomposed into phenol ammonia and car-bonic anhydride.Ethyl salic~?~ylamid~ximecnrboxylate CloH12N20 crys tallises fromdilute alcohol in colourless needles melting at 96".Salicenylpropenylazoxime-w-carboxylic acid,OH*CeH4*C<:&-C *c,H** CO OH,separates from a mixture of benzene and light petroleum in small,well-defined crystals melts at 116-117" and is readily soluble inalcohol ether and chloroform but more sparingly in benzene.Methylsalicylonitrile prepared by treating salicylonitrile withsodium ethoxide and methyl iodide boils a t 255-256" and is volat,ilewith steam; Ahrens (Abstr.1888 266) gives 265-5366" as theboiling point of this conipound.MethylsalicenyZamidoxz??ze OMe.C,H,*C(NH,):NOH prepared bydigesting the nitrile with hydroxylamine for a long time crystallisesfrom benzene in needles melts a t 123" and is readily soluble inalcohol ether chloroform and hot water but insoluble in lightpetroleum.Methylsalicenylbenzenylazoxime OMe.C6HI'C<-N>CPh7 N-0 melts a t117" and is readily soluble in chloroform alcohol ether and benzene,but insoluble in light petroleum. P. S . I(.Action of Hydroxylamine on Orthocyanobenzyl Cyanide.By G. EICHELBAUM (Ber.22 2973-2975).-H0mo-orthophthalene-alszidinaidolrime C6H,< CH,.C'NHz)>N(?)7 C(NH)-0 is most readily obtainedby keeping an alcoholic solution of orthocyanobenzyl cyanide (1 mol.)and hydroxylamine (rather more than 1 mol.) for several days in aphce protected from direct sun-light; it is then filtered from thecrystals which separate arid evaporated down. It crystallises fromwater in long needles (with 2 mols. H20) melting at 95"; theanhydrous substance melts at 158" is very readily soluble in alcohol,insoluble in ether chloroform and benzene &c. It has the samepercentage composition as orthocyanophenylethenylamidoxime butcannot be an amidoxime as it has only basic properties and thusresembles the compound obtained by Beidermnnn from trimethylenedicyanide and hydroxylamine (hhis vol.p. 1536j. The hydrochloride,C9HSN30,HCl crystsllises in small lustrous yellow cryshls issparingly soluble in water almost insoluble in alcohol. The picrate,CgHgN,0,CsH,N30 forms reddish-yellow needles rather more readilORGIANIC CEEMISTRT. 1 4 isolnble in alcohol than i n water and explodes slightly when t,he drysubstance is heated. When the base is dissolved in dilute hydro-chloric acid and treated with sodium nitrite homo-orthophthalicacid is formed. N. H. M.Isophthalenediamidoxime. By G. GOLDBERG (Be,.. 22,2976-2977) .-Metadicyanobenzene is prepared by dist.illing an inti matemixture (15 to 20 gi-ams) of potassium benzeiiemctadisulphonatowith pure potassium cyanide under diminished presswe. It is firstresublimed and then crystallised from alcohol from which i tseparates in slender needles melting at 1.58-159".Isoyhthalenediamidoxime C,H,[C(NH,):N-OHJ r= 1 31 is formedwhen metadicyanobenzene (I niol.) dissolved in benzene is digestedwith hydroxylamine (rather more then 2 mols.) in clmed flasks at 90".It crystallises from alcohol in colourless prisms melta a t 193" withdecomposition dissolves readily in hot water and alcohol sparinglyiu ekher and shows the characteristic properties of the amidosime?.The crystals contain water of crystallisation (probably 8 mol.) whichthey lose when exposed to air.HomoterephthalenediaidoHime.and its Derivatives. ByE. ROSENTHAL ( B e y . 22 2977-29844 .-Hornoterep hthalened inn? itl-oxime OH*N:C(NH2)*C,H4-CR2C(NH,)N*OH [ = 4 I] prepared bykeeping a mixture of liydroxylhmine hydrochloride (3 mols.) withthe necessary amount of sodium carbonate and paracyanohenzylcyanide dissolved in alcohol for some days in a closed flask crystal-lises from hot water in microscopic prisms melts a t 192" with decom-position is rather readily solubble in methyl alcohol and acetone verysparingly i n ethyl and amyl alcohols and is insoluble in ether,beiizene and light petroleum.It shows all the characteristicreactions of the amidoxinies. The h?ydrochZo?ide C9H,N,0,,2HCI,dissolves very readily in water but is not hygroscopic and is alsosoluble in alcohol and glacial acetic acid. The diacety I-derirative,Cl3HI6N4o4 crystallises in groups of needles melts a t 161*5-16f issoluble in hot water alcohol ether and benzene and in acids butnot in alcohol; when boiled with water for some hours i t isquantitatively converted in to ? i o m o t e r ~ h t ~ n E e l ~ e d i a z o x i ~ e ~ ~ e t h e n ! i l ,c M e ~ N - ~ C * C 6 H .C H 2 . C ~ - ~ ~ c M e . The latter melts a t 11 l*:ao,is soluble in hot water methyl ethyl and xmyl alcohols ether aiidbenzene &c. and is insoluble in mineral acids. The dibenzoyl-co?l7-pound C23H20Nb0A crystallises from hot methyl alcohol melts at 184",dissolves in acetone ethyl acetate amyl alcohol and in acids verysparingly in ethyl alcohol and is insoluble i n water benzene aridether. When heated at 150" for four hours it is converted intohornoterephfhalenediuzoxirne dibenzeny 1 C,,H,,N,O,. This forms long,white matted needles melts a t 179*5' and is soluble in alcohol ether,chloroform and.benzene.CN.C6H4* C H2-C (NH,) :N* 0 H,prepared by the action of hydroxylamine (1 mol.) on paracyano-benzyl cyanide (1 mol.) melts at 168". It is converted by nitrousThe h y d n d i l o r i d e is crystalline.N. J3. M.N0.N N.0Paracyanophenylet hen9 Zamidozim e,I:148 ABSTRACTS OF CHEMICAL PAPERS.acid into paracyanophenylacetamide (M. p. 19G" Melliuglioff Inaug.Diss. B e r l i n 1889). The benzoyl-derivative,CIV*C,H,.CH,.C(NH,):N*OBZ,forms small white needles melts at 171*5-172" dissolves in met.hjland ethyl alcohols and glacial acetic acid less readily in benzene andcliloroform ; it is also dissolred by acids.When heated with waterfor six hours it is converted iiito ~aracyanol?heiiylethen ylazoxiiire-bcwzenyl CN*C6H1.CH,*C~-N~CPh which melts a t 105" and issoluble in alcohol ether benzene and chloroform.N-0N. H. M.Hydrazines. By M. FREUND (Ber. 22 2727).-The authorreplies to the statements of Willgerodt (this voL p. 40).Orthonitrophenylhydrazine. By A. BISCHL~R (Rer. 22,2801- 2809 ; compare Abstr. 1889 501) .-Orttionitrophenylhydr-azine N02*C,H4*NzH3 is best prepared by dissolving orthonitraniline(1 0 grams) in warm concentrated hydrochloric acid (100 grams j,adding to the well cooled solution an aqueous solution (35 grams) ofsodium nitrite ( 5 grams) and keeping the mixture at the ordinarytempera ure with frequent stirring until the crystals of thenitraniline hydroohloride have disappeared ; a solution of stannouschloride (32 grams) in Concentrated hydrochloric acid (32 grams) isthen gradually added care beii~g taken that the temperature does notrise much above 0" and the stannochloride which separates from thefiolution is rec~ystallised from hot water.The hydi-ochloride,CGHiN3Or,HC1 obtained by decomposing the stannochloride withhydrogen sulphide crystallises in small yellow plates or in long,alender needles is readily soluble in warm alcohol and warm water,but only sparingly in the cold soheuts and is insoluble in ether,benzene and concentrated hydrochloric acid ; it reduces Fehling'ssolution in hhe cold but ammoniacal silver nitrate solution only onwarming.The yield of this salt is aboct 75 per cent. of tlietheordical quantity. The free base is obtained by treating a hotaqueous solution of the hydrochloride with sodium acetate ; itcrystallises from benzene in long cinnabar-red needles melt's at go",and is readily soluble in warm alcohol benzene and hot water butonly sparingly in ether and light petroleum. The sulphate,(C,HiN,O,),,H2SQ~ crystallises in small pinkish needles and isreadily soluble in h4ot alcohol warm water and dilute sulphuric acid,but insoluble in ether and benzene.Benz y l i ~ i i e o r t h o n i t r o ~ h e n y 2hy d rnzine NOz* C6H4*NH-N CH Ph sepa-rates as a reddish-brown precipitate when benzaldehyde is added toan alcoholic solution of the hydrazine ; it crystallises from boilingbenzene in dark-red plates melts at 186-187" and is moderatelyeasily soluble in hot benzene but very sparingly in hot alcohol andether.and insoluble in water. The formyl-derivative,separates in long pale yellow needles when the hydrochloride iORQANIC CHEMISTRY. 149heated at 100" with sodium formate a D d formic acid for about anhour; it crystallises from alcohol melts a t 177" and is readil solublein hot water and boiling alcohol but only sparingly in ether andbenzene. Solutions of the formyl- acetyl- arid benzoyl-derivativesgive a red or bluish-violet coloration with alkalis. The ucetjyZ-dei*iv I -tive N02*C6H4*NH.NHAc prepared by heating t be hydrochloride ofthe hydraxine with sodium acetate and glacial acetic acid crystallisesfrom alcohol in lemon-yellow needles melts at 140-141" and isreadily soluble in hot benzene alcohol and water.The diacdyl-derivative NO2*C6H4*NAc*NHAc prepared by heating the hydro-chloride with sodium acetate and ace& anhydride crystallises fromdilute alcohol in reddish prisms melts a t 57-58" and is readilysoluble in hot water benzene alcohol and cold glacial scetic acid,but only sparingly in hot ether. The benzoyl-derivative,N02*CsH4*NH-NHBztcrystallises from alcohol in pale-yellow needles melts at 166" and isreadily soluble in ether benzene and hot alcohol but insoluble inwater. The opal$-derivative C202( N2H2*C6H4-NO2) prepared byheating the hydrazine with ethyl oxalate crystallises from hot anilineand nitrobenzene in small Fellow needles and is only sparinglysoluble in most ordinary solvents.a-Phen&inzime C6H4<r's H is obtained together with dihydro-phenotriazine and ortho p heny lenediamine when orthoni trophenyl-hydrazine is reduced with sodium amalgam in dilute acetic acidsolution care being taken that the temperature does not rise muchabove 30".The solution is decanted from the mercury evaporated ata moderate temperatnie the residue dissolved in water and mixedwith excess of soda ; it is then treated with potassium ferricjauidein the cold until the violet colour changes tu yellowish-red mixedwith a large volume st' concentrated soda and extracted three orfour times with ether. When the crude product is fractionated it) isseparated into a portion boiling at 235-245" and a portion boilingabove 360" which consists of phenylethenylamidine.Phenotriazine crysta llises from bt nzene in deep-yellow needles meltsat 65-66" boils at 235-240" and is volatile with steam.It isreadily soluble in alcohol benzene warm ether and warm water butit separates from the aqueous solution on adding concentrated alkalis ;it has a peculiar alkaloid-like odour and is a feeble base the saltsbeing readily soluble in water and alcohol.a-Phenomethyltl-iazine C6H4<T'CMe is formed together with the N.Ndihydro-derivative acetamide. acetamidophenyl hydrazine and phen yl-enediamine when acet~lnitrophenylhydrazine is reduced with sodiumamalgam in acetic acid solution ; the solution is filtered from smallquantities of acetylamidophenyl hydrazine and the triazine is isolateda s described above.It melts at 88-90" boils at 250-2.55" withslight decomposition is readily soluble in alcohol ether and benzene,and moderately easily in cold water but only sparingly in lightN.150 ABSTRACTS OF CHEMICAL PAPERS.petroleum ; its alkaliae solutions oxidise quickly on exposure to theair.Orthucefylamido~l~ereylhy~razine NH,-C,H,*NH*NHA c (see above),crjStullises from benzene in colourless needles and melts a t 162".Metmitrophenylhydrazine and Parabromorthonitrophenyl-hydrazine. By A. B~SCHLER and S. BRODSKY (Ber. 22,2809-2818).-~eta?aitrophenylhydrazine l~ydrochloride N02.C6H,.N2H3,HC1 isprepared from metanitraniline exactly as described in the case of thecorresponding ortho-compound (compare preceding abstract).Theyield is 50-60 per cent. of the theoretical. It mystallises in yel-lowish plates and is readily solwble in warm alcohol and water butotily sparingly in warm concentrated hydroct~loric acid ; i t reducesFehling's solution in lthe cold and ammoniacai silver nitrate andplatinic chloride on warming. The free base N02*C6H4*N2H3 crystal-lises from alcohol in slender yellow needles melts a t 93" and isreadily soluble in glacial acetic acid chloroform warm benzene andalcohol but only sparingly in boiling water. The sulphate,( C,H,N,02),,H2S04 separates from hot water in yellow crystals andis readily soluble in hot water and glacial acetic acid but o d y spar-iiigly in boiling alcohol and insoluble in ether and benzene. Theacetyl-derivative N02*CJ€,.NH*NHAc crystallises in golden plates,melts a t 145" and is readily soluble in alcohol ether glacial aceticacid and boiling water but only moderately easily in benzene.Thediacetyl-derivative N02*C6H,*NAc*NHAc forms brownish plates me1 t sat 150" and is readily soluble in the ordinary solvenks. The bentoyl-derivative N02-C6HI.NH*NHBz crystallises from dilute alcohol inyellow prismatic needles melts a t 151" and is readily soluble inalcohol ether glacial acetic acid and hot benzene b u t iiisoluble inwater. The dibenzo y I- deriuat ive NO,*C&I,-NBz*N HBz c r j s t a1 lisesfrom acetic acid in yellow plates melts at 153" and is readily solublein hot alcohol and benzene but insoluble in water.Is 0 2*C,H4.N B z*N H Ac,prepared by heating the acetyl-derivative with beneoic anhydride at160" separates from eumene in crystalline aggregates melts a t 13i0,and is readily soluble in doohol and glacial acetic acid but insolublein benzene.a-Benzoyl-~-aoetyl.naetanitro~~tenylhydrazine NOz-C6Hd*NAc*NHBz,obtained by heating the benaoyl-derivative with acetic anhydride audsodium acetate separates frtom cumene in yellowish crystalline aggre-gates melts a t 147" and sublimes a t 100" in small iridescent needles ;it is readily soluble in boiling benzene alcohol and glacial acetic acid,and more readily in hot mmene than the preceding compound.E thy liden e m etanitropheny lhyd?*azim N02.C6H,*NH*N CHMe pre-pared by warming the hydrazine with acetaldehyde separates fromalcohol in yellow crystals melts at 98" and is readily soluble inalcohol benzene and ether but only sparingly in hot water.Renzylidene,,~etanitroyhenylhyd?.azi,2e NO,*C,H,*NH*N:CHPh crjs-tallises from boiling alcoliol in small carmine-red needles melts a t117-118" and is sparingly soluble in hot alcohol but readily in ether,hot glacial acetic acid and benzene.F.S. K.a- Acet y 1 - /3- b enzo y lwet aiiitrop heny Zhy d m z i n eORGANIC CHEMISTRY. 151AcetonenitrophenyEhydrazine No2*C6H,*NH*N:CMe2 crystaliisesfrom dilute alcohol in dark-red needles melts at 112" and is readilysoliible in warm alcohol ether benzene and glacial acetic acid butonly sparingly in hot water.Acetophenone.rLitrophmylhydrnzine NO2*C6H4.NH*N:CMePh crystal-lises from benzene melts at 160" and is only sparingly soluble in hotalcohol but more readily in benzene arid ether.BeiizilmetarLitrophenyLhydrazine crystullises from benzene in small,orange-yellow needles melts at 158" and is readily soluble in warmbenzeile but only sparingly in hot alcohol and ether.Metanitrop hen y lizinedih y d roxy tartaric acid se pttrates in crystalswhen sodium dihydroxytartrate (1 rnol.) is treated with hydrochloricacid ( 1 mol.) and nitrophenylhydrazine hydrochloride in aqueonssolution ; it melts a t 175" with decomposition. MetanitrodiphenyZ-izinedihydroxytartaric acid p.repared in like manner but employing2 mols.of the hjdrazine is a yellow micro-crystalline powder,melting at about 200".The l a 4 two compounds are only sparinglysoluble in hot water alcohol benzene and glacial acetic acid.The coin pound N O,.C,H,.N H*N:CMe* CHI,-CO OE t is formed whenthe hydrazine is treated with ethyl acetoacetate in alcoholic solution ;it crystallises from dilute alcohol in yellowish-red plates melts a t 117",and is sparingly soluble in hot water but readily in other warmsol vents.NOz-CeH4*N H*NH C S*NHP h,prepared by warming the hydrazine (1 mol. j with phenylthiocarb-imide (1 mol.) in alcoholic solution is a dark-yellow crystallinecompound melts a t 146-147" and is readily soluble in hot alcohol,but only sparingly in benzene and glacial acetic acid.Uiacety luniidoyhenyllzydruzine B HAc.CcH4.NH.NHAc is obtainedwhen acetylnitrophenylhydrazine is reduced with sodium amalgam inacid alcoholic solution and the crude product boiled with glacialacetic acid; it crystallises from acetic acid in small dark-yellowneedles melting a t 1.50-151".Metanitrod iphny lt hiosemicarbazide,Attempts to prepare par;tnitrophenylhydrazine were unsuccessful.Purabrot~rortl~onitro~henyllz~drazi~~e N020G6H3Br-N2H3 prepared bythe method described in the case of orthonitrophenylhydrazine (com-pare preceding abstract) separates from benzene in dark-red crystals,melts a t 130" and is readily soluble in alcohol ether hot glacialacetic acid and benzene but only spariugly in hot water ; it reducessilver arid platinum salts.The hydrochluride C6H6BrN3O2,H CL crys-tall ises from water in small jellowish-red needles.The sulphate,( C6H6B~-N302)2,H?S04 is a reddish microcrystalline powder sparinglysoluble in cold alcohol and benzene but readily in hot alcohol water,and glacial acetic acid.NOz:C6H313r*NH*N Ha CHO,crystallises from alcohol in slender pale yellow needles melts a t191" and is readily soluble in hot alcohol and benzeue. The acety2-derivative N 02*C6H3Hr*NH*NHAc crystallises from glacial aceticacid in small lemon-yellow needles and is readily soluble in hotbeuzene glacial acetic acid and alcohol but only sparingly iu theThe formyl-derivative152 ABSTRACTS OF CHEMICAL PAPERS.cold solvents. The benzoyl-derivative N02.C6H3Br*NH*NHBz crys-tallises from alcohol in large yellow plates melts at 185" and isreadily solnble in hot alcohol ether and benzene but only sparinglyin the cold solvents.The beiLx?/Zidene-derivnt.ive,NOz*CGH3Br.NH.N CHPh,crystallises from alcohol in red needles melting at 207". The aceto-phenoige-derivative N0,*C,H3Br.NH-N:CMePh crystallises in redneedles and melts at 148".Parabrmnorthonitrod ipheny lthiosemicarbazide,NO2*C,H3Br*NH*NH*C S*NHPh,is a yellow microcrystalline compound melts a t about 160-164" andis readily soluble in hot alcohol and glacial acetic acid but onlysparingly in ether and benzene.Parabrom-a-phenotriazine C,H,Br<y'G H is formed when forrnyl-parabromortbonitrophenylhydrazine is reduced with sodium amalgamand glacial acetic acid in well-cooled alcoholic solution ; the solutionis evaporated the residue dissolved in water treated with potaosiumferricganide and the filtered solution mixed with excess of alkali.It crystallises from boiling water in slender yellow needles and isreadily soluble in hot water and other ordinary Solvents but insolnblein alkalis.N*NNaCMeN*N Parabrom-a-phenomethy ltriazine CsH3Br< I I I prepared fromthe acetyl-derivative of the hydrazine in like manner crystallises fromwater in golden plates melts a t 115" and is readily soluble in ether,benzene alcohol and glacial acetic acid but only sparingly in coldwater.F. S. K.Formation of Phenylhydraxides. By E. FISCHER and F. PASS-MORE (Ber. 22 2728-2736).-The hydroxy-acids of the sugar-group combine very readily with phenylhy drazine in aqueous solu-tion yielding crystalline hydrazides which are only sparingly solublein cold water can be easily purified and are readily reconverted intothe acid when boiled with baryta.The hgdrazides are prepared bytreating a moderately dilute (about 10 per cent.) solution of the acidor lactone with a fair excess of phenylhydmzine and an equalquantity of 50 per cent. acetic acid heating the mixture for from30 minutes to two hours on the water-bath ; the product sometimescrystallises from the hot solution but generally the separation occursonly on cooling.The hydrazides of the monobasic hydroxy-acids are all modeiatelyeasily soluble in hot water but the double hydrazides of the polybasicacids are only sparingly soluble.If the solution contaius free mineral acids it must previously beneutrnlised with soda or sodium carbonate and if large qua.nt,ities ofhydrochloric hydrobromic or sulphuric acid are present the acid iORGANIC CHEMSTRY.153best removed with lead acetate or barytt otherwise rather spavinglysoluble salts are formed ; if the solution contains sugar the osazotie,which is also formed in the reaction can generally be separated fromthe hydrazide by crystallisation from hot water.The hyrlmzides are as a rule easily obtained in a pure condition,and may serve as a means of determining the formula of the acid butthey resemble each other so closely in physical properties that theycannot be suitably employed for purposes of identificatinn. Thehydrnzidcs of gluconic acid galnctonic acid and arabinosecarboxylicacid for example cannot be distinguished with certainty ; in suchcases it is necessary to reconvert the hydrazide into the acid.Forthis purpose the hydrazide is boiled for half-an-hour with 10 percent. baryta-water (30 vols.) the phenylhydrazine is extracted withether and the residual solution together with any precipitate whichhas been produced is heated to boiling and the barium precipitatedwith the requisite quantit,y of sulphuric acid; on evaporation thefiltered solution yields the free acid or lactone.All the monobasic acids of the sugar-group under the conditionsdescribed above give crystalline hydrazides which are sparinglysoluble in cold but moderately easily in hot watJer. Under the sameconditions saccharic acid mucic acid and metasaccharic acid yieldhytlrazides which are almost insoluble.Glycollic lactic and glycericacids gave negative results and the limit of the difference in beha-viour probably lies between erythroglucic acid and arabonic acid.Formic acid succinic acid malic acid tartaric acid and mauyaromatic acids for example cinnamic acid and gallic acid yieldhydrazides under the conditions described above but m alonic acidforms only an acid hydrazide. The readiness with which the hydr-azide formation takes place is evidently dependent on the electro-nrgative character of the acid ; if the latter reaches a certain limit,the hydrazide formation takes place in dilute aqueous solution ahtemperatures below loo" but if the acid is less negative in cha-racter the temperature must be raised ; in such cases the presenceof water does not affect the reaction.If for example a diluteaqueous solution of phenylhydr~zine acetate is heated for severalhours a t 130° a considerable quantity of acetylphenyllirdrazine sepa-rates from the solution on cooling. Benzoic acid glyceric acid andlactic acid are converted into the corresponding hydrazides iinder thesame conditions but the product,s do not crystallise readily. Athigh temperatures the yield is not quantitative as the hydrazide ispartially decomposed by the water.The hydrazides can be readily distinguished from the hydrazones.as they all give a reddish-violet coloration with concentratedsnlphuric acid and a drop of ferric chloride a reaction first observedby Biilow (Abstr.1887 138) ; they are moreover readily decom-posed by alkalis and baryta. They are all colourless and generallymelt not quite constantly with considerable evolution of gas.G ~ u c o l ~ i c acid phenylhydrazide C6H,,O6*??&,Ph can be prepared byheating gluconic acid (1 part) on the water-bath for 45 minuteswith water (10 parts) phen.ylhydrazine (1 part) and 50 per ceut.acetic acid (1 part) ; it separates from the cold solution in crystals15-1- ABSTRACT8 OF CHEMICAL PAPERS.and if the mother liquors are heated a:ain for ihrae hours a furthercrop of crystals is obtained. The total yield IS 81 per cent. of thetheoretical. It cryptallises in small prisms softens at about 1!)5",and melts completelv a t 200" with decomposition. It is almostinsoluble in ether and only very sparingly soluble in cold water andhot alcohol but readilyin hot water.It can be easily converted intocrystalline calcium gluconate by boiling it with haryta as describedabove and treating the acid with calcium carbonate; the yield is85 per cent. of the theoretical.Galactorkc acid phenylhydrazide C ~ 0 6 ~ N z H P h can be obtainedin like mariner from crude galactonic acid ; it crystallises in plates,melts a t 200-205," when quickly heated and is moderately easilysoluble in hot wa'ter but only sparingly in cold water and hotalcollol.Aratrinosecarboxylic acid pheny lhydrazide C6H,,06*NzH2Ph preparedfrom the free acid or the lactone in like manner melts a t 214-216"with decomposition and resembles the preceding compound.Dextrosecurboxylic acid phe.rLylhycirazide C7Hl3O7*NzHZPh obtainedfrom the lactone crystallises in prisms melts and is slowly decom-posed a t l7l-l7Zo and is readily soluble in hot water but muchmore sparingly in alcohol.Mannosecarboxy lic acid phenylhydrazide C,H,,O,-N,H,Ph crystallisesfrom hot water in small prisms; when quickly heated it melts a t220-22.3" with decomposition and is more sparingly soluble thanthe other hydrazides.11)/~arnr~osecat~borcylic acid phenylhydrazide C7H,,O6*N2€IzPh crystal-lises from hot water in small hexagonal plates melting a t 210" withdecomposition,Succharinic acid phpriylliydrazide C,H,,O,-N,H,Ph prepared from thelactone crystdlises from hot alcohol in very slender needles melts a t164--ltj5" with decomposition and is much more readily soluble inwater and alcohol than the preceding conipounds.Formic acid seems t o be the only fatty acid which forms a hydr-azide in aqueous solution but even i i i this case the reaction does nottake place quantitatively as it is accompanied by a slight evolution ofgas.The hydrazides of succinic acid nialic acid and tartaric acid areforriied a t 100" in 10 per cent.aqueous solution but the reactions takeplace only slowly.Succinylphenylhydrazine melts a t 217-218" ; Freund and Gold-smith give 208-209" as the melting point. Malic acid diphenyl-hydieazide melts not quite constantly a t 220-22;3" with decomposi-tioil; Biilow found the melting point to be 2 1 ; 3 O . Tartaric aciddiplienylhydrazide melts at about! 24U" when quickly hsated whereasBiilow gives 226" as its melting point.Allyltricarboxylic acid and citric acid yield sparingly soluble hydra-zides under the conditions described above.The phenylhydrazine salt of phenjlhydrazidemalonic acid separakesin crystals when malouic acid (I part) is heated with phenjlhydra-zine ( 3 puts) dilute acetic acid (3 parts) and water (10 parts) fortwo hours on the water-bath; it separates horn hot alcohol or hoOKGASIC CHEEJIISTRT.155water in crystals melts at 141-143" with decomposition and has thecomposition Cl5Hl6N403.31ulorric acid phsnylhydrazide COOH *CH2*CO*N2H2Ph is obtainedwhen the mother liquors from the preceding compound are acidifiedwith sulphuric a.cid and cxtracted with ether.It crptallises incolourless needles me1 ting at 154" with decomposition is moderatelysoluble in water and gives the hydrazide reaction; i t reducesFehling's solution when warmed therewith and has a. strongly acidreaction co n~aloszylphenylhydrazine CH2<CO>N2HPh is formed togetherwith water and phenylhydrazine when the phenylhydrazine salt ofthe preceding compound is heated at 200" for 15 minutes ; it crystal-lises from hot water in slender colourless needles melts at 128" andis readily soluble i n alcohol.Neither benzoic acid nor phenylhydroxyacetic acid yieldsa hydrazidewhen heated with phenglhydrazine in 10 per cent. aqueous solution ;ciririamic acid on the other hand forms the hydrazide previouslydescribed by Knorr (Abstr. 1887 665) but the yield is not par-ticularly good.Gallic acid phenylhydrazide C19HIJY204 crystallises from hotwater in long prisms melts at about 187" with decomposition and isnioderately easily soluble in alcohol and hot water.Glucom'c acid anilide C,H,,O,*NHPh prepared by heating gluconicacid (5 grams) f o r four hours a t 100" with aniline ( 5 grams) water(50 grams) and acetic acid sufficient for solution separates fromalcohol in crystals melts at 171° and is readily soluble in coldwater.The formation of the anilides does not take place as readily asthat of the hydrazides and the products are much more readilysoluble in water.F. S. K.Action of Phenylhydraiine on a-Hydroxy-acids and theirEthyl Salts. By A. REISSPRT and W.KAYSER (Bey. 22 2 9 2 6292'3).-The authors have obtained phenylhydmzidopropionic acid(hbstr. 1884 11521 by the action of phenylhydrazine on ethyllactate and hydrolysis of the ether formed. When equal mole-cular proportions of phenylhydrazine and a-hydroxybutyric acid areh a t e d together at 150-160" pseudophenyl?) ydr~zido-a-h1/droxybut2/,.icacid CloHlrN20z is formed. This compound is easily soluble inalcohol sparingly in ether crystallises in needles and melts a t151-152". It dissolves in boiling acids and alkalis but is reprc-cipitated unchanged on cooling. When dissolved in concentratedsulphnric acid it gives a violet-red coloration. Boiling alkalis do notdecompose it and it is very stable towards reducing agents; it isdecomposed by boiling concentrated hydrochloric acid but besidesphenol no decomposition-prodocts could be isolated. These charac-leristics seem to show that this compound is not a normal hydrazide.With sulphuric acid and potassium nitrite nitrosopseudohydraaiclo-r-h?ydwzybzttyric acid CIOHl3N3O is formed.This is sparingly soluble in water easily so in aqueous alkalis an156 ABSTRACTS OF CHE~IICXL PAPERS.acids ; it melts a t 96-98' and i s very unstable.Acetic anhydrideis without action on the pseudohydrazide whilst concentratedsulphuric acid and phosphoric chloride and oxychloride yield resinousproducts.Mandelic acid yields with phenylhydrazine a pseuudophenylhydr-azidomanddic acid C,,H14Nz02 analogous to the butyric compound.It crystallises from alcohol in long white needles and meltsat 182".With lactic acid only phenylhydrazine lactate was formed.L.T. T.Acetylenedicarboxylates and Phenylhy lrazine. By E.BUCHNER (Ber. 22 2929-2932). -When phenylhydrazine is addedto an ethereal solution of methyl acetylenedicarboxylate methyloxalacetate phanylhydrazone N HPh*N:C ( COOMe) *CH,*C OOMe isform6d. It is easily soluble in boiling alcohol sparingly solublein ether crystallises in colourless glistening scales and melts a t118". Strong sulphuric acid dissolves i t to a reddish-yellow solution,which gives a violet-red coloration with ferric chloride or a solubledichromate. When heated with alkalis or dilute acids it yields theacid Cl,H,N,O obtained by Wislicenns (Abstr. 1887 233) from thecorresponding ethyl-derivative.The latter acid is spsbritigly solublei n cold water. and forms stable salts. It is prob,zblyphe?~yl?-yrcrxololte-carboxylic acid. L. T. T.Weselsky's Resorcinol Dyes. By R. NIETZKI A. DIETZE andH. MACRLER (Ber. 22 3020-3038).-Resazui in (Weselsky's diazo-resorcinol) Cl ,H,N04 is obtained together with resxufin (diazo-resorufin) by Weselsky and Benedikt's method (Jfonatsh. 1. 8S9) andcan be purified by means of the sodium salts. It crystallises froinglacial acetic acid in snidl greenish prisms which do not melt with-out decomposition. The sodium salt Cl,H6N04Na crystallises inlong green lustrous needles rather readily soluble ill water sparinglyin aqueous sodium csrbonate and sodium chloride. In thin layers tliesolution is almost pure blue and shows.espwixlly in presencch of alittle alcohol a splendid brick-red tluorcscence. The barium salt fornisbrownish sparingly soluble needles the siluer salt is a volumiiious,flaky precipitate. The ethyl-derivative crystallises in long dark-redneedles melting a t 815". The acetyl-derivative CI2HGNOJAc preparedby heating a mixture of sodium resazurin and sodium acetate ( d r j )with acetic anhydride (1 2-15 parts) crystdlises from alwtwl inlong ruby-coloured needles melting a t 22.2" ; when heated withsodium carbonate blue resazurin i s formed. Tetrabronioresnzurin,C12H,Br,N0 (Weselsky and Benedikt's " non-fluorescent blue ") wasprepared by brominnting resazurin ; the sodium salt CizH2 Br4N0,Na + 2H20 crystallises from hot dilute alcohol in lustroos greenneedles. When the bromo-derivative is reduced tetrabromoresornfinis formed as observed by Weselsky and Benedikt ; the potassium salthas the formula they ascribed to it Cl,H,Br4N04K + 2Hz0.The substance obtained by the action of acetic chloride on resRzurin,to which Brunuer and Kranier ascribed tlie formula CI2H9Cl2NO(Abstr. 1884 1333) crystallises in golden plates ard seems to be amixture.Resorufin CL2H,N03 was obtained from the mother liquors fromthe preparation of resazurin and also by heating the latter withhydrogen sodium sulphite solution.It crystallises in small brownneedles. The potassiuin salt forms small brownish plates extremelysoluble in water ; the ethyl salt C,?H,NO,Et crystallisw in orange-redneedles melting at 225".The acetyl-compound crjstallises in loiigneedles melts at 223" and has the formula given to it by Weselskyand Benedikt. Tetrabromoresorufin (" flu ore scent^ blue ") was pre-pared in a manner similar to tetrabromoresazurin ; the sodium salt,C ,,H,Br,NO,Na + 2H,O crystallises in splendid lustrous greenneedles.Hydroresorufin the compound obtained by the action of zincchloride on resorufin or on 1-esazurin has the formula C1,HI,N03. Itcryst'allises in nearly colourless wide needles which soon becomegreen when exposed to air. The ti-iacety I-compound CI2H6NO3Ac3,forms long colourless lustrous needles melts a t 216" and is nearlyinsoluble in water sparingly soluble in hot alcohol and very solublein hot glacial acetic acid.The molecular weight of the acetgl-derivative was determined by Raoult's method. When hgdroresor-ufin is distilled with zinc-dust diphenylamine is formed.The paper concludes with remarks on the constitution of resorutinand resazurin. N. H. M.Dyes of the BenzeYn Group. By I(. HEITMANN and H. REY (Ber.,22 3001-31104) .-l'etrfLmethylrosamin~ C2,H,,N2(OH) (?) is pre-pared by the action of benzotrichloride (1 mol.) on dimethylmetamido-phenol (2 mols.) at 50-60° using sand (;r benzene as a diluent tokeep <own the temperature ; the reaction is completed by heating at60" on a water bath. The product is steam-distilled extracted withboiling water containing hydrochloric acid and precipitated withsodiuiri chloride. It is purified by dissolving in water partially pre-cipitating with sodium carbonate filtering and precipitating withsodium carbonate or ammonia.The hydrochloride C19HllMe4N,0C1,forms black-red needles with steel-hlue reflection ; the platinochlorideis a dark red precipitate soluhle in water; the ozalate and nitrate formdark green and steel-blue needles respectively. The aqueous solutionsof the salts have a splendid bluish-red colour with jdlowish-redfluorescence. The solution in sulphuric acid is orange-yellow thecolour being changed to red by the addition of water. Silk and woolare coloured roee-colour to dark-red by a slightly acid bath of thedye. The colour on silk and jute shows a yellowish-red fluorescence,which is increased by sulphuric acid.The rosamines are decolorised by zinc-dust in acid and alkalinesolutions.Addition of soda does not produce an immediate precipi-tate in solutions of the dyes ; a sodium salt seems to be formed. Thealkaline solutions dye unmordanted wool an intense rose-colour oreven deep-red but the colour is removed by boiling soap solution orby prolonged boiling with water.Tetrethyli osamine was also prepared from diethylmetamidopheno1 58 ABSTRACTS OF CHEJIICAL PAPERS.and benzotrichloride. The salts produce a bluer colour than those ofthe methyl-derivatives.Diphenylrosamiiie from metahydroxydiphenylamine is a violet dye,readily soluble in alcohol sparingly in water.Action of Chlorocarbonylamide (Urea Chloride) on Aro-matic Hydrocarbons in the Presence of Aluminium Chloride.By E.P . HARRIS (Clzem,. Centr. 1889 ; ii. 285-286).-The followingcompounds are obtained by gently warming chlorocarbonylamide withthe corresponding hydrocarbons and finely-pnwdered aluminiumchloride. iMetaxyhnide C6H,Me2*CO*NH forming lufitrons needlesmelting a t lSO" from which Fittig's xylic acid is obtained by saponi-fying with alcoholic potash. Orthoxylamide crystallising in lustrousneedles and melting a t 136-137" from which Fittig's paraxylicacid is obtained by hydrolysis. p- Isoduylamide C,H,Me,*CO*NH,,forming lustrous plates melting at 184". Tetrameth2/Zhenxanzide,C6HMe4.C0.NH2 crystallising in plates melting at 172-173". Ace-napthenecarboxylamide C,sH,,ON forming plates melting a t 198".a-EtA y In apht ha lenecar box y 1 am ide c ,oH&t*C 0.NH2 cry st allisin g incolourless needles melting at 166". All these amides are readilyhydrolysed the corresponding acids being formed. Alkaline potas-sium permanganate oxidises acenaphthenecarboxylic acid to naph-thdenetricarboxjlic acid.In the case of the homolognes of benzene,the amidocarbonyl group enters in the para-position unless this isalready occupied in which case it assumes the meta-position. I n thecase of the homologues of naphthalene only the a-derivatives reactwith chlorocarbonylamide. J. W. L.Behaviour of Aniline towards Substitution-derivatives ofHydroxybenzoic Acids at High Temperatures. By H. LTM PRICHT(lh-. 22 2906-2912). The author before examiniug the action ofaniline on substituted hydroxybenzoic acids repeated other experi-menters work on the action of aniline (14 grams) on the hytlroxy-benzoic acids (10 grams).With the ortho-acid 1.5 grams of anilidewere obtained with the para-acid 1 gram of anilide whilst with themeta-acid apparently nearly all the hydroxy-acid mas converted intothe auilide. Contrary to Kupferberg's statement the author tinds thatsalicylanilide distils a t a high temperature without decomposition.N. H. M.L. T. T.Action of Aniline on Amidosalicylic Acid. By H. LIMPRICHTand v. RECHENRERG (Ber. 2 2908-2912) .-Amidosalicylic acid[OH COOH NH = 1 2 41 is best obtained by heating azo-benzenesalicylic acid with stannous chloride. When amidosalieylicacid is heated with aniline hydrochloride a t 160-210" for some hours,i t yields phenamidophenol NHPh*CsH4.0H and diphenamidopheny-lene C6Hr(NHPh),.The former is soluble in cold alcohol the latteronly in boiling alcohol. Phenamidophenol cr~stallises from waterin large flat colourless prisms which turn brown on exposure to theair. It melts a t 70"' and distils almost withont decomposition. It issoluble in soda and is coloured blue by strong nitric acid. Withetbyl iodide and alcohol it yields a derivative which was not howeverORQANIC C HEJIISTRY. 159obtained in a pure state. With excess of acetic anhydride it yieltlsdiacetylph et/ a t ) ir Joph eiioZ 0 Ac- C6H,*NP h Ac which forms w Iiite cry st a'ssoluble in alcohol ether and benzene and melts a t 119". Phenamido-phenoZsuZphowic acid SO,H*CsH,(OH)*NHPh obtained by heatingthe phenol with strong sulphuric acid crystallises from boiling waterin Small grey prisms which are still solid a t 260" It is easil7 solublein :tlcohol sparingly so in ether and benzene.The barium salt iscrystalline. Diphenamidophenylene ohtained as above forms grey01' brownish needles easily soluble in ether chloroform acetone. bell-zene carbon bisulphide acetic acid and boiling alcohol insoluble inwater and melts a t 141". Nitric acid gives first a blue and then ablood-red coloration concentrated sulphuric acid dissolves the crystalsto a blue solution; hydrochloric acid has no action but if sodiumnitrite is added to the mixture a n unstable nitroso-derivative is formed.Diphenamidophenylene is not formed by the action of pure aniline onphenamidophenol but only when hydrochloric acid or aniline hydro-chloride is present. Both the phenol and phenylene are para-com-pounds and they can also be similarly prepared from the [l 3 41aruidosalicylic acid.L. T. T.(Rer. 2 2 299 1-3001) .-P hen y lprop ylene-~-thiocarbamicte,Aromatic Substituted Pseudothiocarbamides. By B. PRAGERis prepared by heating aIIylphenylthiocarhamide (m. p. 95" 50 grams)with crude hydrochloric acid (100 c.c.) for two hours at 100". Theproduct is evaporated down diluted with water and saturated withammonia It meks at 117" and dissolves readily in chloroform,alcohol ether and benzene. The picrate crystallises in yellowneedles melting at 154" ; the ylutinochloride (C,oH,zN,S),,HzPtCI,,forms microscopic yellow crystals.Phenyl-/3-mef hyltaurocarbainic anhydiide C,oH,2N,S03 is formedwhen the above base is oxidised with potassium chlorate and hydro-chloric acid (Andreasch Abstr.1883 664). It melts at 192" dis-solves in alcohol and glacial acetic acid sparingly i n hot watcr and isindifferent to acids and alkalis. When heated with hydrochloric acidat 230" for five hours it is converted into p-methyltaurine (Gabriel,Abstr. 1889 848) and anilinc.Phen y lmet hy lpop y 1 ene- q- thiocarbnmide NMeP h*CGN. S-YHMe CH isobtained when a mixture of methylaniline (30 grams) and ailylthio-carbamide (30 grams) is heated for a short time then left for Somehours and finally heated with hydrochloric acid (120 c.c.) at 100" fortwo hours (compare Gebhnrdt Abstr.1885 383). The base was notobtained pure by this method but salts were prepared. The base wasalso prepared by the action of an excess of methyl iodide on phenyl-propylenethiocarbamide. It distils at about 300" without decompo-sition. The picrute crystallises from boiling wat,er in yellow needlesmelting a t 125" ; the ylati~~ochlor~de separates from the dilute hydro1 ti0 ABSTRACTS OF CHEMICAL PAPERS.chloric acid solution in orange-red crystals melting a t 183-184" withdecomposition.When phenylmethylpropylenethiocarbnmide is oxidieed with potas-sium chlorate and hydrochloric acid and the product heated withhydrochloric acid at 150-160" p-methyltaurine and methylanilineare formed.dllylorthotoZyZthiocarbnncide Cl,H,,N2S is prepared by heating amixture of orbhotoluidine (25 grams) dissolved in alcohol (20 c.c.)and allylthiocarbamide (25 grams) and evaporating the product on awater-bath.It forms lustrous crystals melt8 a t 98" dissolves readilyi n glacia.1 acetic acid chloroform alcohol and benzene is less solublein alcohol and insoluble in water.Orthotolylpropylene-jb-thiocarbamide C,H,*NH< N-CH obtainedfrom the above compound by the action of hydrochloric-acid crystal-lises in small rhombic plates melts a t 126" dissolves readily in theusual organic solvents and in mineral acids. sparingly in hot water.The yicrate melts a t 3 75-176"; the plutinochloride forms orange-redcrystals melting at 177-178". v S.7 HMe Ort hoto ly 1 met h y lprop y Zen e- 9- thiocarbamide C7H7*NMeGN.~~formed by the action of methyl iodide on orthotolylpropylenethio-carbamide boils a t about 295". The hydrioclide crystallises in longhexagons melting a t 165-166" ; the picrate forms yellow prismsmelting a t 137-138" ; the platinochloride decomposes at above 200".When the base is oxidised and the product heated with hydrochloricacid a-methyltanrine is formed.a-Naphth ylpropyleire-~-thiocarbamide CI4Hl4N2S obtained fromallgl-2-naphthylthiocarbamide (m. p. 145" not 130" ; Zinin An:)iaZen,34 :34cj) crystallises in rhombic plates melts a t 134" dissolves readilyin chloroform alcohol and benzene is less soluble in ether andinsoluble in light pet,roleum and water. The yicrate crystallises inlong rectangular prisms melting at 192" ; the platinochboride is anorange-coloured crystalline salt which melts a t 205-206" with effer-vescence.N. H. M.Piaselenoles and Piazothioles. By 0. HINSBERG (Eev. 22,2895-2902).-Continuing his previous work (Abstr. 1689 785),the author finds that selenious anhydride or acid reacts with aromaticorthodiamines to form piaselenoles but that no similar derivatives areformed from aromatic meta- or para-diamines or from fatty diamines.Sulphurous anhydride forms a similar series of piazothioles witharomatic ort,ho-diamines but phosphorous boric and tellurousanhydrides phosphorous chloride phosphoric oxycliloride andarsenious chloride do not yield any analogous compounds. Thepiaselenoles and piazothioles closely resemble many of the substitutedquirioxalines.Piaselmole CsH4:N2:Se prepared from orthophenylenediamine,forms colourless needles easily soluble i n alcohol ether and benzene,sparingly so in water ; when heated it melts a t 76" and ernits an odouORGANIC CHEMISTRY.161resembling that of quinoxaline. Its salts are yellow in colour andare decomposed by excess of water. Sodium yields a characteristicgreen periodide. EthoxypinseZenoZe OEt*C6H3:N2:Se prepared fromethoxyphenylenediamine crystallises in pale yellowish needles,soluble in alcohol and melting at 103-104". With concentratedsnlphuric acid it yields an intensely yellow solution ; with stannouschloride and potassium periodide i t behaves like the other piaselenoles.AmidopiuseZenoZe NH,*C6H3:N2 Se unlike the other piaselenoles is onlyformed when selenious acid and triamidobenzene (1 2 4) solutionsare mixed in the cold ; at higher temperatures the triamidobenzeneacts as a reducing agent towards the selenious acid.It crystallisesin brownish-red needles soluble in alcohol benzene and ether,sparingly so in water and melting at 149-150". Its salts are dark-brown and crystalline but are rather unstable. Concentrated sulph-uric acid dissolves it forming an almost colourless solution witha reddish fluorescence but it becomes intensely brown on dilution.PiazothioZe C6H4:Nz:S is formed when orthophenylenediamine isheated with concentrated aqueous sulphurous acid (or sodiumhydrogen sulphite) for five or six hours at 180-200". It is alsoformed when a stream of sulphurous anhydride is passed into theboiling diamine but its formation is then generally accompanied bythat of resinous bye-products.It forms colonrless crystals havinga strong odour resembling that of quinoxaline melts at 44" boilsat 206" (uncorr.) distils in a current of steam is sparingly solublein boiling water easily so in organic solvents and is only feeblybasic in character its solutions in strong mineral acids being pre-cipitated on the addition of water. Piazothiole is a very stable sub-stance and very resistent to oxidation ; strong reducing agentsconvert it into phenylenediamine and hydrogen sulphide. Methyl-piuzothiole C6H,Me:N2:S from metaparatoluylenediamine resemblespiazothiole in character melts at 34" and boils at 233-234' (uncorr.).Determination of it8 molecular weight by Raonlt's method gave 143,the formula C7H6N2S requiring 150.Its salts are colourless and aredecomposed by water. The platinochloride ( C7H6N2S)z,H2PfCls formsreddish-yellow crystals ; the periodide is also crystalline. Whenmethylpiazothiole is dissolved in strong sulphuric acid and strong nitricacid then added in excess nitromethy~iazot7zioZe N02*CsH2Me:N2:S isobtained. It forms colourless crystals soluble in alcohol and glacialacetic acid and melting at 154-156". Rromomethy ZpiazothioZe,C6H2MeBr:N3:S formed by the addition of bromine to a cold chloro-form or hot acetic acid solution of methylpiazothiole forms whiteneedles melting at 98". It is volatile in steam and is very stable thebromine-atom not being removed by boiling with potash.Derivatives of Paranitrocinnamaldehyde. By A.EINHORN andC. GEHRENEECK ( A n n d e n 253 348-376 ; compare Abstr. 2889,396) .-Paranitrocinnamaldoxime N02*C6H4-C3H3:N *OH prepared byboiling the aldehyde with hydroxylamine hydrochloride and sodiumcarbonate in dilute alcoholic solution is a yellow crystalline compoundmelting at 178-1 79". The anilide C15H,2N202 crystallises fromalcohol in yellow needles melting at 132-133".L. T. T.VOL. LVIII. 162 ABSTRACTS OF CHEMICAL PAPERS.Paranitro-a-bromocinnamaldehyde (m. p. 136") identical with thecompound obtained by Zincke and Hagen (Abstr. 1884 1343) bynitrating a-bromocinnamaldehyde is formed when nitrocinnamalde-hyde is treated with bromine in glacial acetic acid solution; thedibromide could not be obtained in a pure condition.Paranitrophanytbutine rnethy 1 ketone,N02*C6H,*CH:CH*CH:CH.COMe,is obtained together with paradinitrodiphenyldibutine ketone whenparanitrocinnamaldehyde is treated with acetone in alcoholic sodasolution ; the filtrate from the paradinitro-compound is poured intoacidified water the precipitate digested with dilute sodium carbonatesolution to free it from paranitrocinnamic acid and recrystallised. Itseparates from water in colourless needles melts at 132" and is readilysoluble in the ordinary solvents.The hydrazone CI8H1,N3O2 separatesfrom alcohol in ruby-red crystals melting art 209-210".Paradinitrod~pheny Zdibutine ketone CO ( CH:CH°CH:CH*C6H,*N O,),,crystallises from acetic anhydride in pale yellow needles melts at216-218" and is readily soluble in glacial acetic acid but insolublein water ether chloroform and alcohol.Paranitrophenylbutinecarboxylic acid (compare Einhorn andGehrenbeck Zoc.cit.) can be prepared by gradually adding analcoholic solution of paranitrophenylbutine methyl ketone to a boil-ing concentrated s o h tion of sodium hypochlorite. The ethyl salt,Cl3Hl3NO4 crystallises from alcohol in yellowish plates melting at118". The copper salt C2?H16N,08Cu is crystalline the silver 8dt,CIIH,NOIAg amorphous ; the alkaline salts are very readily solublein water.Paranitrophenylbutine-w-dicarboxylic acid (m. p. 208") is readilysoluble in alcohol hot water and glacial acetic acid but sparingly inbenzene ether and chloroform. The ethyl salt C18H17N06 crystal-lises from dilute alcohol in colourless needles melting at 10&105".The copper salt C,2H7NO&u is crystalline the silver salt.C12H7N06A@ amorphous and the alkaline salts are very readilysoluble in water.Paranitrophenyl-~6-dibromethyl-/3-bromacrylic acid is readilysoluble in ether ethyl acetate and alcohol but only sparingly in&loroform and benzene ; when oxidised with 3 per cent.potassiumpermanganate it yields paranitrobenzoic acid. The ethyl saltC13H12NBr304 crystallises from alcohol in colourless plates melting at124". The sodium salt crystallises with 2 mols. H,O. F. S. K.Constitution of Filicic Acid. By H. SCHIFF (Annulen 253,336-342) .-The author discusses the results obtained by Grabowski(Annulen 143 279) Luck (Abstr.1889 276) and Daccomo(&id. 54) in their investigations of filicic acid and comes to theconclusion that filicic acid is a butyrophloroglucyl ally1 ketone of theconstitution I (oH):CH*$*o*CH2'CHMe2 The criticisms of paterno CHIC( OH) *C*C0.CH2*CH:CH2'(Abstr. 1889 615) on the experimental results of Daccomo (Zoc. cit.ORGANIC CHEMISTRY. 163would seem according to the author to be to a great extent un-grounded. F. S. K.Carbothionylic Acids of Resorcinol and Pyrogallol. By E.LIPPMANN (Monatsh. 10 617-623 ; compare Abstr. 1888 1092).-Dihydroxydithiobenxoic ucid c6&( OHL*CSSH is obtained in 60 percent. of the theoretiad yield by heating in a closed flask €or 12 hoursa t 100" a mixture of resorcinol (50 grams) and potassium xanthate(80 grams).On heating the acid (50 grams) at 130-140" withpotash (250 grams) dissolved in a little water it is converted intoP-resorcylic acid and consequently must be regarded as a metacarbo-thionylic acid.PyroguZloZcarboth~ortyZic acid C,H,(OH),*CSSH + H20 is pre-pared in a manner precisely similar to that used in the case ofdihydroxydithiobenzoic acid. It crystallises unchanged from dilutealcohol in the form of beautiful glistening golden scales which becomeanhydrous at 70" and melt at 154". On heating it with five times itsweight of potash and a little water at 120-130" it gives thepgrogallolcarboxylic acid of Senhofer and Brunner and consequentlyhas the constitution CSSH (OH) = 1 2 3 4.G. T. M.Action of Orthonitrocinnamaldehyde on Malonic Acid. ByA. EINHORN and C . GEHRENBECK (Annalen 253 374-376) .-Ortho-nitrophenylbutine-w-dicurboxylic acid C12H9N06 prepared by heatingorthonitrocinnamaldehyde with malonic acid for six hours in glacialacetic acid solution crystallises from glacial acetic acid in yellowishneedles melts at 212-21 3" and is sparingly soluble in benzene ether,and chloroform but readily in alcohol and hot water. The silver salt,C12H7NOsAg2 crystallises in yellowish plates ; the copper salt,CI2H7NO6Cu is a yellowish-green crystalline compound.Ort honitrophen y lbutene-a-hy droxy - w-dicarbox y 1 ic acid,NO2.C6H4*cH CH*CH (OH) cH( co 0 El),,is the first product of the action of malonic acid on orthonitrocinnam-aldehyde ; it crystallises from alcohol in which it is only sparinglysoluble in colourless needles melts at 269" explodes when heatedstrongly and is insoluble ir- benzene and light petroleum and onlysparingly soluble in ether chloroform and glacial acetic acid but;readily in hot water.F. S. I(.Benzoyltannin. By C. BOTTJNGER (Ber. 22 2706-2709).-Benzoyltannin can be obtained by shaking an aqueous solution oftannin with soda and benzoic chloride ; the dirty-white precipitatewhich is produced is boiled with ether to free it from benzoic acid,and the residue is warmed to expel the ether washed with water anddried. It is a pale yellow crystalline powder insoluble in boilingwater and almost insoluble in boiling alcohol.It is not acted on byammonia and it is only very slowly dissolved and decomposed bycold dilute soda.. When heated with water at 150° it liquefies com-nb 164 ABSTRACTS OF CHEMICAL PAPERS.pletely but it is only partially decomposed even a,fter heating for twohours at 165". It dissolves in hot aniline with formation of benz-anilide and is soluble in hot dimethylaniline. It is decomposed bywarm concentrated sulphuric acid or when heated alone. It dissolvesin warm pbenylhydrazine with slight evolution of gas yielding ayellow substance and a crystalline compound which is soluble in etherand in boiling soda.Other naturally occurring tarinic acids give simiIar benzoyl-derivatives.Tannin dissolves in warm concentrated sulphuric acid and isthereby converted into gallic acid.The benzoyl-derivative of tanriic acid (from oak bark) dissolves inwarm phenylhydrazine with evolution of gas yielding a yellowish-brown substance which is soluble in soda.F. 8. K.Tannins. By C. ETTI (Monatsh. 10 647-664) .-Investigationof the tannins of the formulat! C1,H,609 and C20H2009 (compare Abstr.,1881 277; 1883 994) has proved that they are not glucosides butare to be regarded as derivatives of a ketonic acid,C6&( OH),*CO0C6H( OH),*COOH.The author has now isolated a new tannin which resembles thoseabove mentioned in its general chemical and physical properties,appearing from its behaviour with phenylhydrnzine and hydroxyl-amine to be also a ketonic compound. It has the formula C16H1409,and is obtained as a red powder from the diluted extract of the woodof the common Slavonian oak by careful precipitation with hydro-chloric acid (excess of acid must be avoided as it diminishes theyield).The precipitate is allowed to remain for several days thencollected well washed with water air dried and lastly fractionallydissolved by alcoholic solutions of different strengths and precipitatedwith water. The pure substance whic!i is brownish-red is madeup of microscopic warty spherical masses (recrystallised from alcohol),insoluble in wat,er and ether butl readily soluble in acetone and hasbeen shown by Fuchs (Monatsh. 9,1132-1142) to be a monobasicacid. With phenylhydrazine it gives a yellow amorphous compound,C22H20N20s forms a brown amorphous oxime C16H15N09 and whenheated with dilute snlphuric acid (1 10) for six hours in a sealedtube at 120-130" yislds together with an insoluble anhydride a redsolution from which by extraction with ether a red crystalline massmay be obtained. On pressing this and recrystallising from water,it becomes colourless and is identical with gallic acid (m.p.238-240'). On treatment with magnesia the tannin C16H1409 givesthe following salts :-( C16H1309)2Mg a brownish-yellow amorphousmass ; (C16Hlo0,)zMg~ and (C14 H1109)2Mg3 both bright-yellow powdersscarcely soluble in water ; (c16H1309)nMg + 2Cl6H1409 of a brownish-yellow colour and very soluble in water. In all probability theextract furnishing the tannin contains it as a soluble normal mag-nesium salt.The tannin C,6H& when heated alone at 130-135" or in closeORGANIC CHENISTRY.165tubes with water at loo" loses water forming anhydrides from whichthe acid cannot be again regenerated and which yield methyl iodideon boiling with hydriodic acid. On boiling the tannin with dilutesulphuric acid in an open vessel an acid of the formula C32H24016= 2C16H1409 - 2H20 is formed as a reddish insoluble mass whilst,on heating in a closed tube two anhydrides are formed of whichone CnH2,01a of a dark-red colour is soluble in 95 per cent. alcohol,and according to Fuchs (Zoc. cit.) is of an acid nature whilst theother C32H18013 which is blackish is insoluble and shows no acidreaction. The tannin CI6Hl4O9 on long heating with hydrochloricacid at loo" loses a methoxyl-group and is converted into an acid,CI5HI2O9 of a yellow colour which still contains a methoxyl-group ;so that the tannin itself contains two methoxyl-groups.G. T.M.Dibromosulphanilic Acid and its Derivatives. By 0.HEINKHEN (Annulen 253 267-288) .-Dibromosulphanilic acid canbe conveniently prepared by gradually adding a freshly preparedsolution of bromine (10 c.c.) and soda (16 grams) in water (150 c.c.)to a hot aqueous (500 c.c.) solution of sulphanilic acid (17.3 grams)and 35 per cent. hydrochloric acid (21 grams); the yield of thebarium salt is 39.9 grams or 95 per cent. of the theoretical. Itcan also be prepared by gradually adding a solution of potassiumbromate (11.1 grams) in water (250 c.c.) to a hot aqueous solution(500 c.c.) of sulphanilic acid (17.3 grams) and 43 per cent.hydro-bromic acid (37.6 grams) ; the yield of the barium salt is 38 grams,or 90 pel9 cent. of the theoretical and no tribromaniline is formed inthe reaction.Sulphanilic acid is converted into aniline but only very slowly,when it is heated at 200-220" with dilute sulphuric acid (b. p. 160')in a current of steam. Dibromosulphanilic acid at a temperature ofabout 170-178" other conditions remaining the same is readilyconverted into dibromaniline (m. p. 83-84"); the yield is 83 percent. of the theoretical.Dibromaniline [Br NH = 1 3 21 crystallises from hot dilutealcohol in long colourlesa needles melts at 83-84" sublimes at262-264" and is readily soluble in alcohol ether benzene andchloroform.The hydrochloride prepared by passing hydrogen chlorideinto a benzene solution of the base melts at 126" and is decomposedby alcohol and by water or by exposure to the air. ThepZatinochZo+Ze,(C6H,Br,.NH2)z,H2PtCl~ crystallises in golden plates and is decom-posed by water.Diazodibromobenzene sulphate C6H3Br,N,,HSOa prepared by treat-ing dibromaniline with sulphuric acid and ethyl nitrite in well-cooledalcoholic solution crystallises in colourless needles and is relatively,very stable ; when boiled with water under reduced pressure i t yieldsan oil probably metadibromobenzene but when heated with snl-phnric acid (b. p. l50") it i s converted into dibromophenol (m. p.Metadibromoguinone [02 Br = 1 4 2 61 is obtained when di-bromosulphanilic acid is oxidised with potassium chromate alid55-56")166 ABSTRAOTS OF CHEMICAL PAPERS.sulphuric acid in the cold.It crystallises from hot alcohol in golden,iridescent plates melts at 131" and is readily soluble in alcohol,ether chloroform and benzene but only very sparingly in cold water.The same compound is obtained by oxidising dibromoparaniidophenol ;this quinone is probably identical with the dibromoquinone obtainedby Levy and Schultz (Abstr. 1882 509) by oxidising tribromophenolwith fuming nitric acid. F. S. K.Tin Tetraphenyl. By A. POLIS (Ber. 22 2915-2918).-500grams of a tin-sodium alloy (25 per cent. of sodium and 75 per cent.of tin) 600 grams of bromobenzene and 25 C.C. of ethyl acetate wereheated together at incipient boiling for about 30 hours.The productwas a syrupy brown mass the solution of which in boiling benzenedeposited crystals of tin tetraplzenyl SnPhd on cooling. This sub-stance when pure forms thin colourless prisms belonging to thetetragonal system a c = 1 0.3893 ; 111 110 = 70" 35'. It is thusisomorphous with silicon tetraphenyl and lead tetraphenyl the axialratios following the order corresponding with the positions of themetals in the periodic system. It melts at 225-226" volatilisesunchanged and boils above 420".It resembles the corresponding silicon and lead compounds in soh-bility dissolving readily in boiling benzene glacial acetic acid chloro-form and carbon bisulphide ; very sparingly in alcohol and ether.It inflames spontaneously when exposed to air.When treated withbromine (2 mols.) bromobenzene and tin diphenyl dibromide areformed. The author finds that under 42 mm. pressure the lattercompound distils at 230" without decomposition. Chlorine is similarin its action t o bromine whilst iodine is without action.L. T. T.Derivatives of Diphenyline. By J. REULAND (Ber. 22,3011-3019) .-UibenzyZidenediphenyZine CIPHP( KCHPh) is prepared byheating a mixture of diphenyline (1 mol.) and benzaldehyde (2 mols.)on a water-bath for several hours until clear dissolving the productin ether and precipitating with light petroleum. It crystallises fromalcohol and benzene in lustrous yellow plates melts at 232-233",and is sparingly soluble in alcohol and ether.Dinzetaizitrobenzy lidenedipheny line C12H8(N:CH* C6H4*N02) preparedby heating diphenyline (1 mol.) dissolved in a little alcohol withmetanitrobenzaldehyde (2 mols.) for some time on a water-bath crys-tallises from a mixture of benzene and alcohol as a fine yellow,crystalline powder.It melts at 184-185" and is readily soluble inbenzene less so in alcohol. The dipuranitro-cleri?;ative C2SH18N404 is ayellowish-red powder melting at 208".Diorthohydroxybenzylidinediphen yline Cl2H8(N:CH*C,H,*0H) pre-pared from diphenyline and salicylaldehyde crystallises from alcoholin yellow plates melting at 145".Difurfiwaldiphenyline CuH8(N:C5H40) is formed when furfuralde-hyde (3 grams) is added to a solution of diphenyline (3 grams) inabsoluto alcohol (100 grams) and kept for 24 hours.It crystallises inIt was not analysedORGANIC CHXMISTRY. 167lustrous yellow plates and melts at 137". When the alcoholic solutionis treated with mineral acids splendid red compounds are formed.PhthaZodiphenyZine C J & ( N:C<06->CO)2 c H4 obtained by heatingdiphenyline with phthalic anhydride (2 mols.) for two hours at115-120" crystallises from glacial acetic acid in lustrous whiteplates melting at 25.5-257".is prepared by heating di-phenyline (5 grams) with absolute alcohol (15 grams) and carbonbisulphide (15 grams) for 18-20 honrs in a reflux apparatus on awater-bath distilling off tLhe alcohol and carbon bisulphide and ex-tracting the residue several times with hot alcohol and ether.Itmelts at 238" and does not give an odour of thiocarbimide when heatedwith strong hydrochloric acid.Diphenylenebisazo-P-naphthol C12Ha(N:N*C10H6*OH)2 is obtainedwhen diphenyline is dissolved in hydrochloric acid (4 mols.) wellcooled and treated wit,h the calculated amount of sodium nitrite.The tetrazo-compound is filtered and added to a filtered solution of@-naphthol in just sufficient potash. It is crystallised from benzene.It melts a t 243-245" and dissolves in strong sulphuric acid with redcolour.DiphenylenebisazoresorcinoZ C12Ha(N:N*C6Hb02)2 prepared in amanner similar to the above compound is a reddish-brown powder.Dt$henylenebisazodimethylaniline C12Ha(N:N*C,H4*NMe2)2 is formedas a red precipitate of a metadlic lustre by the action of the tetrazo-compound of diphenyline on methylaniline.Tetramethyldiphenyline NMwC,H4* CsH4.NMe2 is obtained by heat-ing dry diphenyline hydrochloride (1 mol.) with methyl alcohol(4 mols.) at 180" for two hours.The product is poured into hydro-chloric acid treated with potash and extracted with ether ; the etheris distilled off the residue boiled with acetic anhydride and fraction-ally distilled. The oil which distils over at 333-345" solidifies ina short time. It crystallises from absolute alcohol in monoclinicprisms which are phosphorescent when rubbed together ; it melts at51-52". It gives a blue coloration with chloranil. The picratecrptallises from alcohol in long red needles resembling chromic acid,melts at 199-200" and decomposes at 208".The methiodide formsslightly rose-coloured needles melts at 184" and is readily soluble inalcohol and water almost insoluble in ether. The dimethiodide meltsat 196" and is readily soluble in water and alcohol.Diphenylorthoparadicyanide C,,H,(CN) [= 2 4'1 is prepared bySandmeger's method for displacing amido-groups by cyanogen follow-ing exactly the instructions given for benzonitrile (Abstr. 1885,149).It crystallises in slightly yellowish plates and melts at 152-153".Diphenylortho~aradicarboxylic acid CI,H,(COOH) [ = 2 4'1 ob-tained by the hydrolysis of the above dicyanide crystallises in colour-less plates melting at 251-225". The silver salt is a white powder,melting at 235-237" readily soluble in ammonia ; the copper saZt isa sparingly soluble bluish-green crystalline powderNH*$l6Hjs < ~ ~ o ~ ~ Thiocarbodipheny line,N. H.M168 ABSTRACTS OF CHEMICAL PAPERS.Oxidation of Triphenylmethane. By &I. HANRIOT and 0.SALNT-PIERRE (Bull. Roc. Chim. [3] 1 773-774) .-Triphenylmethane,suspected by the authors to contain a higher homologue derivedfrom toluene was oxidised with chromic mixture; in addition totriphenylcarbinol (20 per cent.) and benzophenone (40 per cent.),small quantities of orthobenzoylbenzoic acid and of anthraquinoneresulting from the dehydration of this acid were obtained. Puretriphenylmethane yielded neither of the latter substances on oxida-tion. T. G. N.Paramethylbenzil and Benzilparacarboxylic Acid. By E.BUCHER (Ber. 22 2819-2820).-Paramethyldeoxybenzo~n yields thefollowing bromo-substitution-products :-CHPhBr.CO*C6H4]lfe CBr2Ph*CObC6H4Me CBr2Ph*CO*C6H,*CHBr2,and CBr2Ph*CO*C6H4-CBr3 from which paramethylbenzil dibromo-deox y benzoznparacarboxy lic acid CBrJ? h*C 0- C6H1* CO OH and b e n d -paracarboxylic acid can be obtained.Paramethylbenzil COPh*CO*C6HaMe is formed when dibromo-deoxybenzoin is heated with water at 180" ; it is a yellowish oil.Benzilparucarboxylic acid COPh*CO-C,H,.COOH is obtained byheating the pentabromide with water at 160"; i t crystallises incolonrless plates and decomposes at 280-300" without melting.The acid CBr2Ph*COG6H4*COOH is formed when methyldeoxy-benzoin is heated with bromine (5 mols.) at 160° or when dibromo-paramethyldeoxybenzoin is heated with bromine (3 mols.) and waterat 160" ; it crystallises in yellow needles melts at 218" and is partiallyconverted into benzilcarboxylic acid when heated with magnesia a t190".F. S. I(.1.4'-Iodonaphthalenesulphonic Acid. By R. MAUZELIUS (Ber.,22 2820-2823) .-1.4'- Iodonaphthalenesulphonic acid CloH,I*S 03H,can be prepared by treating a-diazonaphthalenesulphonic acid withwarm 40 per cent. hydriodic acid ; it is purified by converting it into thechloride (see below) and decomposing the latter with water at 150".It crystallises in almost colourless plates with 2 mols. H20 melts at129" and is readily soluble in water.ammonium salt sodium salt with 1 mol. H20 silver salt copper salt,with 2H20 and a number of other salts were prepared; they aremostly crystalline and sparingly soluble in water.The methyl-salt,C,oH61*S03Me crystallises from alcohol in prisms melts at 59-60',and is readily soluble in chloroform and ether but only sparingly incold alcohol. The ethyl-salt crystallises from alcohol in hexagonalplates melts at 74" and is readily soluble in chloroform ether andbenzene. The normal propyl salt crystallises in plates and melts a t67" the isopropyl salt in long pi-isms melting at 90". The chloride,C,oHJ-S02CI crystallises from chloroform in large monoclinicprisms melts at 114" and is readily soluble in hot glacial acetic acid,chloroform and benzene but only sparingly in light petroleum. Thebromide crystallises from benzene and chloroform in short prismsThepotassium salt,,C~OH~I'SO~K + H20ORGANIC CHEMISTRY.169melting a t 153". The amide C1,,HGT-SO2-NH2 crystallises fromalcohol in smull scales melting at 239". F. S. K.Specific Volumes of Camphor and Borneol. By M. KUHARA(Chem. News 60 114).-The camphor employed melted at 177.7"(corr.) and boiled at 205.3" (corr.) the borneol boiled at 209.7" (corr.).Numerous determinations of the specific gravities of these two sub-stances were made by filling small glass cylinders with them a t theirreclpective boiling points and weighing when cold. The sp. gr. ofthe camphor was found to be 0.8110 at 205-3" and its sp. vol.187.42; whilst the mean sp. gr. of the borneol is 0.8083 at 209.7",and its sp. vol. 190.5. D. A. L.An Isomeride of Camphor. By 0. WALLACH and A.OTTO (An-nalen 253 249-267; compare this Jour. 1889 1069 1071 and1072) .-In preparing pinene nitrosochloride by the method alreadydescribed (Abstr. 1888 1098) oily bye-products are formed in con-siderable quantity and can be isolated by distilling them with steam insmall quantities at a time. The same oily compounds are obtainedwhen ethyl nitrite is used in the place of amyl nitrite ; experimentsshowed that under certain conditions the former can be advantage-ously employed instead of amyl nitrite in the preparation of nitroso-chlorides.The crude bye-product distils completely between 160 and 190",the principal portion boiling a t 182-186"; it is most probably amixture of cymene and a compound of the composition CIoH160,which the author names pinoZe as will be shown below.PinoZe dibromide CloH,OBrz is obtained in crystals when thefraction boiling at 182-188" is treated with bromine in glacialacetic solution until a permanent coloration is produced and the solu-tion then allowed to evaporate slowly.The mother-liquors from thedibromide contain cyrnene which can be isolated by distillation withsteam. The dibromide separates from ethyl acetate or alcoholicether in rhombic crystals a b c = 0.57 1 1.5553 melts at 94",boils at 143-144" (11 mm.) and is moderately easily volatile withfitearn. It is insoliible in water but readily soluble in alcohol ether,chloroform and ethyl acetate. When boiled with alcoholic potash itis decomposed yielding an oil which is readily volatile with steamand very easily soluble in dilute alcohol.This oil can be separatedinto two principal fractions boiling at 183-184" and at about 210"respectively.The fraction boiling a t 183-184" consists of almost pure pinole,CloH160. It has an odour hardly distinguishable from that of cineole,a sp. gr. of 0.953 at 20° and a refractive power [aJD = 1.46949 at20". It combines energetically with bromine yielding a dibromide(m. p. 94") also with halogen acids and with nitrosyl chloride buti t does not react with acid chlorides hydroxylamine phenylhy-drazine or hydrogen sulphide. It is readily oxidised by warm dilutepotassium permanganate solution yielding carbonic anhydride oxalicacid and terebic acid (m. p. 173-176") ; nitric acid (1 1) convertsi t into terebic acid and resinous products.The dibromide gives th170 ABSTRACTS OF CHEMICAL PAPERS.same oxidation-products as ginole itself but it is only very slowlyacted on by both the reagents. The constitutional formula,/CHP@*CHz\CH-0- CH,'CH = CMe'is in accordance with the observed properties of pinole.The fraction boiling at about 210" consists of impurepinoleglycot ethy2ether C10H160( OEt),. This compound can be obtained in colourless,compact needles by fractionating under reduced pressure coolingthe portion boiling at 110-120" (14 mm.) in a freezing mixture,and spreading the crystals on well-cooled porous plates; it is thendissolved in a little glacial acetic acid the solution poured into water,and the precipitated oil brought into contact with a crystal of the sub-stance.Pinole nitrosochloride C,oH,60,NOCI is a relatively very stablecompound melting at 103" ; it is readily converted into nitrolamineswhich generally crystallise well and thus serve as a means of dis-tinguishing this compound from other nitrosochlorides.Pinolenitrolaniine hydrochloride NOH:CloH150-NH2,HCl separatesafter some time in crystals when the nitrosochloride is treated withexcess of alcoholic ammonia ; i t crystallises well from water and dilutealcohol.The alcoholic mother-liquors from the hydrochloride con-tain the free base which can be isolated by evaporating under reducedpressure extracting the residue with chloroform and distilling theextract under reduced pressure; it is a yellowish liquid boiling atabout 129-130" (14 mm.) with slight decomposition.Pinolenitrolpi~eridine NOH:CIoH,,0*C5NHlo separates from alcoholin crystals melts at 154" and is insoluble in water.The hydro-chloride c,,Hz6O,N,,HC1 is a colourless crystalline powder veryreadily soluble in water.Pinolenitrolbenzylamine NOH:C10H150*NH*C7H7 is best obtained in apure state by decomposing the hydrochloride as it seems to crystallisefrom alcohol with I mol. of alcohol. It crystallises from ether intransparent prisms melts at 135-136" and soon becomes opaque onkeeping but without change in melting point or composition. Thehydrochloride Cl7HZ,O2N,,HC1 is crystalline and readily soluble inwater.Pinolenitrolaniline NOH:C,,H,,O*NHPh crystallises in yellowishplates melts at 174-I75" and is readily soluble in alcohol and ether.The hydrochloride C16H22N202 HCl is crystalline and decomposes onexposure to the air.PinolenitroZ-P-naphthylamine NOH:C,oH,50*NH*CloH7 crystallisesfrom alcoholic ether melts at 194-195" and is insoluble in waterand only sparingly soluble in alcohol ; solutions of the base and itssalts are highly fluorescent.This compound is isomeric withcamphor. F. S. K.Preparation of Aloin. Ry T. WOODRUFF (Pharm. J . Trans. [ S ] ,19 773-775).-The aloes are exhausted with amyl alcohol a t thetemperature of a water-bath when most of the resinous matterORGANIC CEERIISTRY. 171remain in the residue. The liquid is filtered and evaporated andthe aloin is obtained as a crystalline mass contaminated however,with a small deposit of resinous matters.This product is thenexhausted with cold water the solution is filtered and the filtrateallowed to evaporate spontaneously when the crystals are obtainedquite pure. R. R.Cephalanthin a Bitter By E. CLAASEN (Chem. Centr. 1889 ;ii 258 from Pharm. Zeit. 34 384).-The bark of Cephalanthusoccidentalis (" button bush " or " swamp dogwood") a bush belongingt o the Cinchoneae contains a saponin-like substance having abitter taste and tanning properties. For its separation the bark isdigested with lime the filtrate treated with carbonic anhydride andthe cephalanthin precipitated from the solution by hydrochloric acidand purified by treatment with alcohol and ether. It is amorphous,sparingly soluble in cold and hot water readily soluble in alcohol andether and has the properties of an acid.When warmed with nitricacid i t gives a yellow coloration and with concentrated sulphuric acidan orange coloration changing to reddish- brown. Dilute sulphuricacid seems to split up cephalanthin with formation of sugar.J. W. L.Digitalin and Tanghinin. By ABNAUD (Compt. rend. 109,701-703).-1f digitalin is heated in sealed tubes at 180" with waterand barium hydroxide it yields a crystalline compound which is in-soluble in hot water but somewhat soluble in boiling alcohol. Itmelts at 395-310" with rapid decomposition. It has the composi-tion ( C,lH,101,)2Ba and is the barium-derivative of a compoundC31H52011 formed from digitalin by the assimilation of water.Itfollows that the molecule of digitalin is represented by the formulaTanghinin under similar conditions yields a barium-derivative ofthe compound Cj27H44O10 which is formed by the assimilation of 2 mols.H20 by the tanghinin. The molecule of tanghinin is therefore re-presented by the formula Cz,H400s. (Comp. Abstr. 1889 900 andthis vol. p. 65.)C31H60010.C. H. B.Colouring Matters of Chlorophyll. By A. HANSEN (Amz.AgrorLom. 15,428-429 ; from But. Centr. 38,632).-The author pre-pares the yellow and the green constituents of chlorophyll in what hebelieves to be a pure condition by the following process :-Someleaves of grass are boiled in water for 15-30 minutes then washedmany times with water and dried in the dark.The dry matter isextracted with boiling alcohol and the solution saponified by boilingthree hours with a slight excess of aqueous soda ; a current of carbonicanhydride is then passed through the solution which is afterwardsevaporated to dryness on the water-bath. Ether extracts from thissoap the yellow colouring matter only which is purified by evaporatingdown and crystallising from a mixture of equal parts of ether andlight petroleum. The soap after extraction with ether is extractedwith a mixture of alcohol and ether which dissolves only traces of thecombination of the green colouring matter with soda. On addin172 ABSTRACTS OF CHEMICAL PAPERS.another quantity of alcohol-ether and also phosphoric acid the greenmatter is liberated and passes at once into solution from which it isobtained by evaporation in the form of a brilliant fragile greenish-black solid insoluble in water benzene and carbon bisulphide sparinglysoluble in pure ether very soluble in alcohol with strong red fluores-cence.The crystals of yellow colouring matter form orange-redplates insoluble in water soluble in alcohol ether chloroform andbenzene to a deep-yellow colour and in carbon bisulphide to a brick-red. These crystals are transformed in the light into cholesterin.The author considers this yellow substance to be identical with theyellow colouring matter of flowers and fruits in general includingthat of the carrot. J. M. H. M.Dibromoquinolines. By 9. CLAUS and C. GEISLER (J.pr. Chem. [a],40,375-362).-1 4-Dibromoquinoline has been obtained by Metzger(Abstr.1884 757) who asserts that it is identical with La Coste'sdibromoquinoline (Abstr. 1881 74 ; 1882 980). When oxidised bypotassium permanganate it yields only pyridinedicarboxylic acid,which is converted into nicotinic acid (m. p. 229') at 180". It yieldsno methiodide and only one nitro-compound.Nitro-1 4-dibromoquinoZine obtained by nitrating the above com-pound with a cold mixture of two parts of nitric acid (sp. gr. 1.52)and four parts of water forms colourless silky needles melting at 155"(uncorr.) and sparingly soluble in water and cold alcohol but freelyin other solvents. The hydrochloride forms small yellowish crystalsmelting at 228" (uncorr.) when sharply heated. The PZatinochlorideis described.Amido-1 4-dibromopuinoline C9NH4BrZ*NH2 formed by reducingthe nitro-compound with stancous chloride and hydrochloric acid inalcohol distils with steam as small colourless needles melting at 165"(uncorr.). Bromine converts it into a tribromoquinoline melting at174" (uncorr.) perhaps identical with Lubavin's (m.p. 173-175').By directly brominating 1 4-dibromoquinoline a tribromide of meltingpoint 115" (uncorr.) and another substance are obtained.1 3-~ibromoquinoline (La Coste Abstr. 1882 978) forms nomethiodide and only one nitro-compound.4-1Viitro-l 3-diEibromoquinoline crystallises in lustrous leaflets whichhave a greenish shimmer and melt at 162' (uncorr.) ; it forms well-crystallised unstable salts.4-Amido-1 3-dibronzoquinoline crystallises in needles melting at184" (uncorr.).2 4-DibromoquinoZine obtained from symmetrical dibromaniline,crystallises in beautiful white lustrous needles melting at 110"(uncorr.) and freely soluble in the usual solvents except water.Thehydrochloride forms small colourless needles melting at 158". Theplaatiraochloride is described.When 2 3-dibromaniline is quinolised two dibromoquinolines areproduced and are separated by crystallising from ether and sortingthe crystals.2 3-Dibromoquinoline forms prisms which melt a t 95" uncorr. ; itshydrochloride melts at 144" (uncorr.).The platinochloride is describedORQANIC CHEMISTRY. 1733 4-Dibromoquinoline crystallises in slender needles melting at124' (uncorr.) ; its hydrochloride and platinochloride are described.1 2-Dibromoquinoline and Derivatives of 2-Bromoquino-line and 4-Bromoquinoline.By A. CLAUS and G. N. VIS (J.pr.O h m . [2] 40 382-387).-l-Nitro-2-bromoquinoline and 1-amido-2-bromquinoZine have been already described as a-nitrometabromo-quinoline and a-amidometabromoquinoline respectively ( Abstr. 1889,281). The 1 2 :-amidobromoquinoline platinochloride is here de-scribed.1 2- Dibromopziinoline obtained by diazotising 1-amidobromoqnino-line and treating the diazo-compound with cuprous bromide crystallisesin beautiful white needles melting at 112" (uncorr.).4-Bromoquinoline melts at 52" not 48" (loc. a't.) ; it is best obtainedas follows :-The mixture of bromoquinolines prepared from meta-bromaniline (70 grams) is dissolved in warm dilute nitric acid (1 litre),when 2-bromoquinoline nitrate separates ; the mother-liquor is mixedwith potash the precipitatcd oil dissolved in alcohol (100 c.c.) and asolution of oxalic acid (15 grams) in alcohol (25 c.c.) added ; 4-bromo-quinoline oxalate (m.p. 143' uncorr.) crystallises out and is saponifiedwith ammonia to obtain the pure base.The nitro-4-bromoquinoline melting a t 146" (Abstr. 1889 281) is3 4-nitrobromoquinoline; its basic properties are very feeble so thatit is only soluble in concentrated acids and forms no methiodide.3 4-AmicZobromopuinoline forms small yellowish crystals melting a t103" (uncorr.) sparingly soluble in water and dissolving in diluteacids with an intensely red colour ; it gives the carbylamine reactionwith alcoholic potash.ItsplatinochZoride is described. A. G. B.Bromine-derivatives of Quinoline. By A. CLAUS and A.WELTER ( J . pr. Chem. [2]? 40 387-395).-The authors point outthat La Coste's bromoquinoline (Abstr. 1881 741) is not 3-bromo-quinoline but 4'-bromoquinoline and that the dibromoquinoline ob-tained from it is not identical with 1 4-dibrornoquinoline alreadydescribed (above abstract) ; the former dibromoquinoline can also beobtained by brominating 4'-bromoquinoline and is therefore 3 4'-bromoquinoline. A tribromopuinoline melting at 169" (uncorr.) isobtained at the same time.3 4'-DibrornopuinoZine crystallises from alcohol in lustrous silkyneedles melting at 130" (uncorr.).The hydrochloyide forms colour-less four-sided prisms melting a t 185" and easily decomposed bywater alcohol or dilute acids. The nitrate forms colourless needlesand prisms which melt at 158". The platinochZoride and the meth-iodide are described.Generally speaking whenever a bromoquinoline with the brominein the benzene-ring is brominated the new bromine-atom enters intothe 4'-position ; this is the case with anabromoquinoline the 4 4'-dibromoquinoline previously described by Claw and Decker (Abstr.,1889 7259 being obtained. 4 4'-Dibromoquinoline hydrochloride€orms lustrous rhombic tables melting at 183" (uncorr.) and decom-posed by water ; the nitrate crystallises in colourless four-sided tablesA. G. B174 ABSTRACTS OF CHEMICAL PAPERS.melting at 147" (uncorr.).The sulphate the r/tethiodide and themethochloride and its platinochloride are described,2 4'-Dibromoquinoline obtained by heating metabromoquinolinedibromide hydrobromide crystallises from alcohol in beautiful thick,colourless rhombohedra which are strongly refractive whilst immersedin the liquid. The hydrochloride isvery sparingly soluble ; the nitrate forms colourless prisms melting a t178" ; the platinochloride is described ; the methiodide forms micro-scopic needles melting at 271" (uncorr.).1 4'-bromoquinoline has been described by Claus and Tornier(Abstr. 1888 164).It melts at 126-127" (uncorr.).A. G. B.Kynurin. By Z. H. SKRAUP (Nonatsh. 10 726-73l).-Kynurin,an oxidation-product of cinchonine and of cinchonidine but not ofquinine is obtained to the extent of about 10 per cent.of the weightof the cinchonic acid taken when the latter (50 grams) is oxidisedwith a mixture of chromic acid (20 grams) and snlphnric acid(30 grams) dissolved in water (200 grams). The kynurin (hydr-oxyquinoline) thus prepared melts a t 'LOl" and has all the propert.iesof the compound obtained by the direct oxidation of cinchonine.On heating at 100-110" with 1$ times its weight of phosphoruspentachloride it is converted into a chloroquinoline which melts a t34" and is reconverted into kynurin by heating with acidified watei-at 120" ; consequently it cannot be a-chloroquinoline since that com-pound melts a t 38" and is converted into carbostyril on heating withwater.G . T. M.Alkyl-derivatives of 1-Hydroxyquinoline. By E. LIPPMAKNalid F. FLEISSNER (Monatsh. 10 665 67'L).-A molecular cornpoundof methoxyquinoline hydriodide and hydroxyquinoline methiodide,CgNH6*OMe,HI + CgNH6*OH,MeI + 2H2O [OH = 1 ; OMe = 11,is obtained by heating together in sealed tubes at 100" for severalhours a mixture of 1-hydroxyquinoline and methyl iodide in mole-cular proportion with methyl alcohol. It is insoluble in ether butsoluble in alcohol and water crystallising from the former in yellow,triclinic plates decomposes a t 143" gives a hydrochloride,C9NH6Me0,HC1 + CgNH,O,MeC1 4- 5H20 forming miuute red'crys-tals easily soluble in water and a platinochloride C,oH,,N,02,H2PtCI + 2H20 crystallising in orange-red prisms which decompose a t248".Methoxyquinoline-hydroxyguinoline methiodide C20H,gN2021 may Iceprepared by treating the above compound with ammonia or soda.Itcrystallises from hot alcohol in orange-red needles and combines withmethyl iodide to form the compound C21Hz2N20J2 + 2H,O whichcrystallises in yellow needles and is converted by silver Gxide into thedeliquescent compound GOH,,N,O3. The iodide C20H,gN20,1 onreduction with tin and hydrochloric acid was expected to yield kairinand tetrahydroxymethoxyquinoline but only the formation of tlleformer of these compounds could be ascertained. The ethyl-compound,C22H,3N2021 is prepared by a method similar to that used in the caseof the methyl-compound above described. It crystallises i n reORGANIC CHEMISTRY.175needles which melt at 202" and furnishes a platinochloride whichcrystallises with 2 mols. HzO.Quinolineparamethenylaslidoxime and its Derivatives. ByJ. BIEDERMANN (Ber. 22 2761-2767).-&uinolincparamethenylan~id-oxime CgNH6*C(NH,):NOH is formed when paracyanoquinoline(m. p. 135") prepared from paraquinolinesulphonic acid by Fischerand Willmack's method (Abstr. 1884 1051) is treated with hydr-oxylamine hydrochloride aud sodium carbonate in dilute alcoholicsolution. It crystallises from boiling alcohol in yellowish needles,melts at 105" and is readily soluble in alcohol and ether moresparingly in benzene chloroform and hot water and almost insolublein light petroleum. It dissolves freely in acids but is only sparinglysoluble in alkalis ; it gives a greyish-green precipitate with Fehling'ssolution and a deep-red coloration with ferric chloride.In aqueoussolutions silver nitrate produces a colourless crystalline precipitatewhich darkens after some time with separation of silver. The hydro-chloride CloH9N30,HCI crystallises in colourless needles and isreadily soluble in alcohol and water but insoluble in ether benzene,light petroleum and chloroform.(CloHgN30) 2 HzPtCl6,crystallises in well-defined prisms. The ethyl-derivative ClzHI3N30,crystallises from dilute alcohol in colourless needles melts at 85" andis readily soluble in alcohol ether chloroform benzene and hot water,but almost insoluble in cold water. The ncetyl-derivative Cl2HllN3O2,prepared by treating the amidoxime with acetic chloride in ethercalaolution crystnllises from hot benzene in colourless needles melts at115" and is sparingly soluble in alcohol ether chloroform andbenzene and almost insoluble in cold water.G.T. M.The platin,ochloride,f&?uinolineparamethenylethenylazo~nae c,NH,*c<?$&Me pre-pared by dissolving the amidoxime in hot acetic anhydride or bydigesting the acetyl-derivative with alkalis or water crystallises fromdilute alcohol in slender needles melts at 175" and is soluble inalcohol ether benzene and chloroform but almost insoluble in water.It gives with ferric chloride a bluish-violet coloration and mercuricchloride and auric chloride produce precipitates in a hydrochloricacid solution.E t hy 1 puinolinep arameth en y 1 amidoxiin ecarbolc y late,CgNH6.C (NHZ) :NO.C 0 OE t,is formed when the amidoxime is treated with ethyl chlorocarbonatein chloroform solution.It crystallises from boiling alcohol in colour-less needles melts a t 97" and is soluble in ether chloroform benzene,and acids but almost insoluble in light petroleum and cold water,and insoluble in alkalis.Quinolineparamethenylcarbon ylamidoxirne CgNH6*C<NH N-0 > co pre-pared by boiling the preceding compound with alkalis or by digestingthe amidoxime with excess of ethyl chlorocarbonate crystallises fro176 ABSTRACTS OF CHEMICAL PAPERS.boiling benzene in colourless needles melts at 155" and is soluble inalcohol ether chloroform and alkalis but almost insoluble in coldwater.In aqueous solutions of the ammonium-derivative coppersulphate produces a green lead acetate and silver nitrate a colourless,crystalline precipitate.CgNH6- C (NOH)*NH*C ONH2,separates in colourless ci-ystals when a concentrated aqueous solutionof the amidoxime hydrochloride is treated with potassium cyanate ;i t crystallises from boiling water in small coiourless needles melts at164-5" and is only sparingly soluble in cold water and acids butmore readily in hot water alcohol ether benzene light petroleum,and alkalis.Quinolinepuramet heny lurainidoxinz e,Quinolineparametheny 1 b enzen y 1 azoximeparacarbox y lic acid,prepared by melting the amidoxime with phthalic anhydride crystal-lises from hot alcohol in colourless needles melts at 203" and issoluble in ether and chloroform but only sparingly in benzene andwater and almost insoluble in light petroleum.F. S. K.a-Cinnamenylcinchonic Acid and 2 4-QuinolinedicarboxylicAcid. By 0. DOEBNER and J. PETERS (Ber. 22 3006-3011)-a- Cinnamelz y lcinchoizic acid C HP h CH. C < N-y6& is preparedby gradncllly adding from a dropping funnel an alcoholic soh-tion of aniline (52 grams) to a. solution of cinnamaldehyde (75 grams)and pyruvic acid (50 grams) in absolute alcohol. The whole is boiledin a reflux apparatus on a water-bath for four to five hours; theliquid is then concentrated and the crystals which separate washedwith ether and crystallised from hot alcohol. The yield is 10 grams.The acid crystallises in yellow needles melts at 295" wit,h evolu-tion of carbonic anhydride is insoluble in water sparingly solublein ether benzene and chloroform more soluble in hot alcohol,especially if a few drops of hydrochloric acid are added.The acidsolution has a green fluorescencc. The potassium sodium andammonium salts are readily soluble ; the magnesimn salt,(CleH,zN02)2Mg crystallises in concentrically-grouped lustrous,yellow needles; the silcer salt is a flaky precipitate; the nickel andcopper salts are yellowish-green and the zinc and lead salts yellow.When the acid is distilled it decomposes into benzylidenequinaldine(Jacobsen and Reimen Abstr. 1884 335) and carbonic anhydride.Cinnamenylcinchonic acid is also formed by heating =-methyl-cinchonic acid with benzaldehyde and zinc chloride and by the actionof aniline on pyruvic acid and cinnamaldehyde at the ordinarytemperature. In the latter case an indifferent compound of theformula C2rHzoNz0 is obtained which crystallises from glacial aceticacid in yellowish needles melting at 194".2 4-Quinoliitedicarboxylic acid CgNH,( COOH)2 is obtained byadding a solution of potassiam permanganate (7-5 grams) inwater (500 c.c.) to a solution of a-cinnamenylcinchonic acid inCH C C 0 OHORGANIC CHEMISTRY.177soda diluted to 500 C.C. After 24 hours i t is filtered evaporateddown to one-third of its bulk treated with dilute hydrochloric acid,and allowed to cool. The acid separates in slender needles and iscrystallised from water. It melts at 246' with decomposition issparingly soluble in cold water alcohol and ether insoluble inhenzene and chloroform.The calcium salt C,,H,NO,Ca crystallisesiu slender white lustrous needles ; the barium salt forms gronps oflong needles ; the copper salt (with 1 mol. H,O) is a sparingly soluble,hluish-green precipitate ; the silver salt is a very gelatinous whiteprecipitate other salts were prepared. When the acid is heatedabove its melting point i t partly sublimes and is partly decomposedinto quinoline and carbonic anhydride.Hydroquinoline-derivatives. By 0. SRPEK (Monatsh. 10,701-729).-A solution of the hydrochloride of quinic acid (20 grams)in concentrated hydrochloric acid (100 grams) was mixed with stan-nous chloride (10 grams) and then heated with metallic tin (28grams).When the metal had dissolved the solution was saturatedwith hydrogen sulphide to precipitate the tin filtered and concentratedi n an atmosphere of carbonic anhydride whereby the hydrochlorideof tetrahydmquininic acid CllHI3NO3,H C1 crystdlising in smallneedles melting at 205-206" (uncorr.) separated out. The acid hasprobably all four but certairily two hydrogen-atoms attached to theyyridine nucleus since it gives an acetyl-derivative Cl1Hl2AcNO,,melting at 240-241" (uncorr.) and therefore contains an imidogen-group. On treatment with bromine the acid furnishes what is probablyan additive product which has a red colour and on treating this w i t hhot hydrochloric acid washing with water boiling with sodiumhydrogen sulphite and recrystallising from xylene it gives tribromo-quinanisoil C10H6Br3N0 a substaitce which crystallises in whiteneedles melts a t 233" and is identical with the compound obtained bySkraup from thalline ; on heating it with concentrated hydrocliloricacid first a t 150" and afterwards at 170"-1~0" it gives a tdromhcydr-oxyquinoZine.This tribromhydroxyquinoline crystallises from aceticacid in needles melting at 818" (uncorr.) and is also produced,together with tribromoquinanisoil on bromination of thalline hydro-chloride.Tribromoquinanisoil is oxidised by boiling concentrated nitric acidto a bromop~ridinecarboa~Zic acid which melts at 182" (uncorr.) andproves to be identical with the bromonicotinic acid obtained by Clansand Collishonn (Abstr.1887 158). Tribromohydroxjquinoline isconverted by potassium perrnangmate into a bromoquinolinic acid,C,H2Br(COOH)2 + H20 which appears to be identical with the acidobtained by Claus and Collishonn (Zoc. cit.) and decomposes at 165"into carbonic anhydride and the above-mentioned bromoiiicotinic acid.On fusion with potash these bromonicotinic acids furnish an acidfree from bromine and 4'-hydroxypyridine. The tribromo-compoundsmust consequently be regarded as having one bromine-atom in the4'-position of the pyridine nucleus and the other two atoms in thebenzene niicleus.Tetrah y drobroinhy d w x yq uinoline hydrochloride C,N H,Br 0 H HCl,VOL. LVIIL. nN. H. M t 78 ABSTRACTS OF CHEMICAL PAPERS.which crystallises in needles melting at 238" is obtained on rediicingtribromohydroxyquinoline with tin and hydrochloric acid.G.T. M.Formation of Azines from Orthodiamines and Polyamines.By R. NIETZRI (Ber. 22 3039-3040).-A discussion of the bearingof recent work on this subject.Derivatives of Ortharnidobensyl Alcohol. By H. G. S~DER-BAUX and 0. WIDMAN (Ber. 22 2933-2942).-The platinochlorideof the benzophenyldihydroketometadiazine previously described(Ahstr. 1889 973) forms prismatic crystals melting with decomposi-tion a t 199" ; the awochloride yellow needles melting at 170-172". - I CHz.NMePhenometh~ldihydrothiometadiazl:ne C6&<NH As is formed byheating orthamidobenzyl alcohol with methyl thiocynnate in benzenesolution. Hydroxytolylmethylthioc.arbamide is first formed as a brownoil which becomes thick on cooling b u t does not crystallise and if thisis heated with hydrochloric acid it is converted into the diazine whichcrystallises from methyl alcohol in long glistening needles and meltsat 139".The platinochloride crystallises in four-sided plates meltingwith decomposition a t 195" ; the aurochloride forms yellow microscopicneedles melting a t 1.51-153".w-Hydroxytolyl~thylthiocarbamide formed like its methyl analogue isalso an oil and with hydrochloric acid yields phenethyldihy drothiometadi-CHz'yEt which crystallises from alcohol in long needlesNH* CS azine C6Ha<melting a t 103". The platinochloride is a pale-yellow powder meltingat 208" ; the aurochloride forms crystals melting at 118".When the methylthiocarbamide is heated with mercuric oxide itThis is yields phenomethzJldih2/droketometadiazine C6H4<easily solublc i n organic solvents sparingly SO in waker. The platino-chloride ( C,H,~,0),,H,PtC16 crystallises in needles or plates meltingat 202-203" the aurochloride ( C9HloN20),HAuC14 in yellow glisten-ing prisms melting a t 185".The ethylthiocarbamide in like manneryields phenethyldihydroketometadiazine which crys tallises from alcoholin flat colourless needles and melts at 94-56". The platinochloridecrystallises in yellow needles melting with decomposition at 205" ; theaurochloride forms golden-yellow scales melting a t 116-118".C Hz*T MeNH*CO *Phenallyldihydroketometadiazine C6H4<NH. CHz*T*C,H co prepared fromthe allylthiocarbamide is very soluble in alcohol crysfallises inmicroscopic prisms and melts a t 77-78". The platinochloride crystal-lises in needles and melts at 169-171'.CH,*rPh prepared from NH-CO Benzophenodihydroketometadiazine CsHa<the benzothiocarbamide crystallises from alcohol in needles or prismsmelting at 145-146". It forms a crystalline platinochloride and auro-chloride.All attempts to obtain phenodihydrothiodiazine proveORGANIC CHEMISTRY. 179futile. The author points out the regularity of the melting points inthese thio- and oxy-series.When oxidised with chromic acid in acetic acid solution phenodi-CO.S;IHhydroketometadiazine yields benzoylencarbamide C6H4<NH co 9described by Griess and by Abt.The formation of these two groups of compounds appears at firstsight to be analogous to that of the pseudo-carbamides lately describedby Gabriel (Abstr.1889 848). But after a careful examination ofthe evidence the author concludes that the formula ascribed by himto the diazine is correct and that his and Gabriel's compounds arenot strictly analogous.Codeine Methiodide. By Z. H. SKRAUP and D. WIEGMANN(Monatsh. 10 732-733). It has been previously shown (Abstr.,1889 1018) that in all probability the nitrogen-atom in morphine hasboth a methyl- and an ethyl-poup directly attached to it. If thisview is a correct one codeine methiodide which on heating withalkalis is converted into methylmorphemethine should give rise toethyldimethylamine when treated with alcoholic potash and not todimethylamine (the product said to be obtained by Knorr Abstr.1889.417). On repeating Knorr's experiments the authors find thatethyldimethylamine together with a small quantity of trimethylamine,is really produced and furnishes a characteristic platinochloride,which is sparingly soluble with alcohol and crystallises from water inoctahedra melting at 193". G. T. MI.Oxidation-products of Quinoidine. By H. STRACHE (Monatsh.,10 642-646 ; compare Abstr. 1889 1016).-When quinoidine (800grams) is oxidised by boiling with commercial nitric acid (about 26kilos.) added a little at a time until the solution is no longer renderedturbid by ammonia a mixture of a-pyridinetricarboxylic acid(73 grams) cinchorneronic acid (48 grams of the hydrochloride),aud cinchonic acid (34 grams) is obtained.At the sa.me time a hydro-chloride of a nitroquinolinecarhoxylic acid is formed which onsnblimation gives a ni troquinoline crystallising in needles melting at153-154". The properties of this base agree with those of La Coste's4-nitroquinoline. G. T. M.L. T. T.Action of Potash on Alkyl Halogen-derivatives of Papa-verine. By G. GOLDSCHMIEDT (Monntsh. 10,673-69l).-The authordefends the views of Stransky (Abstr. 1889 166) against those ofClans and Edinger (ibid. 415) and has made the following observa-tions on repeating Stransky's experiments. According to Claus thebases obtained on treating the alkyl halogen additive products ofpapaverine with silver oxide and with potash respectively differ con-siderably for whereas the hydrochloride a11d alkyl chlorides of theformer give a platinochloride which is crystalline anhydrous andmay be crystallised from hot water the hydrochloride of the lattergives a platinochloride containing water of crystallisation and whichreadily decomposes when attempts are made to recrystallise it fromn 180 ABSTRACTS Ol!' CHEMICAL PAPERS.boiling water.Clam and Edinger obtained from the methyl base anuncrystalJisable platinochloride containing 1 mol. H20 and Hutleinfound that the ethvl base gave a crystalline platinochloride also con-taining 1 mol. H20. The author shows that the platinochloride ofethylpapaverinium oxide ( CmH21N04Et,)2PtC16 + 3$H20 prepared bymeans of potash and the corresponding methyl-compound,similarly prepa.mil are both stable in presence of boiling water whilstthe methyl-compound obtained by means of silver oxide is ananhydrous salt. On the other hand the liydrobromide obtained byStransky from ethylpapaverinium oxide and hydrobroinic acid iscrystallographically identical with the papaverine ethyl bromide pre-viously described by the author. Of these apparently coiitradictoryfacts no explanation can at present be offered.Claus and Hutlein have expressed the opinion that during the actionof potash on the alkyl halogen-derivatives of papaverine the alkyl-groups swing from the nitrogen- to a carbon-atom ; the author how-ever finds that ethylamine is formed by boiling pspaverine ethylbromide with potash ; at the same time a compound melting at 240",and also one melting at 186-187" cryatallising from alcohol in whiteneedles having the formula CIgH,o05 or ClgHl& and containingfour methoxyl-groups are formed.Papaverinic and Pyropapaverinic Acids. By G. GOLDSCHMIEDTand H. STRACHE (Monatsh. 10 692-700; compare Abstr. 1888,302) .-Correcting a previous communication (Abstr. 1886 4 i 9 ) theauthors state that papaverinic acid (Abstr. 1885 lOSO) C,,H13N0,,crystallises with 1 mol. H20 and furnishes a ketoxime C16H14NZ0,,which crystallises from alcohol in small needles melting at 154-157".Ammonium pyropapaverinate gives precipitates with many metallicsalts and may be used to prepare the undermentioned compounds:Calcium pyropapaverinate ( C15H,2N0,)2Ca + 4 H20 crystallises ingroups of needles ; barium pyropapaverinate ( C15EI12N05)2Ba + 4H20,in plates ; the hydrochloride C1,H,sN05,HC1 + H,O crystallises inoisange-red needles ; the phenylhy drazone C15H,,N04:N2HPh crystal-lises from alcohol in yellow prisms softens and turns red a t 210°,melts with decomposition a t 223" and forms a hydrochloride,G. T. M.C l,H13NOa:N,HPh HC 1,a vermilion-coloured powder. The ketoxime of pyropapaverinic acid,C15H14N205 crystallises from alcohol in needles melting ah 266" itshydrochloride C15H14N205,HC1 + H20 crystallises in lemon-yellowneedles which lose HC1 and HZO when heated at 105" and areslowly decomposed on boiling with water. G. T. M.Ulexine. By A. W. GERRARD and W. H. SYMONS (Pharm. J. Trans.[ 3 3 19 1029-1030).-Ulexine C11H,4N20 the alkaloid previouslyobtained by the authors from the seeds of the common furze UlexEuropceus (Abstr. 1886 1048) forms colourless odourless deli-quescent crystals freely soluble in chloroform but insoluble iORQANlC CHEMISTRY. 181absolute ether. The. substance fuses at 151" and begins to char a t175". It is a strongbase for it precipitates quinine coca'ine and strychnine and alsoliberates ammonia from its compounds.It cannot be sublimed without decomposition.The platinochloride,(C,lH,,N,o)2,H2PtC1,,forms lustrous crystalline plates ; the aurochloride CllH,,N,O,HAuC1,,was also analysed.When ulexine is treated with alkaline permanganate it gives offtwo-thirds of its nitrogen as ammonia. Ulexine has a powerfulphysiological action and ane-tenth of a grain has been found to pro-duce toxic effects. It raises arterial tension produces diuresis andacts as a nerve and muscle poison affecting the respiratory organsespecially.A second base seems also to occur in the seeds but has not yetbeen obtained in quantity sufficient for examination. R. R.Bile-Pigments. By J. B. HAYCRAFT and H. SCOFIELD (Zeit. physiol.Chem. 14 I7;<-181).-When bilirubin is oxidised biliverdin isformed ; if the oxidation be carried further as by nitric acid a bluepigment bilicyanin is formed then a violet (perhaps a mixture of theblue and red) then a red and lastly a yellow pigment (chaletelin) areformed. There have been however very few experiments recordedin which by means of reducing agents the lower terms of the serieshave been obtained from the higher. Lauder Brunton (Hudb. ofPhysiot. Lab. p. 498) alone mentions that sulphuric acid colours analkaline solution of bilirerdin yellow and that if this pellow solutionis then treated with nitric acid a solution of bilirubin is obtained.In the present research it was noticed that ox bile on being allowedto remain for some hours changed in colour fram green to orange-brown. This is regarded as reduction for it' nitric acid be added toit bilirubinis first obtained and then the usual' series of green blue,violet red and yellow pigments. It was also noticed that the bile inthe gall-bladder was yellowish where it came in contact with the wallof that viscus ; this is an instance of reduction brought about by livingtissues Another instance of reduction is the presence of gall-stones coloured by bilirubin in the bile of the ox of which the naturalpigment is biliverdin.Experiments were then carefully performed in which bile wasobserved under different conditions in the air in closed sterilisedtubes mixed with pieces of mucous membrane and so forth fromwhich the following conclusions are drawn :-That biliverdin partswith its oxygen as easily as oxyhaemoglobin ; in steriliscd vessels thereduction stops at bilirubin ; the reduction is hastened by exposure tolight putrefaction and admixture with mucus or mucous membrane,but hindered by darkness and drying the bile. When putrefactionoccurs reduction goes on to the formation of a brownish pigment,which gives no play of colours with Gmelin's test but which differsfrom hydrobilirubin by being insoluble in ether and easily soluble inalcohol. It moreover shows no absorption-bands. Copeman andWinston (Abstr. 1889 792) have observed that human bile is olive182 ABsTRACTS OF CHEMICAL PAPERS.green ; probably this undergoes reduction after death ; hence thepigment usually described in human bile is bilirubin.The play of colours can be obtained at the positive pole of a battery(4 Grove cells) placed in the bile indicating successive stages ofoxidation ; if the negative pole be then placed in the bile the seriesis reversed indicating reduction.Preparation of Crystalline Egg-albumin. By F. HOFME~STER(Zeit. physiol. Chem. 14 165-172).-Fresh white of egg freedfrom membranes was mixed with an equal volume of saturatedsolution of ammonium sulphate to precipitate the globuliu andthe filtrate allowed to evaporate in flat dishes at the ordinary tem-perature. In a few days st deposit of granules or scaly aggregationsof g r a d e s was observed and later needles or stellate collections ofneedles were mixed with these. Whether these are pure egg-albuminor a compound of egg-albumin with ammonium sulphate and whetherother animal prote'icls act similarly are questions which have still tobe investigated. Remarks on the differences between colloids andcrystalloids and the necessity of modifying our ideas concerning thisdifference conclude the paper.Peptone and Similar Substances. By J. SERELIEN ( B i dCentr. 1889 71 7-718).-Pure milk csse'in was digested with peptoneand hydrochloric acid the nuclein filtered off all albumoses sepa-rated by ammonium sulphate and the resulting filtrate mixed withtannin. The precipitate thus obtained was decomposed by baryta-water and then the barium removed. A solution of pure peptonewas thus obtained and was only precipitated by alcohol phospho-tungstic acid and tannin and was redissolved by excess of thelatter. Optical estimation of the amount of peptone present indicateda percentage of only 1.2-2-7 per cent. which was obviously too low ;hence it was concluded that the compound was almost or even quite,inactive. E. W. P.W. D. H.W. D. H

ISSN:0368-1769    

DOI:10.1039/CA8905800116

出版商:RSC    

年代:1890

数据来源: RSC

摘要:

182 ABsTRACTS OF CHEMICAL PAPERS. P h y s i o l o g i c a l Chemistry. Calorimetric Investigations on Heat Production in Animals. By J. ROSENTHAL (Arch. Anat. PhySiol.,.physiol, Abth., 1889, 1-53). -A long account of investigations relating chiefly to the influence of body weight and food on the production of heat, together with full descriptions of the methods employed, including that of the air- calorimeter. W. D. H. Conditions of Absorption of various Haemoglobins. By S . JOLIN (Arch. Anat. Physiol,, phpiol. Abth., 1889, 265--SSS).- Bohr (Ludwig’s Festschrift, 1886) has shown in experiments with the baemoglobin of the dog, by the use of st new absorptiometric method, how the dissociable unions of hsmoglobin with oxygen and with car-PHYSIOLOGICAL CHEMISTRY. 183 bonic anhydride vary with differences of pressure.This is not strictly proportional to the pressure, but falls at first slowly, but with low pressures (below 20 or 30 mm. of mercury) very quickly. This can be represented graphically by a curve constructed from abscissae representing the pressure, and ordinates represent,ing the amount of gas absorbed by 1 gram of hemoglobin; the curve so ob- tained with oxygen is quite differeut from that obtained with carbonic anhydride. In the present research, the same methods were applied first to guinea-pig’s hemoglobin, which crystallises in rhombic tetrahedra, not in prisms, as dog’s henioglobin does ; and secondly with goose’s hernoglobin, as an instance of blood pigment occurring i n nucleated red corpuscles. In the first case, the results obtained were practically the same as in Bohr’s researches, the difference of crystalline form causing no difference in the type of the curves produced, the general conclusion being that there are two possible compounds of each of the gases with the hslsmoglobin.With regard to the second series of experiments, those with birds’ haemoglobin, the curves are in respect to both gases of a character different from those obtained with mamma- lian blood pigment. The curves are flatter, and show that the quan- tity of gas absorbed in the first place is less, and in the second place does not increase with the pressure beyond a certain point, namely, 95 mm. in the case of oxygeu, 65 mm. in that of carbonic anhydride. W. I). H. Gases in the Swimming-bladder of Fishes. By M.TRAUBE- MENGARINI (Arch. Anat. Physiol., physiol. Abth., 1889, 54--63).-1f fish are placed in water containing hydrogen in solution, the swim- ming-bladder, whether it be of the open or closed variety, becomes in a few hours filled or partially so with the gas. This fact shows that the gases of the swimming-bladder are more or less directly obtained from water in which the fish is living. W. D. H. Digestion in the Pig. By ELLENBERGER and HOFMEISTER (Arch. Anat. Physiol., physiol. Abth., 1889,137-153).--This is an account of experiments on the pig carried out on the same lines as previous experiments by the same authors on other animals. The anatomy of the stomach, the process of digestion with different foods in different parts of the alimentary canal, and the process of absorption are de- scribed.With regard to gastric digestion, an important point made out is that the proteolytic period is preceded by a period in which no secretion of acid takes place, and when amylolytic action proceeds freely. W. D. H. Absorption of Fat in the Intestine. By A. GRUENHAGEN and RROHN ( B i d Centr., 18, 617-619 ; from Arch. Phys., 24, 535-545). -The author showed some time ago that the epithelium cells of the intestine cut, out of a frog, as well as those in the living organism, are capable of taking up drops of fat from the intestinal tube filled with fat or emulsion. The experiments were made with frogs which had not been fed for184 ABSTRACTS OF OHEMICAL PAPERS. some time, so that the intestine should be free from food constituents. The substances employed were milk, olive oil, lanolin emulsion, and, to determine whether the epithelium absorption is confined to fatty substances (Funke's view), a solution (?) of the finest Chinese ink.The results of the experiments show that the assumption of a me- chanical activity of the epithelium of the intestines in taking up of fat is inadmissible, inasmuch as only fat and not even the finest grains of other substances enter into the protoplasma of the border cells. It is also established that the intestinal epithelium of hiber- nating frogs forms a store place for excess of fat, and wiIl retain fatty substances enclosed in it with great tenacity. Origin of Urea in the Animal Economy. By F. COPPOLA (Chew. Centr., 1889, ii, 375 ; from Rend.Acad. dei Lincei [4], 5, 1).-A dog was fed with an insufficient amount of bread f o r a month, a t the end of which time its weight remained constant. The urea and acidity were determined in the voidings f o r five days, and then varying quantities of cyanuric acid were administered in addition to the daily ration of bread, the urea and acidity being still determined. The administra- tion of the cyanuric acid had no influence on the weight of the animal. Up to 1 gram of administered cyanuric acid, the amount of urea increased ; an excess of this amount had no further influence on the quantity of urea formed. Some of the cyanuric acid passed away with the excreta, and the total acidity increased with the amount of cyanuric acid administered. The author concludes that one part of the cyanuric acid is changed into carbimide, which is further decom- posed into water and carbonic anhydride, the ammonia then com- bining with a second portion of cyanuric acid, with formation of urea.J. W. L. N. H. M. Origin of Uric Acid in Mammals. By J. HORBACZEWSKI (Nonatsh., 10, 624-641) .--Since uric acid is a derivative of acrylic acid, and is produced in abnormally large quantities when glycerol is taken internally, it was thoaght probable that it might be built up spthetically in mammals from acrylic acid, and some nitrogenous compound, such as urea. In order to ascertain whether this was the case, sodium acrylate was mixed with the food of a strictly dieted subject, but no iucrease in the quantity of uric acid formed could be observed.The urine, however, showed indications of becoming alkaline, a result probably due to the formation of sodium carbonate from the sodium acrjlnte. Minkovski has suggested (Arch. exper. Path. Phann., 21) that in birds the formation ot uyic acid is probably due to some function of the liver, whereby the acid is built up from lactic acid and ammonia, but the author now shows that in the case of men whose death results from cirrhosis hepatis, the amount of uric acid formed does not vary with the progress of the disease, and that mixtures of fresh spleenic juice and defibrinated blood, obtained from recently-killed calves, through which, a t 37-40", a slow stream of air is passed, give rise to very considerable quantities of uric acid. This result is not produced by the blood alone, and must be regarded as due to a function of thePHYSIOLOGICAL CHEMISTRY.185 spleen, which perhaps uuder some circumstances brings about the degradation of the white corpuscles of the blood. Changes in the Glycogen, Sugar, and Lactic Acid of the Muscle while performing Work. By A. MOLINARI (Chem. C‘entr., 1889, ii, 372-373, from Ann. Chim. Fawn., 9,351-366).-T he mnscles of two dogs, one of which had rested and weighed 20.5 kilos., whilst the other had run 92 kilometres (57 miles) and weighed 25.5 kilos., were analysed, and the respective amounts of glycogen, sugar, and lactic acid determined. The glycogen was estimated by Wind- gradoff’s method. In the filtrate from the precipitated glycogen, the sugar was deter- mined by Fehling’s solution.The lactic acid was estimated by two methods. By the first, 350 grams of muscle is extracted with water, concentrated somewhat, 99 per cent. alcohol added, the filtrate dis- tilled and concentrated, and the residual alcohol-free liquid diluted with a little water. A slight excess of lead acetate is added, the filtrate and washing concentrated in order to allow the creatine to crystallise out, the mother-liquor acidified and extracted with ether, the ether distilled off, the residue dissolved in a litkle water, powdered zinc oxide added, the filtrate again concentrated, and treated with four or five volumes of 99 per cent. alcohol, and the precipitate filtered off, dried, and weighed. I n the second method, baryta is used to remove the phosphates.The results obtained by the two different methods did not agree very closely, and the author recommends the former as the more exact. In the muscles of the tired dog, less glycogen and lactic acid b u t more sugar was found, showing that the lactic acid is not formed from the glycogen. Diastatic Ferment of the Liver. By KAUFMAXN (Compt. rend. SOC. Bid. [9], 1, 600- 603).-Bernard first advanced the doctrine that the hepatic glycogen is transformed into sugar by a ferment which is separable from the liver substance. Recent observations by Dastre (and others not quoted) have thrown doubt on the existence of such a special ferment. In the prcsent research, i t was sought to further elucidate the question by examining the secretion of the liver, not the liver substance itself.Dog’s bile was found to be free from a saccharifying ferment. Cat’s bile was feebly saccharifying. The bile of the pig, sheep, and ox was found to be powerful in coriverting starch into sugar. These facts are considered as additional evidence that a diastatic ferment is formed by the liver ; the dog, however, is supposed to transform its glycogen into sugar by some other means. W. D. €3. G. T. M. J. W. L. Quantity of Iron in the Spleen and Liver of Young Animals. By L. LAPICQUE ( C o ~ ~ p t . rend. SOC. Biol. [9], 1, 510-512). -The spleen of young animals is poor in iron. Four rabbits born a t the same time were taken. Intravenous injection of distilled water was performed on two of these in order to destroy some of their red- blood corpuscles ; their spleens contained respectively 0.24 and 0.26 parts of iron per 1000 ; the amount of iron in the spleens of the other186 ABSTRACTS OF CHEMICAL PAPERS.I n blood. two animals, which served as control specimens, was 0.4.4 and 0.19 per 1000 respectively. Estimations wei-e then made to determine if the quantity of iron in the liver varies with age. The organs were in each case freed from blood, and the results were a8 follows :- The result is thus an uncertain one. I n liver. Age of rabbit. Weight in kilos. Parts of iron per 1000. 8 day8 ................ 11 days.. .............. 21 days.. .............. 3 months ............. 3 months ............. 3 months ............. 0 -120 0 -137 0 *320 1 *170 1 -350 1.360 0 -45 0 -40 0 *41 0 *42 0 *36 - 1 ‘00 0.20 0 *14 0 *043 0.035 0 *OM The quantity of iron thus diminishes with the age of the animal.W. D. H. The Physiological R6le of Lactose. By A. DASTRE (Compt. rend. SOC. Bid. [9], 1, 145--149).-Although lactose is so important as a food, it is stated that very little is known of the part i t plays in the organism. The present communication relates to the question whether lactose is itself assimilable. The conclusion arrived at is that which others have found before, that lactose is not directly assimilable, but is first inverted in the alimentary canal. What agent accomplishes this change is still uncertain. After injecting into the circulation a mixture of galactose and glucose, a small quantity of the sugar which is not utilised passes into the urine. This sugar is a reducing one, but does not undergo the alcoholic: fermentation.Its nature is, however, uncertain. W. D. H. By F. REINITZER (Chenz. Centr., 1889, ii, 292-293, from Ber. deut. bot. Gesell., 7, 187--196).-The author contends that the assertion of Kraus (Abstr., 1889, 917), that the tannins of various origins are physiologically alike, is not correct, and that the methods at present employed for the determination of tarinin are not suitable for physiological investigation, however useful they may be for the practical valuation by the tanner. By P. SPALLANZANI (Chem. Centr., 1889, ii, 339-341, from Staz. sperem. agric. ital., 16, 277- 293).-The author has carried out an investigation into the cause of butter fat containing so variable a quantity of volatile fatty acids.Four different breeds of cows, namely, that of the Province Reggio d’Emilia, Dutch, Schwitz, and Simmenthal, were employed and fed exactly in the same way. The cream of the milk of the several different breed8 was separately churned, as wm also cream which was 12 hours, and that which was 36 hours old. Further, the influence of leiigth of time from calving, the sudden changing of food, and the Physiology of the Tannins. J. W L. Volatile Fatty Acids of Butter.PHYSIOLOGICAL CHEMISTRY 187 age of the butter, with regard to the quantity of volatile fatty acids in the butter, was investigated. The amount of volatile fatty acids, expressed in terms of C.C. of deci- normal alkali per 5 grams of butter fat, varied from 20.63 to 30.60. Nor could any regularity in the quality of butter obtained from the different sources be observed.The butter from cows stationed at high lying places contained usually more volatile fatty acids than that from low lying stations. Of the different breeds t h a t of Schwitz gave butter containing most fatty acids, then followed the breeds Simmenthal and Reggio, alike ip this respect, and last the Dutch. Lastly, with regard to the influence of length of time since calving, the percentage of fatty acids declined as this period advanced. J. W. L. Urobilin in the Bile. By J. WINTER (Compt. rend. SOC. Biol. 191, 1, 139).-In reference to the method adopted by Engel and Kiener (Abstr., 1889, 637) for the separation of urobilin, it is pointed out that the precipitates of the biliary constituents produced by adding calcium salts, especially the phospbate, carry urobilin down with them.The final filtrate, even in urines rich in urobilin, is always colourless. The conclusion drawn by Engel and Kiener, that urobilin is absent from the bile, is therefore not proved, as their method was one unsuited for discovering small quantities of that pigment. W. D. H. The Behaviour of Tgrosine Ethyl Ether in Animal Meta- bolism. By R. COHN (Zeit. physiol. Chern., 14, 189--202).-Con- sidering the amount of proteid daily ingested by an animal, the amount of tyrosine formed cannot be inconsiderable. Blenderniann (Ahstr., 1883,876)md Jaffe (Zeit. physiol. Chem., 7 ) by feeding animals with tyrosine could, however,find no increase in the aromatic substances in the urine, nor indeed any constant relation between tyrosine or any urinary constituent.Baas (Abstr., 1887,1133) found no increase in the hippuric acid secreted in similar experiments. I n the present experiments on dogs and rabbits, the tyrosine ethyl ether hydro- chloride was injected both subcutaneously and intravenously. Large doses acted fatally : but no tyrosine was ever found in the urine or bile ; nor was there an increase in aromatic hydroxy-acids, pbenol, or hippuric acid. It is thus probable that tyrosine undergoes complete destruction in the organism. W. D. H. Determination of Potassium in Urine as Potassium Hydrogen Tartrate. By A. ROBIN (Compt. rend. Soo. Biol. [9], 1, 356-363).- When the potassinm in urine is estimated by the weight of the pre- cipitate obtained by adding tartaric acid to concentrated urine, the results obtained as compared with those obtained from the platinic chloride method are fouud to be from 9 to 70 per cent, too high.All conclusions drawn from such estimations are therefore null. Roger and Gaume have stated that the output of potassium salts is increased i n ague and certain other diseases ; their conclusions regarding this subject, and also regarding the toxicity of urine from the presence in it of potassium salts, rest on experiments performed by the tartaric188 ABSTRACTS OF CHEMICAL PAPERF. acid method. The precipitate produced by tartaric acid in urine carries down with i t uric acid, hippuric acid, albumin, and other organic substances. W. L). H. Reducing Substances in Urine. By GAUBE (Comnpt.rend. SOC. Bid. [9], 1, 383--390).--Various urines were examined with regard to the substances in them that reduce alkaline solutions of cupric hydroxide. I n one case, that of an emaciated child, the reducing substance is stated to ha,ve been aldehyde. The following stat,ements are also made :-In acetonzemia and acetonuria, lactic acid exists in the urine, in combination conjointly with phosphoric acid, producing acid salts, principally of potassium, to which the acidity of the urine in these cases is chiefly due. Lactose is said to be met with in the urine of cases of what the author terms oxycrasia. W. D. H. Benzamide in Urine after Administration of Benaaldehyde. By R. COHK (Zeit. phys':oZ. Chenz., 14, 203--808).-After feeding dogs on benzaldehyde (10 grams per diem), the urine was collected, extracted with hot alcohol, the extracts evaporated, and the deposit dissolved in water strongly acidified with sulphuric acid.This was shaken with ether ; the ethereal extracts concentrated, and the hippuric acid so deposited filtered off. The ether was distilled off, and the small crystalline residue was dissolved in a concentrated solu- tion of sodium carbonate, and again shaken with ether ; the ether was again evaporated, and the crystalline residue was recrystallised from hot water, animal charcoal being used to decolorise it. The crystals were right-angled plates soluble in water, giving a neutral reaction, sparingly soluble in cold ether and light petroleum, easily in hot ether, in alcohol, and in hot benzene. They melted easily (127-128' uncor.), sublimed withont decomposing, and contained no water of crystallisation, and proved to be benzamide ; about 4 grams of it were obtained in the urine for every 100 grams of benzaldehyde given to the animal.I n the ra,bbit no benzamide was found in the wire, even after sub- cutaneous injection of ammonium benzoate ; probably in this animal the ammonia derived from the benzoate is completely used in building up urea. W. D. H. Uroleucic Acid and Alcaptonuria. By R. KIRK (Brit. Med. J., 2, 1889, 1149-1150) .-Prof. Huppert, in a private communication to the author, regards the uroleucic acid (C9Hl,,05) previously described by him (Abstr., 1888, 1121) in the urine of cases of alcaptonuria as a homologue of gallic acid and probably pyrogallol- propionic acid, or a t least a trihydroxyphenylpropionic acid, C,H,( HO),.CH2*C K2.COOH.It does not give the genuine Millon's reaction, and therefore contains either no hydroxgl-group in the benzene nucleus, or more than one; it is optically inactive, and therefore contains no asymmetrical carbon-atom. Uroleucic acid was found to have considerable antiseptic power. It is entirely absent in normal urine. The substance previously described as uroxanthic acid, which accompanies uroleucic acid in these peculiar.VEGETABLE PHYSIOLOGY AND AGRICULTURE. 189 urines, has been more fully investigated, and found to consist simply of uroleiicic acid mixed with hippuric acid as an impurity. W. z). H. Cystinuria. By B. MESTER (Zeit. physiol. Clzem., 14, 109-150). -This paper relates to the examination of the urine of patients suffering from cystinuria, and many of the considerations introduced are of clinical, therapeutical, historical, and theoretical interest.The chief points of chemical importance relate to :- (1.) The solubility of cystin in urine ; it appears that even in acid urine as much as 0.5 gram of cystin will dissolve per litre. (2.) The sulphur in cystin is doubtless combined in a non-oxidised form; numerous analyses in this direction are tabulated; and the average result of estimations on the urine from nine individuals shows that the non-oxidised sulphur forms 18.1 per cent. of the tctnl sulphur; from these numbers a method is devised for estimating the amount of cystin in urine. (3.) Different kinds of diet, and the use of alcohol, appeared to be without influence on the amount of cystin excreted. (4.) Bysadministering sulphur arid also salol as drugs, the amount of unoxidised sulphur in tbe urine was practically unchanged.W. D. H.182 ABsTRACTS OF CHEMICAL PAPERS.P h y s i o l o g i c a l Chemistry.Calorimetric Investigations on Heat Production in Animals.By J. ROSENTHAL (Arch. Anat. PhySiol.,.physiol, Abth., 1889, 1-53).-A long account of investigations relating chiefly to the influence ofbody weight and food on the production of heat, together with fulldescriptions of the methods employed, including that of the air-calorimeter. W. D. H.Conditions of Absorption of various Haemoglobins. ByS . JOLIN (Arch. Anat. Physiol,, phpiol. Abth., 1889, 265--SSS).-Bohr (Ludwig’s Festschrift, 1886) has shown in experiments with thebaemoglobin of the dog, by the use of st new absorptiometric method,how the dissociable unions of hsmoglobin with oxygen and with carPHYSIOLOGICAL CHEMISTRY.183bonic anhydride vary with differences of pressure. This is notstrictly proportional to the pressure, but falls at first slowly, but withlow pressures (below 20 or 30 mm. of mercury) very quickly.This can be represented graphically by a curve constructed fromabscissae representing the pressure, and ordinates represent,ing theamount of gas absorbed by 1 gram of hemoglobin; the curve so ob-tained with oxygen is quite differeut from that obtained with carbonicanhydride.In the present research, the same methods were applied first toguinea-pig’s hemoglobin, which crystallises in rhombic tetrahedra,not in prisms, as dog’s henioglobin does ; and secondly with goose’shernoglobin, as an instance of blood pigment occurring i n nucleatedred corpuscles.In the first case, the results obtained were practicallythe same as in Bohr’s researches, the difference of crystalline formcausing no difference in the type of the curves produced, the generalconclusion being that there are two possible compounds of each ofthe gases with the hslsmoglobin. With regard to the second series ofexperiments, those with birds’ haemoglobin, the curves are in respect toboth gases of a character different from those obtained with mamma-lian blood pigment. The curves are flatter, and show that the quan-tity of gas absorbed in the first place is less, and in the second placedoes not increase with the pressure beyond a certain point, namely,95 mm.in the case of oxygeu, 65 mm. in that of carbonic anhydride.W. I). H.Gases in the Swimming-bladder of Fishes. By M. TRAUBE-MENGARINI (Arch. Anat. Physiol., physiol. Abth., 1889, 54--63).-1ffish are placed in water containing hydrogen in solution, the swim-ming-bladder, whether it be of the open or closed variety, becomes ina few hours filled or partially so with the gas. This fact shows thatthe gases of the swimming-bladder are more or less directly obtainedfrom water in which the fish is living. W. D. H.Digestion in the Pig. By ELLENBERGER and HOFMEISTER (Arch.Anat. Physiol., physiol.Abth., 1889,137-153).--This is an account ofexperiments on the pig carried out on the same lines as previousexperiments by the same authors on other animals. The anatomy ofthe stomach, the process of digestion with different foods in differentparts of the alimentary canal, and the process of absorption are de-scribed. With regard to gastric digestion, an important point madeout is that the proteolytic period is preceded by a period in which nosecretion of acid takes place, and when amylolytic action proceedsfreely. W. D. H.Absorption of Fat in the Intestine. By A. GRUENHAGEN andRROHN ( B i d Centr., 18, 617-619 ; from Arch. Phys., 24, 535-545).-The author showed some time ago that the epithelium cells of theintestine cut, out of a frog, as well as those in the living organism, arecapable of taking up drops of fat from the intestinal tube filled withfat or emulsion.The experiments were made with frogs which had not been fed fo184 ABSTRACTS OF OHEMICAL PAPERS.some time, so that the intestine should be free from food constituents.The substances employed were milk, olive oil, lanolin emulsion, and,to determine whether the epithelium absorption is confined to fattysubstances (Funke's view), a solution (?) of the finest Chinese ink.The results of the experiments show that the assumption of a me-chanical activity of the epithelium of the intestines in taking up offat is inadmissible, inasmuch as only fat and not even the finestgrains of other substances enter into the protoplasma of the bordercells.It is also established that the intestinal epithelium of hiber-nating frogs forms a store place for excess of fat, and wiIl retain fattysubstances enclosed in it with great tenacity.Origin of Urea in the Animal Economy. By F. COPPOLA (Chew.Centr., 1889, ii, 375 ; from Rend. Acad. dei Lincei [4], 5, 1).-A dogwas fed with an insufficient amount of bread f o r a month, a t the end ofwhich time its weight remained constant. The urea and acidity weredetermined in the voidings f o r five days, and then varying quantitiesof cyanuric acid were administered in addition to the daily ration ofbread, the urea and acidity being still determined. The administra-tion of the cyanuric acid had no influence on the weight of theanimal.Up to 1 gram of administered cyanuric acid, the amount ofurea increased ; an excess of this amount had no further influence onthe quantity of urea formed. Some of the cyanuric acid passed awaywith the excreta, and the total acidity increased with the amount ofcyanuric acid administered. The author concludes that one part ofthe cyanuric acid is changed into carbimide, which is further decom-posed into water and carbonic anhydride, the ammonia then com-bining with a second portion of cyanuric acid, with formation ofurea. J. W. L.N. H. M.Origin of Uric Acid in Mammals. By J. HORBACZEWSKI(Nonatsh., 10, 624-641) .--Since uric acid is a derivative of acrylicacid, and is produced in abnormally large quantities when glycerol istaken internally, it was thoaght probable that it might be built upspthetically in mammals from acrylic acid, and some nitrogenouscompound, such as urea.In order to ascertain whether this was thecase, sodium acrylate was mixed with the food of a strictly dietedsubject, but no iucrease in the quantity of uric acid formed could beobserved. The urine, however, showed indications of becomingalkaline, a result probably due to the formation of sodium carbonatefrom the sodium acrjlnte.Minkovski has suggested (Arch. exper. Path. Phann., 21) that inbirds the formation ot uyic acid is probably due to some function ofthe liver, whereby the acid is built up from lactic acid and ammonia,but the author now shows that in the case of men whose death resultsfrom cirrhosis hepatis, the amount of uric acid formed does not varywith the progress of the disease, and that mixtures of fresh spleenic juiceand defibrinated blood, obtained from recently-killed calves, throughwhich, a t 37-40", a slow stream of air is passed, give rise to veryconsiderable quantities of uric acid.This result is not produced bythe blood alone, and must be regarded as due to a function of thPHYSIOLOGICAL CHEMISTRY. 185spleen, which perhaps uuder some circumstances brings about thedegradation of the white corpuscles of the blood.Changes in the Glycogen, Sugar, and Lactic Acid of theMuscle while performing Work. By A. MOLINARI (Chem. C‘entr.,1889, ii, 372-373, from Ann. Chim. Fawn., 9,351-366).-T he mnsclesof two dogs, one of which had rested and weighed 20.5 kilos., whilstthe other had run 92 kilometres (57 miles) and weighed 25.5 kilos.,were analysed, and the respective amounts of glycogen, sugar, andlactic acid determined.The glycogen was estimated by Wind-gradoff’s method.In the filtrate from the precipitated glycogen, the sugar was deter-mined by Fehling’s solution. The lactic acid was estimated by twomethods. By the first, 350 grams of muscle is extracted with water,concentrated somewhat, 99 per cent. alcohol added, the filtrate dis-tilled and concentrated, and the residual alcohol-free liquid dilutedwith a little water. A slight excess of lead acetate is added, thefiltrate and washing concentrated in order to allow the creatine tocrystallise out, the mother-liquor acidified and extracted with ether,the ether distilled off, the residue dissolved in a litkle water, powderedzinc oxide added, the filtrate again concentrated, and treated withfour or five volumes of 99 per cent.alcohol, and the precipitate filteredoff, dried, and weighed. I n the second method, baryta is used toremove the phosphates. The results obtained by the two differentmethods did not agree very closely, and the author recommends theformer as the more exact.In the muscles of the tired dog, less glycogen and lactic acid b u tmore sugar was found, showing that the lactic acid is not formedfrom the glycogen.Diastatic Ferment of the Liver. By KAUFMAXN (Compt. rend.SOC. Bid. [9], 1, 600- 603).-Bernard first advanced the doctrinethat the hepatic glycogen is transformed into sugar by a fermentwhich is separable from the liver substance.Recent observations byDastre (and others not quoted) have thrown doubt on the existenceof such a special ferment. In the prcsent research, i t was sought tofurther elucidate the question by examining the secretion of the liver,not the liver substance itself. Dog’s bile was found to be free froma saccharifying ferment. Cat’s bile was feebly saccharifying. Thebile of the pig, sheep, and ox was found to be powerful in corivertingstarch into sugar. These facts are considered as additional evidencethat a diastatic ferment is formed by the liver ; the dog, however, issupposed to transform its glycogen into sugar by some other means.W.D. €3.G. T. M.J. W. L.Quantity of Iron in the Spleen and Liver of YoungAnimals. By L. LAPICQUE ( C o ~ ~ p t . rend. SOC. Biol. [9], 1, 510-512).-The spleen of young animals is poor in iron. Four rabbits born a tthe same time were taken. Intravenous injection of distilled waterwas performed on two of these in order to destroy some of their red-blood corpuscles ; their spleens contained respectively 0.24 and 0.26parts of iron per 1000 ; the amount of iron in the spleens of the othe186 ABSTRACTS OF CHEMICAL PAPERS.I n blood.two animals, which served as control specimens, was 0.4.4 and 0.19per 1000 respectively.Estimations wei-e then made to determine if the quantity of iron inthe liver varies with age. The organs were in each case freed fromblood, and the results were a8 follows :-The result is thus an uncertain one.I n liver.Age of rabbit. Weight in kilos.Parts of iron per 1000.8 day8 ................11 days................21 days.. ..............3 months .............3 months .............3 months .............0 -1200 -1370 *3201 *1701 -3501.3600 -450 -400 *410 *420 *36-1 ‘000.200 *140 *0430.0350 *OMThe quantity of iron thus diminishes with the age of the animal.W. D. H.The Physiological R6le of Lactose. By A. DASTRE (Compt.rend. SOC. Bid. [9], 1, 145--149).-Although lactose is so importantas a food, it is stated that very little is known of the part i t plays inthe organism. The present communication relates to the questionwhether lactose is itself assimilable. The conclusion arrived at isthat which others have found before, that lactose is not directlyassimilable, but is first inverted in the alimentary canal.What agentaccomplishes this change is still uncertain. After injecting into thecirculation a mixture of galactose and glucose, a small quantity ofthe sugar which is not utilised passes into the urine. This sugar is areducing one, but does not undergo the alcoholic: fermentation. Itsnature is, however, uncertain. W. D. H.By F. REINITZER (Chenz. Centr.,1889, ii, 292-293, from Ber. deut. bot. Gesell., 7, 187--196).-Theauthor contends that the assertion of Kraus (Abstr., 1889, 917), thatthe tannins of various origins are physiologically alike, is not correct,and that the methods at present employed for the determination oftarinin are not suitable for physiological investigation, however usefulthey may be for the practical valuation by the tanner.By P.SPALLANZANI (Chem.Centr., 1889, ii, 339-341, from Staz. sperem. agric. ital., 16, 277-293).-The author has carried out an investigation into the cause ofbutter fat containing so variable a quantity of volatile fatty acids.Four different breeds of cows, namely, that of the Province Reggiod’Emilia, Dutch, Schwitz, and Simmenthal, were employed and fedexactly in the same way. The cream of the milk of the severaldifferent breed8 was separately churned, as wm also cream which was12 hours, and that which was 36 hours old. Further, the influence ofleiigth of time from calving, the sudden changing of food, and thePhysiology of the Tannins.J.W L.Volatile Fatty Acids of ButterPHYSIOLOGICAL CHEMISTRY 187age of the butter, with regard to the quantity of volatile fatty acidsin the butter, was investigated.The amount of volatile fatty acids, expressed in terms of C.C. of deci-normal alkali per 5 grams of butter fat, varied from 20.63 to 30.60.Nor could any regularity in the quality of butter obtained from thedifferent sources be observed. The butter from cows stationed athigh lying places contained usually more volatile fatty acids thanthat from low lying stations. Of the different breeds t h a t of Schwitzgave butter containing most fatty acids, then followed the breedsSimmenthal and Reggio, alike ip this respect, and last the Dutch.Lastly, with regard to the influence of length of time since calving, thepercentage of fatty acids declined as this period advanced.J.W. L.Urobilin in the Bile. By J. WINTER (Compt. rend. SOC. Biol.191, 1, 139).-In reference to the method adopted by Engel andKiener (Abstr., 1889, 637) for the separation of urobilin, it is pointedout that the precipitates of the biliary constituents produced byadding calcium salts, especially the phospbate, carry urobilin downwith them. The final filtrate, even in urines rich in urobilin, isalways colourless. The conclusion drawn by Engel and Kiener, thaturobilin is absent from the bile, is therefore not proved, as theirmethod was one unsuited for discovering small quantities of thatpigment.W. D. H.The Behaviour of Tgrosine Ethyl Ether in Animal Meta-bolism. By R. COHN (Zeit. physiol. Chern., 14, 189--202).-Con-sidering the amount of proteid daily ingested by an animal, theamount of tyrosine formed cannot be inconsiderable. Blenderniann(Ahstr., 1883,876)md Jaffe (Zeit. physiol. Chem., 7 ) by feeding animalswith tyrosine could, however,find no increase in the aromatic substancesin the urine, nor indeed any constant relation between tyrosine orany urinary constituent. Baas (Abstr., 1887,1133) found no increasein the hippuric acid secreted in similar experiments. I n the presentexperiments on dogs and rabbits, the tyrosine ethyl ether hydro-chloride was injected both subcutaneously and intravenously.Largedoses acted fatally : but no tyrosine was ever found in the urine orbile ; nor was there an increase in aromatic hydroxy-acids, pbenol, orhippuric acid. It is thus probable that tyrosine undergoes completedestruction in the organism. W. D. H.Determination of Potassium in Urine as Potassium HydrogenTartrate. By A. ROBIN (Compt. rend. Soo. Biol. [9], 1, 356-363).-When the potassinm in urine is estimated by the weight of the pre-cipitate obtained by adding tartaric acid to concentrated urine, theresults obtained as compared with those obtained from the platinicchloride method are fouud to be from 9 to 70 per cent, too high. Allconclusions drawn from such estimations are therefore null. Rogerand Gaume have stated that the output of potassium salts is increasedi n ague and certain other diseases ; their conclusions regarding thissubject, and also regarding the toxicity of urine from the presence init of potassium salts, rest on experiments performed by the tartari188 ABSTRACTS OF CHEMICAL PAPERF.acid method.The precipitate produced by tartaric acid in urinecarries down with i t uric acid, hippuric acid, albumin, and otherorganic substances. W. L). H.Reducing Substances in Urine. By GAUBE (Comnpt. rend. SOC.Bid. [9], 1, 383--390).--Various urines were examined with regardto the substances in them that reduce alkaline solutions of cuprichydroxide. I n one case, that of an emaciated child, the reducingsubstance is stated to ha,ve been aldehyde. The following stat,ementsare also made :-In acetonzemia and acetonuria, lactic acid exists inthe urine, in combination conjointly with phosphoric acid, producingacid salts, principally of potassium, to which the acidity of the urinein these cases is chiefly due.Lactose is said to be met with in theurine of cases of what the author terms oxycrasia. W. D. H.Benzamide in Urine after Administration of Benaaldehyde.By R. COHK (Zeit. phys':oZ. Chenz., 14, 203--808).-After feedingdogs on benzaldehyde (10 grams per diem), the urine was collected,extracted with hot alcohol, the extracts evaporated, and the depositdissolved in water strongly acidified with sulphuric acid. This wasshaken with ether ; the ethereal extracts concentrated, and thehippuric acid so deposited filtered off. The ether was distilled off,and the small crystalline residue was dissolved in a concentrated solu-tion of sodium carbonate, and again shaken with ether ; the etherwas again evaporated, and the crystalline residue was recrystallisedfrom hot water, animal charcoal being used to decolorise it.Thecrystals were right-angled plates soluble in water, giving a neutralreaction, sparingly soluble in cold ether and light petroleum, easily inhot ether, in alcohol, and in hot benzene. They melted easily(127-128' uncor.), sublimed withont decomposing, and contained nowater of crystallisation, and proved to be benzamide ; about 4 gramsof it were obtained in the urine for every 100 grams of benzaldehydegiven to the animal.I n the ra,bbit no benzamide was found in the wire, even after sub-cutaneous injection of ammonium benzoate ; probably in this animalthe ammonia derived from the benzoate is completely used in buildingup urea.W. D. H.Uroleucic Acid and Alcaptonuria. By R. KIRK (Brit. Med. J.,2, 1889, 1149-1150) .-Prof. Huppert, in a private communicationto the author, regards the uroleucic acid (C9Hl,,05) previouslydescribed by him (Abstr., 1888, 1121) in the urine of cases ofalcaptonuria as a homologue of gallic acid and probably pyrogallol-propionic acid, or a t least a trihydroxyphenylpropionic acid,C,H,( HO),.CH2*C K2.COOH. It does not give the genuine Millon'sreaction, and therefore contains either no hydroxgl-group in thebenzene nucleus, or more than one; it is optically inactive, andtherefore contains no asymmetrical carbon-atom.Uroleucic acid was found to have considerable antiseptic power. Itis entirely absent in normal urine. The substance previously describedas uroxanthic acid, which accompanies uroleucic acid in these peculiarVEGETABLE PHYSIOLOGY AND AGRICULTURE. 189urines, has been more fully investigated, and found to consist simplyof uroleiicic acid mixed with hippuric acid as an impurity.W. z). H.Cystinuria. By B. MESTER (Zeit. physiol. Clzem., 14, 109-150).-This paper relates to the examination of the urine of patientssuffering from cystinuria, and many of the considerations introducedare of clinical, therapeutical, historical, and theoretical interest. Thechief points of chemical importance relate to :-(1.) The solubility of cystin in urine ; it appears that even in acidurine as much as 0.5 gram of cystin will dissolve per litre.(2.) The sulphur in cystin is doubtless combined in a non-oxidisedform; numerous analyses in this direction are tabulated; and theaverage result of estimations on the urine from nine individualsshows that the non-oxidised sulphur forms 18.1 per cent. of the tctnlsulphur; from these numbers a method is devised for estimating theamount of cystin in urine.(3.) Different kinds of diet, and the use of alcohol, appeared to bewithout influence on the amount of cystin excreted.(4.) Bysadministering sulphur arid also salol as drugs, the amountof unoxidised sulphur in tbe urine was practically unchanged.W. D. H

ISSN:0368-1769    

DOI:10.1039/CA8905800182

出版商:RSC    

年代:1890

数据来源: RSC

摘要:

VEGETABLE PHYSIOLOGY AND AGRICULTURE. 189 Chemistry of Vegetable Physiology and Agriculture. Colouring Matters and Aromatic Products from the Bacillus Pyocyanicus. By A. BAB~S (Compt. rend. SOC. Biol. [9], 1,438-440). -A pure culture of the B. pyocyanicus /3 (Ernst) in neutralised peptonised gelatin gave rise to other colouring matters than those named pyocyanin and pyoxanthin by Fordos. Certain aromatic substances are simultaneously formed. The cultivation was greenish- blue, and its odour that of limes. The following are the substances which were separated :- 1. An azure-blue pigment turned red by acids, and as sensitive as litmus. It dissolves in chloroform, from which i t crystallises in the rhombic system. The absorption spectrum of the blue (alkaline) pigment shows two bands, (1) X30-66, (2) X150-ultra-violet.The absorption spectrum of the red (acid) pigment shows also t w o bands, (I) ultra-red--XEG, (2) h40-ultra-violet. This substance is doubt- less pyocyanin. 2. Pyocyanin being separated, the cultures remain coloured reddish-brown by reflected, emerald-green by transmitted light ; when acidified the liquid loses its dichroism, which, however, returns when it is made alkaline once more. The colonring matter is a mixture of two pigments : one, soluble in alcohol, of a green colour by reflected, and blue by transmitted light ; the other, insoluble in alcohol, is orange-red by reflected, greenish- blue by transmitted light. Neither of these corresponds with pyoxanthin, which is apparently n o t formed by the /3 bacillus.190 ABSTRACTS OF CHEJIICAL PAPERS.3. The aromatic substances are not yet identified, a further corn- munication on this part of the subject is promised; the methods adopted for their separation are briefly described. Relation between the Assimilation and Transpiration produced by Chlorophyll. By H. JUMELLE (Compt. rend. SOC. Bdol. [9], 1, 9--10).-1n sunlight, chlor.ophyl1 is stated to have two functions, that of assimilation of carbon from carbonic anhydride, and that of vaporising the water contained in the plant (transpira- tion). In order to investigate the relationship between these two phenomena, a certain number of plants were placed in air containing carbonic anhydride, and another number of similar plants in air free from carbonic anhydride; otherwise, the two sets of plants were under the same conditions.It was found that those in air free from carbonic anhydride, that is, those in which no assimilation was taking place, gave out more water than the other set. It-thus appears that when assimilation is in abeyance, the greater part of the radiant energy absorbed from the light serves for the evaporation of water. W. D. H. W. D. H. Influence of Acids on the Evolution of Gases by Plants. By L. MANGIN (Cornpt. rend., 109, 716-719).-The researches of de Saussure, Mayer, and de Vries, have shown that Cacts and Crassulacese, which contain a notable proportion of organic acids, have the power of evolving oxygen without absorbing carbonic anhydride when placed in sunlight, this change being accompanied by a reduction in the quantity of the organic acids.The leaves of fusain, which contain practically no free acids, were injected with a dilute solution (2 to 3 per cent.) of some organic acid, and exposed to light. With malic, citric, and tartaric acids, oxygen was evolved, but acetic, formic, oxalic, and succinic acids gave negative results, p.robably because they killed the protoplasm. The volume of oxygen liberated varied with the nature of the acid, but, other conditions being the same, it was greatest with malic, less with citric, and least with tartaric acid. The volume of oxygen decreases with the concentration of the acid injected, because of the destructive action of the acid on the protoplasm. The respiration of plants in the dark is also affected by the presence of free acid, the volume of oxygen absorbed, and the volume of car- bonic anhydride liberated, being largely increased.Moreover, in normal leaves, the ratio CO$O isless than or at most equal to unity, whilst in presence of acids it is always greater than unity, and in some cases considerably greater. The presence of certain organic acids in plants exerts a double influence. In the dark, it causes the evolution of a volume of car- bonic, anhydride greater than that of the oxygen absorbed, and, in light, the evolution of oxygen without a correlated absorption of carbonic anhydride. The cause of these disturbances is in the leaves themselves ; the chlorophyll simply reduces, under the influence of light, the excess of carbonic anhydride which is exhaled by the tissues under the influence of the acids. C.H. B.VEGETABLE PHYSIOLOGT AND AQRICULTURE. 191 Formation of Calcium Oxalate in Plants. By KOHL (Ann. Agronom,, 15, 418-420, from Bot. Centr., 38, 471).-The author’s view is that asparagine and other amides are built up into albn- mindids with the aid of carbon and hydrogen derived from the carbo- hydrates. The oxygen liberated goes to form organic acids, especially oxalic, and this acid combines with the lime which is distributed through the tissues in combination with sugar and other soluble carbohydrates. The building np of the nlbuminoids can only take place in the cells exposed to light ; therefore the amides accumulate in any organ kept in the dark, and but little acid is found in these parts. I n the parts exposed to light, acid is, on the contrary, abundant.When starch is stored up in roots, rhizomes, bulbs, seeds, &c., the lime which held the carbohydrate in solution is set free, and it is in these places that most calcium oxalate is found. In the Gramines much of the calcium oxalate is replaced by potassinm oxalate. J. M. H. M. Calcium Oxalate in the Leaves of Alnus glutinosa, Sympho- ricarpus racemosa, and Crataegus oxyacantha. By C. WEHMER (Ann. Agronom., 15, 420-421, from Bot. Zeit., 1889, 141, 165).-By comparing corresponding leaves in shoots of different aga, the author concludes t,hat there is no solution and migration of the calcium oxalate at first formed, as contended by Schimper, but that the deposits of oxalate increase at different rates in tissues of different age.J. M. H. M. Occurrence of Scatole in the Vegetable Kingdom. By W. R. DUNSTAN (Pharnz. J. Trans. [33, 19, 1010; and Proc. Roy. Soc., 46, 211).-From the wood of Celtis reticulosa, a tree which grows in Java, Ceylon, and Eastern India, and which when freshly cut has a very disgusting odour, the author has obtained a substance of the com- position of scatole (3’-methylindole.) This corresponds in all its properties with synthetical ~catole from propylidene phenylhydrazide. Indole is found with scatole in human faeces, but none was detected in the wood of Celtis reticulosa. R. R. Inulin in the Capitula of Composites. By L. DANIEL (Compf. rend. SOC. Biol. [9], 1, 182--1~4).--Inulin has been found in the roots of a large number of composites, but has not been before noted in the capitules.It is, however, present in large quantities in the bracts, the receptacle, and even the seeds in course of development, especially in the Cynarocephala. It is always absent in parts exposed to light, and darkness appears to be favourable or perhaps essential for its elaboration. The flowers were examined in different stages of development, and the conclusion drawn from these observatioris is that inulia is a reserve ma.teria1, lasting, however, only a short time, and used up entirely in the development of the ovary and embryo. W. D. H.192 ABSTRACTS OF CHE3IICAL PAPERS. Analysis of White Soja Bean. By C. A. GOESSMANN (Bied. -. p. c. 5.85 5.57 5 -15 18'42 35.98 34 *88 Cen.fr., i889, 719). __________~ p. c. 17-38 5.22 5.35 21.89 33.36 34-18 --- p.c. - - 14.50 89'80 90.00 62-00 Moisture. ............. Ash .................. Fibre ................ Fa.t .................. Albumin .............. Estrac tive. ............ 6.47 20.76 5.62 15 %7 51.28 Whole plant, on Aug. 30th, 1888. I Seeds. New York. - 34.75 65.07 57.45 64-51 Massachusetts. I Digestible matter. I I I Digestible Digestible matter. -- p. c. 14 *50 89 -80 90 *oo 62 '00 - - H20. CaO. MgO. K20. Na20. Fe203. Seed ........ 17.380 0.342 0.869 2.085 0.166 0.231 Whole plant.. 6.120 2.770 1.190 0.617 0.198 0.131 Seed ........ 1.851 5.308 0.090 Whole plant.. 0.753 2.380 0.967 p205. N. Insol. matter. E. W. P. Chemical Examination of Moorland and Peat Soils. By C. G. EOGERTZ and L. I?. NILSON (Bied. Centr., 1889, 664-668).- Various soils in Sweden were examined as to their volume-weight, percentage of organic matter and nitrogen, as well as of silicic acid, &c.The mineral constituents were dissolved out by a 2 per cent. solution of hydrochloric acid, and this strength of acid was found to be amply sufficient for the removal of all plant-food, and to render the soil sterile for barley; but to sterilise the fertile soils for oats, a 4 per cent. solution was requisite. These two solutioiis removed about equal quantities of silicic acid, which amounted to 0.1 per cent. of the dry soil. If the soil was exhausted with the acid, both directly and after ignit,ion, then a very considerable difference in the quantities of sulphuric acid removad was noted, namely, 0.4 per cent. in the first case, and 0.96 in the second ; also there was a great difference i n the quantities of sulphates found, depending on the source of the soil, and the authors con- sider that, as the sulphates were not found in the hydrochloric extract, but only after ignition, the sulphur must be in many cases present as an organic compound.Only in 5 out of 32 cases did the sulphuric acid exceed 0.1 per cent., and it never amounted t o 0.2 of the dried soil. The phosphoric acid estimations were of a similar kind, so that this elementl (phosphorus) must be considered as also being present in organic compounds, which are only rendered soliible by ignition ; hence the advantage of burning a moorland soil without further nddi tion of phosphatic manures.ANALYTICAL CHEMISTRY. 193 In most cases the ignited soil yielded the most lime to dilute hydro- chloric acid, the excess being 0.5-1.0 per cent.more than that found in the natural soil ; but the opposite wits found to be the case with the Gotland samples. A soil derived from Sphagnum, which contained only 0.22 per cent. of CaO, was completely sterile for oats, even after a, heavy manuring with basic slag, potassium sulphate, and iiitre, but 4,000 kilos. of chalk per hectare rendered i t fertile. Con- cerning magnesium nothing remarkable was noticed ; neither was much difference noticed in the case of potassium, except in those soils where potassium silicates were present in large quantities ; these, being readily acted on by hot lime, naturally yielded after iguitioii n larger quantit,y of potassiiim to the acid.The percentages of nitrogen varied fporn 1.38 to 4.57. E. W. P.VEGETABLE PHYSIOLOGY AND AGRICULTURE. 189Chemistry of Vegetable Physiology and Agriculture.Colouring Matters and Aromatic Products from the BacillusPyocyanicus. By A. BAB~S (Compt. rend. SOC. Biol. [9], 1,438-440).-A pure culture of the B. pyocyanicus /3 (Ernst) in neutralisedpeptonised gelatin gave rise to other colouring matters than thosenamed pyocyanin and pyoxanthin by Fordos. Certain aromaticsubstances are simultaneously formed. The cultivation was greenish-blue, and its odour that of limes. The following are the substanceswhich were separated :-1. An azure-blue pigment turned red by acids, and as sensitive aslitmus. It dissolves in chloroform, from which i t crystallises in therhombic system.The absorption spectrum of the blue (alkaline)pigment shows two bands, (1) X30-66, (2) X150-ultra-violet. Theabsorption spectrum of the red (acid) pigment shows also t w o bands,(I) ultra-red--XEG, (2) h40-ultra-violet. This substance is doubt-less pyocyanin.2. Pyocyanin being separated, the cultures remain colouredreddish-brown by reflected, emerald-green by transmitted light ; whenacidified the liquid loses its dichroism, which, however, returnswhen it is made alkaline once more. The colonring matter is amixture of two pigments : one, soluble in alcohol, of a green colourby reflected, and blue by transmitted light ; the other, insoluble inalcohol, is orange-red by reflected, greenish- blue by transmitted light.Neither of these corresponds with pyoxanthin, which is apparentlyn o t formed by the /3 bacillus190 ABSTRACTS OF CHEJIICAL PAPERS.3.The aromatic substances are not yet identified, a further corn-munication on this part of the subject is promised; the methodsadopted for their separation are briefly described.Relation between the Assimilation and Transpirationproduced by Chlorophyll. By H. JUMELLE (Compt. rend. SOC. Bdol.[9], 1, 9--10).-1n sunlight, chlor.ophyl1 is stated to have twofunctions, that of assimilation of carbon from carbonic anhydride,and that of vaporising the water contained in the plant (transpira-tion). In order to investigate the relationship between these twophenomena, a certain number of plants were placed in air containingcarbonic anhydride, and another number of similar plants in air freefrom carbonic anhydride; otherwise, the two sets of plants wereunder the same conditions. It was found that those in air free fromcarbonic anhydride, that is, those in which no assimilation was takingplace, gave out more water than the other set.It-thus appears thatwhen assimilation is in abeyance, the greater part of the radiantenergy absorbed from the light serves for the evaporation of water.W. D. H.W. D. H.Influence of Acids on the Evolution of Gases by Plants.By L. MANGIN (Cornpt. rend., 109, 716-719).-The researches ofde Saussure, Mayer, and de Vries, have shown that Cacts andCrassulacese, which contain a notable proportion of organic acids,have the power of evolving oxygen without absorbing carbonicanhydride when placed in sunlight, this change being accompanied bya reduction in the quantity of the organic acids.The leaves of fusain, which contain practically no free acids, wereinjected with a dilute solution (2 to 3 per cent.) of some organicacid, and exposed to light. With malic, citric, and tartaric acids,oxygen was evolved, but acetic, formic, oxalic, and succinic acidsgave negative results, p.robably because they killed the protoplasm.The volume of oxygen liberated varied with the nature of the acid,but, other conditions being the same, it was greatest with malic, lesswith citric, and least with tartaric acid.The volume of oxygendecreases with the concentration of the acid injected, because of thedestructive action of the acid on the protoplasm.The respiration of plants in the dark is also affected by the presenceof free acid, the volume of oxygen absorbed, and the volume of car-bonic anhydride liberated, being largely increased. Moreover, innormal leaves, the ratio CO$O isless than or at most equal to unity,whilst in presence of acids it is always greater than unity, and insome cases considerably greater.The presence of certain organic acids in plants exerts a doubleinfluence.In the dark, it causes the evolution of a volume of car-bonic, anhydride greater than that of the oxygen absorbed, and, inlight, the evolution of oxygen without a correlated absorption ofcarbonic anhydride. The cause of these disturbances is in the leavesthemselves ; the chlorophyll simply reduces, under the influence oflight, the excess of carbonic anhydride which is exhaled by thetissues under the influence of the acids. C.H. BVEGETABLE PHYSIOLOGT AND AQRICULTURE. 191Formation of Calcium Oxalate in Plants. By KOHL (Ann.Agronom,, 15, 418-420, from Bot. Centr., 38, 471).-The author’sview is that asparagine and other amides are built up into albn-mindids with the aid of carbon and hydrogen derived from the carbo-hydrates. The oxygen liberated goes to form organic acids, especiallyoxalic, and this acid combines with the lime which is distributedthrough the tissues in combination with sugar and other solublecarbohydrates. The building np of the nlbuminoids can only takeplace in the cells exposed to light ; therefore the amides accumulate inany organ kept in the dark, and but little acid is found in these parts.I n the parts exposed to light, acid is, on the contrary, abundant.When starch is stored up in roots, rhizomes, bulbs, seeds, &c., thelime which held the carbohydrate in solution is set free, and it is inthese places that most calcium oxalate is found.In the Graminesmuch of the calcium oxalate is replaced by potassinm oxalate.J. M. H. M.Calcium Oxalate in the Leaves of Alnus glutinosa, Sympho-ricarpus racemosa, and Crataegus oxyacantha. By C. WEHMER(Ann. Agronom., 15, 420-421, from Bot. Zeit., 1889, 141, 165).-Bycomparing corresponding leaves in shoots of different aga, the authorconcludes t,hat there is no solution and migration of the calciumoxalate at first formed, as contended by Schimper, but that thedeposits of oxalate increase at different rates in tissues of differentage.J. M. H. M.Occurrence of Scatole in the Vegetable Kingdom. By W.R. DUNSTAN (Pharnz. J. Trans. [33, 19, 1010; and Proc. Roy. Soc.,46, 211).-From the wood of Celtis reticulosa, a tree which grows inJava, Ceylon, and Eastern India, and which when freshly cut has avery disgusting odour, the author has obtained a substance of the com-position of scatole (3’-methylindole.) This corresponds in all itsproperties with synthetical ~catole from propylidene phenylhydrazide.Indole is found with scatole in human faeces, but none was detectedin the wood of Celtis reticulosa.R. R.Inulin in the Capitula of Composites. By L. DANIEL (Compf.rend. SOC. Biol. [9], 1, 182--1~4).--Inulin has been found in theroots of a large number of composites, but has not been before notedin the capitules. It is, however, present in large quantities in thebracts, the receptacle, and even the seeds in course of development,especially in the Cynarocephala. It is always absent in partsexposed to light, and darkness appears to be favourable or perhapsessential for its elaboration.The flowers were examined in different stages of development,and the conclusion drawn from these observatioris is that inulia isa reserve ma.teria1, lasting, however, only a short time, and used upentirely in the development of the ovary and embryo.W.D. H192 ABSTRACTS OF CHE3IICAL PAPERS.Analysis of White Soja Bean. By C. A. GOESSMANN (Bied.-.p. c.5.855.575 -1518'4235.9834 *88Cen.fr., i889, 719).__________~p. c.17-385.225.3521.8933.3634-18---p. c.--14.5089'8090.0062-00Moisture. .............Ash ..................Fibre ................Fa.t ..................Albumin ..............Estrac tive. ............6.4720.765.6215 %751.28Whole plant, onAug. 30th, 1888. I Seeds.New York.-34.7565.0757.4564-51Massachusetts.IDigestiblematter.I I IDigestible Digestiblematter.--p. c.14 *5089 -8090 *oo62 '00- -H20. CaO. MgO. K20. Na20. Fe203.Seed ........ 17.380 0.342 0.869 2.085 0.166 0.231Whole plant.. 6.120 2.770 1.190 0.617 0.198 0.131Seed ........1.851 5.308 0.090Whole plant.. 0.753 2.380 0.967p205. N. Insol. matter.E. W. P.Chemical Examination of Moorland and Peat Soils. ByC. G. EOGERTZ and L. I?. NILSON (Bied. Centr., 1889, 664-668).-Various soils in Sweden were examined as to their volume-weight,percentage of organic matter and nitrogen, as well as of silicicacid, &c. The mineral constituents were dissolved out by a 2 percent. solution of hydrochloric acid, and this strength of acid wasfound to be amply sufficient for the removal of all plant-food, andto render the soil sterile for barley; but to sterilise the fertile soilsfor oats, a 4 per cent. solution was requisite. These two solutioiisremoved about equal quantities of silicic acid, which amounted to0.1 per cent.of the dry soil. If the soil was exhausted with theacid, both directly and after ignit,ion, then a very considerabledifference in the quantities of sulphuric acid removad was noted,namely, 0.4 per cent. in the first case, and 0.96 in the second ;also there was a great difference i n the quantities of sulphatesfound, depending on the source of the soil, and the authors con-sider that, as the sulphates were not found in the hydrochloricextract, but only after ignition, the sulphur must be in many casespresent as an organic compound. Only in 5 out of 32 cases didthe sulphuric acid exceed 0.1 per cent., and it never amounted t o0.2 of the dried soil. The phosphoric acid estimations were of asimilar kind, so that this elementl (phosphorus) must be consideredas also being present in organic compounds, which are only renderedsoliible by ignition ; hence the advantage of burning a moorland soilwithout further nddi tion of phosphatic manuresANALYTICAL CHEMISTRY. 193In most cases the ignited soil yielded the most lime to dilute hydro-chloric acid, the excess being 0.5-1.0 per cent. more than thatfound in the natural soil ; but the opposite wits found to be the casewith the Gotland samples. A soil derived from Sphagnum, whichcontained only 0.22 per cent. of CaO, was completely sterile for oats,even after a, heavy manuring with basic slag, potassium sulphate, andiiitre, but 4,000 kilos. of chalk per hectare rendered i t fertile. Con-cerning magnesium nothing remarkable was noticed ; neither wasmuch difference noticed in the case of potassium, except in those soilswhere potassium silicates were present in large quantities ; these,being readily acted on by hot lime, naturally yielded after iguitioiin larger quantit,y of potassiiim to the acid.The percentages of nitrogen varied fporn 1.38 to 4.57.E. W. P

ISSN:0368-1769    

DOI:10.1039/CA8905800189

出版商:RSC    

年代:1890

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ANALYTICAL CHEMISTRY. 193 An a 1 y t i c a1 C h e m i s t r y. Filter Holder for Drying and Weighing. By C. REINHARIYT (Zeit. ang. Chetn., 1889, 61).-l'his is a glass box, in shape like a funnel, with a short, wide neck, and having a light ground cover. The filter, whether full or empty, is dried in it whilst retaining its conical form, whereby not only is drying accelerated, but any sub- sequent treatment of the precipitate is much facilitated. Estimation of Sulphur in Burnt Pyrites. By G . LUKCS (Zeit. ang. Chern., 1889, 639--240).--Of methods depending on the neutralisation of an alkali by the conversion of the sulphur into a sulphate in the dry way, that of Watson (Abstr., 1889, 306) is the only accurate, as weli as the simplest and most expeditious one. Estimation of Nitrites.By W. R. DUNSTAN and T. S. DYMOND (Pkarm. J. Trans. [3], 19, 741--743).-The authors have devised an apparatus for titrating, in an air-free space, the iodine liberated by nitrites from an acid solution of potassium iodide. All sources of error are thus eliminated, and the process has distinct advantages over the gasometric methods, especially in the case of organic nitrites. Astout glass flask of about 100 C.C. capacity is fitted with ail india-rubber stopper, through which pusses a short glass tube connected with a small tube-funnel by means OF a short piece of thick ii.dia-rubber tubing carrying a steel screw clamp. 5 C.C. of 30 per cent. potassium iodide solution, 5 C.C. of 10 per cent. sulphuric acid, :hnd 40 C.C. of water are introduced, and tlie mixture boiled in tlie flask with the tubes open until all the air and iodine that niay hare been liberated have been expelled; when the steam is escaping freely from the funnel, the clip is closed tightly a t the same momeiit that the source of heat is withdrawn.Then the flask is cooled. A known quantity of the nitrite solution, equivalent to about 0.1 gram of nitroiis acid, is placed i n the funnel a.iid caut;onsly drawn into the flask by unscrewing the clip, receiltly boiled water M. J. S. M. J. S. VOL. C'FIII.194 ABSTRACTS OF CHEMICAL PAPERS. being used for waclhing it down. The iodine liberated is estimated by a decinormal sodium thiosulphate s o h tion, gradually introduced into the flask with due precactions for the exclusion of air. The colour of the dissolved iodine is a sufficient indicator, but starch may be used.Many test determinations of volatile organic nitrites are given, with the figures controlled by other methods. The results are very accordant, and speak well for the accuracy of the process. R. R. Estimation of Arssnic in Iron. Bs M. A. v. REIS (Chem. CeTttr., 1889, ii, 379; from Stahl. u. Eisen, 9, 720-723).--10 grams of pig iron is dissolved with 100 C.C. of wat,er and 20 C.C. of concentrated sulphuric acid. The insoluble residue, consisting of those metals precipitable by hydrogen sulphide in acid solution, especiallv arsenic and copper, is collected, and dissolved with hydrochloric acid and potassium clrloyate. The chlorine is expelled, the ferric chloride rzdnced by sodium hypophosphite, and the arsenic and copper pre- cipitated by ammonium thiocsrbamate, filtered, washed with dilute hydrochloric acid and watep, then oxidised with concentrated nitric a ,id, filtered and the arsenic precipitated with magnesia mixture.The precipitate is washed into a platinum crucible with nitric acid, evaporated to dryness, and weighed after driving off the ammonium salts by ignition. Carbonic Oxide Detector. By RAUNE (Bull. SOC Chim. [3], 1, 555-558) .-To indicate the presence of deleterious quantities of carbonic oxide in dwelling rooms, an apparatus is described in which tlie fact, that gunqotton dusted with platinum black fires in air con- taining 2 5 per 1,000 of carbonic oxide, is made use of to determine the closure of an electric circuit containing an alarum.Improvement in the Method of Estimating Carbonic An- hydride by Volume. By F. E'UCHS (Monatsh., 10, 602-604).--Tlle acid solution used to decompose the carbonate is previously saturated with and is kept in an at'mosphere of carbonic anhydride, whereb-y tlie usual error due to the retention of the gas in the acid is avoided. Estimation of Silica and Analysis of Siliceous Material. By G. CRAIG (Chem. News, 60, 227).-Taking into consideration the errors and di6culties attached to the estimation of silica by the method of fusion with alkaline carbonates, the author prefers to drive off the silica by means of hydrofluoric and sulphuric acids, and to estimate other substance6 in the residue. About 1.5 gram of finely- powdered substance is treated with sulphuric acid diluted with an equal volume of wat'er, about 4 grams of pure hydrofluoric acid added, the whole mixed well by shaking gently, and heated over a smdl flame until almost dry; the operation is reptt,ited, and the heating continued until sulphuric acid vapour is evolved in order to be sure that all the fluorides are decomposed.The residue is subsequenhly dissolved in hydrochloric acid and examined in the usual manner. By ISBERT and VENATOR (Zd. UUQ. C h m . , 1&9, t;C --ti7).--E'or many pi:rpnscs a i*,zpid a:id fairly J. W. L. T. G. N. G. T. M. D. A. L. Analysis of Sodium Sulphate.A SALY'TIC AL C H EM1 STRT. 195 accurate estimation of the sodium sulphate in the commercial article is required. Ahout 2 grams of the sample is dissolved in a little hot water, ammonia and ammonium carbonate are added, and the mixture is filtered ; the precipitate is dissolved off the filter by hydrochloric acid, again precipitated as before, and then collected and thoroughly washed.A little sulphuric acid is added to the filtrates and washings, which are then evaporated in a platinum basin and ignited. From the weight of the residue is deducted the sodium sulphate corre- sponding tmo the sodium chloride in the original substance, as estimated by titration for chlorine. The remainder is the sodium snlphate in the substance taken. M. J. S. Chromium and Barium in Foods. By L. DE KONINGH ( A r c h . Pharm. [3], 27, 944 ; from Ned. Tij. Pharm. Chem. Tox., 1889, 257).- At least 25 gi-ams of the substance is burnt in a platinum dish, and the ash is weighed.To the ash is added four times its weight. of potas- sium sodium carbonate arid the same amount of potassinm nitrate, ancl the whole is fused €or 15 minutes. After boiling with water and filter- ing, the liquid is yellow it' chromium is present ; but the presence of manganese may produce a greenish colour, which is removed by boil- ing for a few minutes with a little alcohol. The liquid is then concen- trated to 20 c.c., filtered into a test-tube, and compared with mate)* to which potassium chromate solution is added until the two tints are of the same intensity. To prove that the colour is due to chromium, acidify with acetic acid and add lead acetate. If lead is present in the original substance, a yellow precipitate is obtained before the acetate is added.The portion of ash insoluble in water is dissolved in hydrochloric acid, and if lead is to be sought for, this is carefully neutralised before hydrogen sulphide is added. To detect barium carbonate, the strongly acid solution of the ash is treated with a large excess of calcium sulphate solution, by which the barium is quickly precipitated as sulphate free from lead, as the Litter is readily soluble in the strong acid. J. T. Magnesium as a Reagent. By H. N. WARREN (Chem. NPU+.S, 60, 187--188).--It is pointed out that magnesium, on account of its purity and activity, is an excellent reducing agent. In the dry way it reduces niost metals, and even silica and boric anhydride when intensely heated in closed vessels with them. It does not reduce the alkalis and alkaline earths, but is attacked by molybdic anhydride with explosive violence.Being free from arsenic, it is well suited for use in Narsh's test, and as it contains neither iron, phosphorus, nor sulphur, scarcely reacts with potassium ferricyanide, and is more active than zinc, it may be used with advantage for reducing ferric to ferrous salts. If a solution of zinc acetate is boiled with magnesium, the whole of the zinc is precipitated, even though the solution also con- tains metals of the fourth grcup. Iron may be separated from chromium in the following manner: the acid solution of iron and chromium is precipitated with sodium carbonate, the precipitate dissolved in acetic acid and magnesium added. The reducing action is a t first violent ancl then ceases, but196 ABSTRACTS OF CEEhIICAL PAPERS.on applying heat, the colour oE the solution changes from green tht-ough pink, red, violet back to green, the iron in the meantimc! being precipitated on the magnesium. Volumetric Estimation of Zinc. By A. VOIGT (%it. ang. Chem., 1889, 307-308) .-The solution of the substance in hydrochloric acid is oxidised with nitric acid and diluted to ahout 100 O.C. Sufficient potassium tartrate to keep the iron in solution is added, and then ammonia to feeble alkalinity, and the liquid is further diluted to about 2.50 C.C. Standard solution of potassium ferroq-anide is then rnn in, until a drhp of the iiiixtnre brought in contact with strong acetic acid develops a permanent blue. The ferrocyanide is of suitable strength if 1 C.C.is equal to 0.01 gram of zinc. About 46 grams of the salt is dissolved to a litre, and the solution is standardised against one of zinc made by dissolving 12.461 grams of zinc oxide in hydrochloric acid and diluting t o a litre ; 10 C.C. of this solution is mixed with 5 grams of pctassium tartrate, a few drops of ferric chloride, ammonia, and water to 250 c.c., and should require 10 C.C. of the ferrocyanide. An essential condition is that the excess of ammonia should be as small a s possible. Incorrect results are obtained when much manganese is present; lead is not injurious. The process is more rapid than Sjchaffner’s. M. J. S. Standardisation of Permanganate. By R. JAHODA (Zeit. ang. Chein., 1889, 87).-1n dissolving iron wire for the above purpose, the flask is fitted with a cork and a hent tube which dips into a beaker containing solution of ,.odium hydrogen carbonate.Any of this solntion drawn in during the cooling of the iron solution produces an evolution of carbonic anhydride in the flask. M. J. S. Incineration of Vegetable Matter. By G. LECHARTIER (Conyt. rend., 109, 727-7:31) .-When vegetable matter is incinerated with frze exposure to air or in a current of oxjgen, there is always volatilis- ation of a portion of tbe sulphur, which may be absorbed by conduct- ing the operation in a retort and passing the products of decomposition tlrrongh a tube containing sodium carbonate. Phosphorus, however, is not. volntilised, if the matter is first care- fully carbonised and then incinerated in presence of air or oxygen. Incineration is best conducted in a platinum dish with a glass funnel supported a short distance above it.The temperature is raised very gradually, and when thoroughly carbonised the residue is extractcd with warm water, washed, and the insoluble portion mois- tened thoroughly with milk of lime, dried, and heated until nil carbonaceous mattel- is burnt away. The phosphoric acid in the aqueous solution and the final residue is estimated in the usual way. D. A. L. C. H. B. Water Analysis. (Chem. Xews, 60, 203-204.) Report of the! Committee appointed by the British Association to confer with the Com- mittee of the American Association with a v i ~ w 0.f forming a uniform system of recording rpsulfs qf Water Analysis ; B. A. Meeting, 1889.-The cnmmittee recommend a system of statement for 8 complete analysis of which the following is an epitome. Results to be expressed iu partsASALYTICXL CHEMISTRY.197 per 100,000. Tn a potable water, t,he nunibers to be given in the follow- ing order :-Total solid matters, ( a ) in suspension, (tt) in solution ; organic carbon ; organic nit'rogen ; oxygen consumed, as indicated by decoloration of permanganate ; ammonia expelled on boiling with sodium carbonate ; ammonia expelled on boiling with alkaline perman- ganate ; nitrogen a s nitrates and nitrites ; chlorine ; hardness-tem- pomry, permanent, total ; in ti mineral water-carbonate of lime ; carbonate of magnesia ; carbonate of soda (calculated from residunl alkalinity aft,er boiling and filtering off precipitated CsCO, and MgCOs) ; total of each of the following elements-calcium, magnesium, potassium, sodium, iron (ferrous), iron (ferric), and each of the following radicles-sulphuric (SO,), nitric (NO,), nitrous ( NO2), phosphoric (PO,), silicic (SiO,) ; then each of the elementts-chlorine, bromine, and iodine, and of sulphiir at8 sulphide.Qi.ssoZz.ed gases; C.C. a t 0" C. and 760 mm. in 1 lit.re of water. Carbonic anhydride (CO,) ; oxygen ; nitrogen ; sulphuretted hydrogen. They consider that this uniform method should be adopted in all cases where communications come before learned bodies and when- ever possible in professional practice ; that the decimal numericn 1 notation is to be preferred ; tliat the different scales f o r potable and mineral waters suggested by the American Committee are undesirable ; that all result,s obtained by calculation should be sharply distin- guished from those obtained by direct determination ; that a state- iiient of mineral constituentas combined as salts is not t.0 be approved of unless the analytical da.ta upon which it is based are clearly stated ; that the American Committee's suggestion of recording the propor- tion of each element of binary compounds, and recording all the oxygen in oxy-compounds in combination with the negative element, as indicated above, is the most convenient for all purposes of calculn- tion, although the want of a name for these negative groups and the custom of quoting metallic elements as bases are objections to this system ; finally, that volumes of dissolved gases ma.y be given as above or in volumes of gas per 100 volumes of water.Estimation of Carbonic Acid in Potable Waters containing Magnesia. By H. TRILLICH ( Z e i t . ang. Chew., 1889, 337).-100 C.C. of the water is mixed in a stoppered cylinder with 5 C.C. of barium chloride solution (1 : 10) and 45 C.C. of titrated baryta-water (7 grams of barium hydroxide and 0.2 gram of chloride per litre) and allowed t o subside for 12 hours. Two quantities of 50 C.C. each are then removed without disturbing the sediment and are titrated with hydro- chloric acid, of which 1 C.C. equals 1 mg. of carbonic anhydride (using phenolphthalein). The magnesia is determined gravimetrically. Putting a for the number of C.C. of acid required by 45 C.C. of the baryta, b for the acid required by 50 C.C.of the clarified mixture, and m for the number of milligrams of magnesia in 100 c.c., then 1U(a - 3b - l.lm) gives the number of milligrams of free and loosely- combined carbonic anhydride per litre. The remaining 50 C.C. in the settling vessel with the precipitate is titrated with the same acid (using cochineal). If d is the number of C.C. used, 1O(d - b - 1.1111) is the total carbonic anhSdride in milligrams per litre. D. A. L. M. J. S .198 ABSTRACTS OF CHEMICAL PAPERS. Standard Solution for Clark’s Soap-test. By F. E. NEI,SON (Chenz. News, 60, 132).-The author suggests the following mode of preparing a standard soap solution of constant composition :-A gram of pure palmitic acid is dissolved in a little pure spirit, neutralised with 4 C.C.of normal soda solution and diluted to 200 C.C. with so much aqueous spirit as to retain 35 per cent. of alcohol in the standard solution. Fatty acids separated from ordinary tallow may be used instead of palmitic acid. Detection of Mercuric Cyanide in Toxicological Investiga- tions. By D. VITAL[ (Chem. Centr., 1889, ii, 391-392 ; from L’OTOR‘I., 12,181-196).--T he author recommends the following modification of Selmi’s method for the detection of mercuric cyanide in toxicological i t i ves t iga t,i on R.. The substance is acidified with tartaric acid, neutralised again with precipitated calcium carbonate, a, slight excess of aqueous hydrogen sulphide solution added, the flask closed and allowed to remain a t rest for 24 hours in the cold, then a further quantity of hydrogen sulphide water is added and a current of hydrogen passed through the liquid.The gases ai-e passed first through a solution of bismuth nitrate in dilut,e nitric acid to absorb the hydrogen sulphide, and secondly through aqueous potash for absorption of hydrogen cyanide ; in thc latter solution, the usual tests for hydrogen cyanide may be made. D. A. L. J. W. L. Reaction of Sodium Nitroprusside with Alkaline and Alka- line Earthy Hydroxides. By H. BKUNNER (Chem. News, 60, 16b). -Sodium nitroprusside produces an intensely yellow cdoyation with sodium, potassium, barium, or calcium hydroxide, but does not react with the soluble carbonates or hydrogen carbonates, By adding aqueous sodium nitroprusside to sodium hydroxide nntil an orange-colour appears, shaking with alcohol and allowing to settle, a deep-yellow oil separates, which ultimately solidifies to orange-coloured crystals.A n aqueous solution of this salt givc.s coloured precipitates with metallic salts ; moreover, with acids it gives a green colour, becoming violet on exposure to the air, finally giving :i green precipitate. Estimation of Glycerol by Oxidation with Permanganate in Acid Solution. By H. GR~~NWALD (Zeit. ang. Chew., 1889, 34-35). -Planchon’s method (Abstr., 1888, 1345) affords very service- able results ; in 12 determinations, the mean error of a single result was 1-81 per cent. Potash in Liebig’s bulbs is, however, more suit- able than soda-lime for absorbing the carbonic anhydride. D. A. L. M. 3 . S. Copper Solution for the Estimation of Glucose.Bg E. SOLDAINI (Chem. Centr., 1889, ii, 389-390; from L’Orosi, 12, 196--198).-The author recommends a more dilute solution of cupric sulphate in potassium hydrogen carbonate than that generally de- scribed under the name of “ Soldaini’s solution ” (compare Abstr.,ANALYTICAL CHEMISTRY. 1 Y!) 1589, 313). 3.464 gramsof cupric sulphate ( 5 as.) and 297 grams of potassium hydrogen carbonate are dissolved in 1 litre. This solution will detect 0*0005 gram of glucose in 10 C.C. of water by boiling with the reagent for 10 minutcs. For quantitative pur- poses it is applied as when using Fehling’s reagent, approximate tests being first made, and finally the quantity thns found added all a t once to the copper solution and boiled for 6ve minutes, when an excebs of neither copper nor sugar should be present.J. W. L. Iodine Absorption of Essential Oils. By R. H. DAVIES (Pharm. J. Trans. [3], 19, 821--824).-This paper records the results of the application of Hubl’s reagent to determine the “ iodine absorption ” of essential oils. A weighed quantity of the oil was al!owed to remain all night with an excess of the iodine solution. The differences ere greater than tliose found with fixed oils, as they ranged from 0 to nearly 400 per cent. A table of the results obtained with 64 essential oils and their derivatives shows the percentages obtained. Oil of almonds is ni2, menthol 0-12, camphor 0.46 per cent. English and Japanese oil of peppermint 43.5 to 57.7 per cent,. ; but American, 121.8 to 132.2. Testing Oil of Peppermint for Adulterants.By H. W. SNOW (Pharnr. J. Trans. [3], 19, 1056--1058).--The author gives the results of his trials of some tests which have been proposed for detecting the presence of certain adulterants in oil of peppermint. IVhen 5 per cent. or more of alcohol has been added, the oil will be coloured distinctly red on agitating it for a few seconds with a little magenta, which is insoluble in the perfectly pure oil. Oil of camphor n a y be detected by agitating two drops of the sample with a little nitric acid (sp. gr. 1-42>, when a reddish-brown colour may appear, even in the absence of oil of camphor, but this fades in two or three hours, while the distinct red colour due to the presence of this adulterant persists for two days. For detecting turpentine, the optical test is not cox~cIusive, as French oil of tuipentine has itself left- handed rotation.The non-solubility of turpentine in 80 per cent. alcohol fails to detect even 50 per cent. of it when mixed with oil of peppermint. Fractional distillation is useful, and when followed by determinations of the iodine ab>orptioa, trust worthy indicationa may be obtained in certain cases. Gold chloride in chloroform solutiou, bided with a few drops of a n essential oil, gives characteristic re- actions. Oil of turpentine reduces the solution quickly with little or no colour ; oil of camphor acts slowly with only a faint-blue colour ; oil of copaiba gives a fine blue solution which gradually loses its colour ; oil of peppermint quickly gives a brown, changing into violet- red.These reactions can, however, seldom be used with confidence, except under special circumstances. Thyrnol and anethoil 171.5 t o 182.9 per cent. R. R. R. R. Reactions of Essential Oils. By R. WILLIAMS (Chew. News, 60, 1 75--176).-The author has examined a great number of essential 011s with regard to their potash aud iodine absorption. noting also their boiling poiiits and specific gravities ; a table of results is given.200 ABSTRACTS OF CHEMICAL PAPERS. In h i s opinion concordant results have been obtained with oils of hi*gamot, caraway, cassia, cedar-wood, cinnamon, citron, citroneile, cloves, lemon, mace, nutmeg, orange, thyme, and verbena, and it is suggested that by examining these oils in this manner adulterations may be detected with certainty.Oils of aniseed, cajeput, eu- calyptus, juniper, lavender (various), spike, lemon grass, pennyroyal, peppermint (various), rosemary, rue, sage, and sassafras, did not yield coilcordant results, for which various causes are assigned, hnch as adulteration, difference in age, and change in composition. Oil of spike has a lower boiling point and a lower potash absorption than the more expensive oil of lavender. Oil of cinnamon has a lower gravitg, boiling point, and potash absorption, but a much higher iodine absor1)tir)n than the cheaper oil of cassia. At least two, aiid in some cases more samples of each oil have been examined. D. A. L. Reactions of Essential Oils. By R. A. CRwPs (Chem. News, 60, 236).-In reference to the iodine absorption of essential oils, attention is called to the importance of time and temperature in these reactions; the latter has already been recognised by both R.H. Davies and H. W. Snow (preceding page), but disregarded by R, Williams (precedicg abstract). The author now compares the results obtained by Barenthin, Davies, Snow, and Williams; there are discrepancies which are probably due to want of uniformity as regards the two factors mentioned above. H. W. Snow, in a letter (Chew. News, 60, 245), points out that he found the iodine absorption extremely useful in connection with the examination of oil of pepper- milit f u r adulteration with oil of turpentine ; he also gives references his own contributions and to the work of others on the subject. D. A. L. Tests for Fixed Oils. By P.X. MGRK (Pharnz. J. Trans. [3], 19, i85).-A reaction proposed by Hirschsohn (Abstr., 1889, 658) for the detection OF cotton-seed in other fixed oils was to mix 5 C.C. of the oil with 10 drops of a. chloroform solution of gold chloride (1 gram in 200 c.c.), and to htbat to 100”. The red coloration produced in from three to five minutes is found by the author not to be character- istic of cotton-seed oil, for he has obtained the like result with the oils of arachis, ben, poppy, sesame, walnut-kernel, &c. The paper contains extended lists of the gold chloride, and also of the silver nitrate reactions with these and many other kinds of fixed oils-pure, doubtful, and comniercial. R. R. Estimation of Neutral Fats. By M. GR~GER (&it. arcg. Cheni., 1889, 61-62).--1n the saponification of a neutral fat by alcoholic potash, it does not.suffice to boil for half an hour with a bare excess of the alkali, but it is necessary that the excess should not be less than a certain amount. For 5 grams of fat, the residual alkali ought to consume a t least 5 C.C. of semi-normal acid, otherwise saponification is very liable to be incomplete. This may account for many of the recorded wwiatiolis in the saponification equivalents of fats. M. J. S.ANALYTICAL CHEMISTRY. 193An a 1 y t i c a1 C h e m i s t r y.Filter Holder for Drying and Weighing. By C. REINHARIYT(Zeit. ang. Chetn., 1889, 61).-l'his is a glass box, in shape like afunnel, with a short, wide neck, and having a light ground cover.The filter, whether full or empty, is dried in it whilst retaining itsconical form, whereby not only is drying accelerated, but any sub-sequent treatment of the precipitate is much facilitated.Estimation of Sulphur in Burnt Pyrites.By G . LUKCS(Zeit. ang. Chern., 1889, 639--240).--Of methods depending on theneutralisation of an alkali by the conversion of the sulphur into asulphate in the dry way, that of Watson (Abstr., 1889, 306) is theonly accurate, as weli as the simplest and most expeditious one.Estimation of Nitrites. By W. R. DUNSTAN and T. S. DYMOND(Pkarm. J. Trans. [3], 19, 741--743).-The authors have devised anapparatus for titrating, in an air-free space, the iodine liberated bynitrites from an acid solution of potassium iodide. All sources oferror are thus eliminated, and the process has distinct advantagesover the gasometric methods, especially in the case of organicnitrites.Astout glass flask of about 100 C.C. capacity is fitted withail india-rubber stopper, through which pusses a short glass tubeconnected with a small tube-funnel by means OF a short piece of thickii.dia-rubber tubing carrying a steel screw clamp. 5 C.C. of 30 percent. potassium iodide solution, 5 C.C. of 10 per cent. sulphuric acid,:hnd 40 C.C. of water are introduced, and tlie mixture boiled in tlieflask with the tubes open until all the air and iodine that niay harebeen liberated have been expelled; when the steam is escapingfreely from the funnel, the clip is closed tightly a t the same momeiitthat the source of heat is withdrawn.Then the flask is cooled.A known quantity of the nitrite solution, equivalent to about0.1 gram of nitroiis acid, is placed i n the funnel a.iid caut;onslydrawn into the flask by unscrewing the clip, receiltly boiled waterM. J. S.M. J. S.VOL. C'FIII194 ABSTRACTS OF CHEMICAL PAPERS.being used for waclhing it down. The iodine liberated is estimatedby a decinormal sodium thiosulphate s o h tion, gradually introducedinto the flask with due precactions for the exclusion of air. Thecolour of the dissolved iodine is a sufficient indicator, but starch maybe used. Many test determinations of volatile organic nitrites aregiven, with the figures controlled by other methods. The results arevery accordant, and speak well for the accuracy of the process.R.R.Estimation of Arssnic in Iron. Bs M. A. v. REIS (Chem. CeTttr.,1889, ii, 379; from Stahl. u. Eisen, 9, 720-723).--10 grams of pigiron is dissolved with 100 C.C. of wat,er and 20 C.C. of concentratedsulphuric acid. The insoluble residue, consisting of those metalsprecipitable by hydrogen sulphide in acid solution, especiallvarsenic and copper, is collected, and dissolved with hydrochloric acidand potassium clrloyate. The chlorine is expelled, the ferric chloriderzdnced by sodium hypophosphite, and the arsenic and copper pre-cipitated by ammonium thiocsrbamate, filtered, washed with dilutehydrochloric acid and watep, then oxidised with concentrated nitrica ,id, filtered and the arsenic precipitated with magnesia mixture.The precipitate is washed into a platinum crucible with nitric acid,evaporated to dryness, and weighed after driving off the ammoniumsalts by ignition.Carbonic Oxide Detector.By RAUNE (Bull. SOC Chim. [3], 1,555-558) .-To indicate the presence of deleterious quantities ofcarbonic oxide in dwelling rooms, an apparatus is described in whichtlie fact, that gunqotton dusted with platinum black fires in air con-taining 2 5 per 1,000 of carbonic oxide, is made use of to determinethe closure of an electric circuit containing an alarum.Improvement in the Method of Estimating Carbonic An-hydride by Volume. By F. E'UCHS (Monatsh., 10, 602-604).--Tlleacid solution used to decompose the carbonate is previously saturatedwith and is kept in an at'mosphere of carbonic anhydride, whereb-ytlie usual error due to the retention of the gas in the acid is avoided.Estimation of Silica and Analysis of Siliceous Material. ByG.CRAIG (Chem. News, 60, 227).-Taking into consideration theerrors and di6culties attached to the estimation of silica by themethod of fusion with alkaline carbonates, the author prefers to driveoff the silica by means of hydrofluoric and sulphuric acids, and toestimate other substance6 in the residue. About 1.5 gram of finely-powdered substance is treated with sulphuric acid diluted with an equalvolume of wat'er, about 4 grams of pure hydrofluoric acid added, thewhole mixed well by shaking gently, and heated over a smdl flameuntil almost dry; the operation is reptt,ited, and the heating continueduntil sulphuric acid vapour is evolved in order to be sure that allthe fluorides are decomposed.The residue is subsequenhly dissolved inhydrochloric acid and examined in the usual manner.By ISBERT and VENATOR (Zd.UUQ. C h m . , 1&9, t;C --ti7).--E'or many pi:rpnscs a i*,zpid a:id fairlyJ. W. L.T. G. N.G. T. M.D. A. L.Analysis of Sodium SulphateA SALY'TIC AL C H EM1 STRT. 195accurate estimation of the sodium sulphate in the commercial articleis required. Ahout 2 grams of the sample is dissolved in a little hotwater, ammonia and ammonium carbonate are added, and the mixtureis filtered ; the precipitate is dissolved off the filter by hydrochloricacid, again precipitated as before, and then collected and thoroughlywashed.A little sulphuric acid is added to the filtrates and washings,which are then evaporated in a platinum basin and ignited. Fromthe weight of the residue is deducted the sodium sulphate corre-sponding tmo the sodium chloride in the original substance, as estimatedby titration for chlorine. The remainder is the sodium snlphate inthe substance taken. M. J. S.Chromium and Barium in Foods. By L. DE KONINGH ( A r c h .Pharm. [3], 27, 944 ; from Ned. Tij. Pharm. Chem. Tox., 1889, 257).-At least 25 gi-ams of the substance is burnt in a platinum dish, and theash is weighed. To the ash is added four times its weight. of potas-sium sodium carbonate arid the same amount of potassinm nitrate, anclthe whole is fused €or 15 minutes. After boiling with water and filter-ing, the liquid is yellow it' chromium is present ; but the presence ofmanganese may produce a greenish colour, which is removed by boil-ing for a few minutes with a little alcohol.The liquid is then concen-trated to 20 c.c., filtered into a test-tube, and compared with mate)* towhich potassium chromate solution is added until the two tints areof the same intensity. To prove that the colour is due to chromium,acidify with acetic acid and add lead acetate. If lead is present inthe original substance, a yellow precipitate is obtained before theacetate is added. The portion of ash insoluble in water is dissolvedin hydrochloric acid, and if lead is to be sought for, this is carefullyneutralised before hydrogen sulphide is added.To detect bariumcarbonate, the strongly acid solution of the ash is treated with a largeexcess of calcium sulphate solution, by which the barium is quicklyprecipitated as sulphate free from lead, as the Litter is readily solublein the strong acid. J. T.Magnesium as a Reagent. By H. N. WARREN (Chem. NPU+.S, 60,187--188).--It is pointed out that magnesium, on account of its purityand activity, is an excellent reducing agent. In the dry way it reducesniost metals, and even silica and boric anhydride when intenselyheated in closed vessels with them. It does not reduce the alkalisand alkaline earths, but is attacked by molybdic anhydride withexplosive violence. Being free from arsenic, it is well suited for use inNarsh's test, and as it contains neither iron, phosphorus, nor sulphur,scarcely reacts with potassium ferricyanide, and is more active thanzinc, it may be used with advantage for reducing ferric to ferroussalts.If a solution of zinc acetate is boiled with magnesium, thewhole of the zinc is precipitated, even though the solution also con-tains metals of the fourth grcup.Iron may be separated from chromium in the following manner:the acid solution of iron and chromium is precipitated with sodiumcarbonate, the precipitate dissolved in acetic acid and magnesiumadded. The reducing action is a t first violent ancl then ceases, bu196 ABSTRACTS OF CEEhIICAL PAPERS.on applying heat, the colour oE the solution changes from greentht-ough pink, red, violet back to green, the iron in the meantimc!being precipitated on the magnesium.Volumetric Estimation of Zinc.By A. VOIGT (%it. ang. Chem.,1889, 307-308) .-The solution of the substance in hydrochloric acidis oxidised with nitric acid and diluted to ahout 100 O.C. Sufficientpotassium tartrate to keep the iron in solution is added, and thenammonia to feeble alkalinity, and the liquid is further diluted to about2.50 C.C. Standard solution of potassium ferroq-anide is then rnn in,until a drhp of the iiiixtnre brought in contact with strong acetic aciddevelops a permanent blue. The ferrocyanide is of suitable strengthif 1 C.C. is equal to 0.01 gram of zinc. About 46 grams of the salt isdissolved to a litre, and the solution is standardised against one ofzinc made by dissolving 12.461 grams of zinc oxide in hydrochloric acidand diluting t o a litre ; 10 C.C.of this solution is mixed with 5 gramsof pctassium tartrate, a few drops of ferric chloride, ammonia, andwater to 250 c.c., and should require 10 C.C. of the ferrocyanide. Anessential condition is that the excess of ammonia should be as smalla s possible. Incorrect results are obtained when much manganese ispresent; lead is not injurious. The process is more rapid thanSjchaffner’s. M. J. S.Standardisation of Permanganate. By R. JAHODA (Zeit. ang.Chein., 1889, 87).-1n dissolving iron wire for the above purpose, theflask is fitted with a cork and a hent tube which dips into a beakercontaining solution of ,.odium hydrogen carbonate. Any of thissolntion drawn in during the cooling of the iron solution produces anevolution of carbonic anhydride in the flask.M. J. S.Incineration of Vegetable Matter. By G. LECHARTIER (Conyt.rend., 109, 727-7:31) .-When vegetable matter is incinerated withfrze exposure to air or in a current of oxjgen, there is always volatilis-ation of a portion of tbe sulphur, which may be absorbed by conduct-ing the operation in a retort and passing the products of decompositiontlrrongh a tube containing sodium carbonate.Phosphorus, however, is not. volntilised, if the matter is first care-fully carbonised and then incinerated in presence of air or oxygen.Incineration is best conducted in a platinum dish with a glassfunnel supported a short distance above it. The temperature israised very gradually, and when thoroughly carbonised the residue isextractcd with warm water, washed, and the insoluble portion mois-tened thoroughly with milk of lime, dried, and heated until nilcarbonaceous mattel- is burnt away.The phosphoric acid in theaqueous solution and the final residue is estimated in the usual way.D. A. L.C. H. B.Water Analysis. (Chem. Xews, 60, 203-204.) Report of the!Committee appointed by the British Association to confer with the Com-mittee of the American Association with a v i ~ w 0.f forming a uniformsystem of recording rpsulfs qf Water Analysis ; B. A. Meeting, 1889.-Thecnmmittee recommend a system of statement for 8 complete analysis ofwhich the following is an epitome. Results to be expressed iu partASALYTICXL CHEMISTRY.197per 100,000. Tn a potable water, t,he nunibers to be given in the follow-ing order :-Total solid matters, ( a ) in suspension, (tt) in solution ;organic carbon ; organic nit'rogen ; oxygen consumed, as indicatedby decoloration of permanganate ; ammonia expelled on boiling withsodium carbonate ; ammonia expelled on boiling with alkaline perman-ganate ; nitrogen a s nitrates and nitrites ; chlorine ; hardness-tem-pomry, permanent, total ; in ti mineral water-carbonate of lime ;carbonate of magnesia ; carbonate of soda (calculated from residunlalkalinity aft,er boiling and filtering off precipitated CsCO, andMgCOs) ; total of each of the following elements-calcium, magnesium,potassium, sodium, iron (ferrous), iron (ferric), and each of thefollowing radicles-sulphuric (SO,), nitric (NO,), nitrous ( NO2),phosphoric (PO,), silicic (SiO,) ; then each of the elementts-chlorine,bromine, and iodine, and of sulphiir at8 sulphide.Qi.ssoZz.ed gases;C.C. a t 0" C. and 760 mm. in 1 lit.re of water. Carbonic anhydride(CO,) ; oxygen ; nitrogen ; sulphuretted hydrogen.They consider that this uniform method should be adopted in allcases where communications come before learned bodies and when-ever possible in professional practice ; that the decimal numericn 1notation is to be preferred ; tliat the different scales f o r potable andmineral waters suggested by the American Committee are undesirable ;that all result,s obtained by calculation should be sharply distin-guished from those obtained by direct determination ; that a state-iiient of mineral constituentas combined as salts is not t.0 be approvedof unless the analytical da.ta upon which it is based are clearly stated ;that the American Committee's suggestion of recording the propor-tion of each element of binary compounds, and recording all theoxygen in oxy-compounds in combination with the negative element,as indicated above, is the most convenient for all purposes of calculn-tion, although the want of a name for these negative groups and thecustom of quoting metallic elements as bases are objections to thissystem ; finally, that volumes of dissolved gases ma.y be given as aboveor in volumes of gas per 100 volumes of water.Estimation of Carbonic Acid in Potable Waters containingMagnesia.By H. TRILLICH ( Z e i t . ang. Chew., 1889, 337).-100 C.C.of the water is mixed in a stoppered cylinder with 5 C.C. of bariumchloride solution (1 : 10) and 45 C.C. of titrated baryta-water (7 gramsof barium hydroxide and 0.2 gram of chloride per litre) and allowedt o subside for 12 hours. Two quantities of 50 C.C. each are thenremoved without disturbing the sediment and are titrated with hydro-chloric acid, of which 1 C.C. equals 1 mg. of carbonic anhydride (usingphenolphthalein). The magnesia is determined gravimetrically.Putting a for the number of C.C. of acid required by 45 C.C. of thebaryta, b for the acid required by 50 C.C. of the clarified mixture,and m for the number of milligrams of magnesia in 100 c.c., then1U(a - 3b - l.lm) gives the number of milligrams of free and loosely-combined carbonic anhydride per litre.The remaining 50 C.C. inthe settling vessel with the precipitate is titrated with the same acid(using cochineal). If d is the number of C.C. used, 1O(d - b - 1.1111)is the total carbonic anhSdride in milligrams per litre.D. A. L.M. J. S 198 ABSTRACTS OF CHEMICAL PAPERS.Standard Solution for Clark’s Soap-test. By F. E. NEI,SON(Chenz. News, 60, 132).-The author suggests the following mode ofpreparing a standard soap solution of constant composition :-A gramof pure palmitic acid is dissolved in a little pure spirit, neutralisedwith 4 C.C. of normal soda solution and diluted to 200 C.C. with somuch aqueous spirit as to retain 35 per cent. of alcohol in thestandard solution.Fatty acids separated from ordinary tallow maybe used instead of palmitic acid.Detection of Mercuric Cyanide in Toxicological Investiga-tions. By D. VITAL[ (Chem. Centr., 1889, ii, 391-392 ; from L’OTOR‘I.,12,181-196).--T he author recommends the following modification ofSelmi’s method for the detection of mercuric cyanide in toxicologicali t i ves t iga t,i on R..The substance is acidified with tartaric acid, neutralised again withprecipitated calcium carbonate, a, slight excess of aqueous hydrogensulphide solution added, the flask closed and allowed to remain a t restfor 24 hours in the cold, then a further quantity of hydrogen sulphidewater is added and a current of hydrogen passed through the liquid.The gases ai-e passed first through a solution of bismuth nitrate indilut,e nitric acid to absorb the hydrogen sulphide, and secondlythrough aqueous potash for absorption of hydrogen cyanide ; in thclatter solution, the usual tests for hydrogen cyanide may be made.D.A. L.J. W. L.Reaction of Sodium Nitroprusside with Alkaline and Alka-line Earthy Hydroxides. By H. BKUNNER (Chem. News, 60, 16b).-Sodium nitroprusside produces an intensely yellow cdoyation withsodium, potassium, barium, or calcium hydroxide, but does not reactwith the soluble carbonates or hydrogen carbonates,By adding aqueous sodium nitroprusside to sodium hydroxidenntil an orange-colour appears, shaking with alcohol and allowingto settle, a deep-yellow oil separates, which ultimately solidifies toorange-coloured crystals.A n aqueous solution of this salt givc.scoloured precipitates with metallic salts ; moreover, with acids it givesa green colour, becoming violet on exposure to the air, finally giving:i green precipitate.Estimation of Glycerol by Oxidation with Permanganate inAcid Solution. By H. GR~~NWALD (Zeit. ang. Chew., 1889, 34-35).-Planchon’s method (Abstr., 1888, 1345) affords very service-able results ; in 12 determinations, the mean error of a single resultwas 1-81 per cent. Potash in Liebig’s bulbs is, however, more suit-able than soda-lime for absorbing the carbonic anhydride.D. A. L.M. 3 . S.Copper Solution for the Estimation of Glucose. Bg E.SOLDAINI (Chem.Centr., 1889, ii, 389-390; from L’Orosi, 12,196--198).-The author recommends a more dilute solution of cupricsulphate in potassium hydrogen carbonate than that generally de-scribed under the name of “ Soldaini’s solution ” (compare Abstr.ANALYTICAL CHEMISTRY. 1 Y!)1589, 313). 3.464 gramsof cupric sulphate ( 5 as.) and 297 grams ofpotassium hydrogen carbonate are dissolved in 1 litre.This solution will detect 0*0005 gram of glucose in 10 C.C. of waterby boiling with the reagent for 10 minutcs. For quantitative pur-poses it is applied as when using Fehling’s reagent, approximatetests being first made, and finally the quantity thns found added alla t once to the copper solution and boiled for 6ve minutes, whenan excebs of neither copper nor sugar should be present.J.W. L.Iodine Absorption of Essential Oils. By R. H. DAVIES (Pharm.J. Trans. [3], 19, 821--824).-This paper records the results of theapplication of Hubl’s reagent to determine the “ iodine absorption ” ofessential oils. A weighed quantity of the oil was al!owed to remainall night with an excess of the iodine solution. The differencesere greater than tliose found with fixed oils, as they ranged from 0to nearly 400 per cent. A table of the results obtained with 64essential oils and their derivatives shows the percentages obtained.Oil of almonds is ni2, menthol 0-12, camphor 0.46 per cent. Englishand Japanese oil of peppermint 43.5 to 57.7 per cent,. ; but American,121.8 to 132.2.Testing Oil of Peppermint for Adulterants.By H. W. SNOW(Pharnr. J. Trans. [3], 19, 1056--1058).--The author gives theresults of his trials of some tests which have been proposed fordetecting the presence of certain adulterants in oil of peppermint.IVhen 5 per cent. or more of alcohol has been added, the oil will becoloured distinctly red on agitating it for a few seconds with a littlemagenta, which is insoluble in the perfectly pure oil. Oil of camphorn a y be detected by agitating two drops of the sample with a littlenitric acid (sp. gr. 1-42>, when a reddish-brown colour may appear,even in the absence of oil of camphor, but this fades in two or threehours, while the distinct red colour due to the presence of thisadulterant persists for two days. For detecting turpentine, the opticaltest is not cox~cIusive, as French oil of tuipentine has itself left-handed rotation.The non-solubility of turpentine in 80 per cent.alcohol fails to detect even 50 per cent. of it when mixed with oil ofpeppermint. Fractional distillation is useful, and when followed bydeterminations of the iodine ab>orptioa, trust worthy indicationa maybe obtained in certain cases. Gold chloride in chloroform solutiou,bided with a few drops of a n essential oil, gives characteristic re-actions. Oil of turpentine reduces the solution quickly with little orno colour ; oil of camphor acts slowly with only a faint-blue colour ;oil of copaiba gives a fine blue solution which gradually loses itscolour ; oil of peppermint quickly gives a brown, changing into violet-red.These reactions can, however, seldom be used with confidence,except under special circumstances.Thyrnol and anethoil 171.5 t o 182.9 per cent.R. R.R. R.Reactions of Essential Oils. By R. WILLIAMS (Chew. News, 60,1 75--176).-The author has examined a great number of essential011s with regard to their potash aud iodine absorption. noting alsotheir boiling poiiits and specific gravities ; a table of results is given200 ABSTRACTS OF CHEMICAL PAPERS.In h i s opinion concordant results have been obtained with oils ofhi*gamot, caraway, cassia, cedar-wood, cinnamon, citron, citroneile,cloves, lemon, mace, nutmeg, orange, thyme, and verbena, and it issuggested that by examining these oils in this manner adulterationsmay be detected with certainty.Oils of aniseed, cajeput, eu-calyptus, juniper, lavender (various), spike, lemon grass, pennyroyal,peppermint (various), rosemary, rue, sage, and sassafras, did notyield coilcordant results, for which various causes are assigned,hnch as adulteration, difference in age, and change in composition.Oil of spike has a lower boiling point and a lower potash absorptionthan the more expensive oil of lavender. Oil of cinnamon has a lowergravitg, boiling point, and potash absorption, but a much higher iodineabsor1)tir)n than the cheaper oil of cassia. At least two, aiid in somecases more samples of each oil have been examined. D. A. L.Reactions of Essential Oils. By R. A. CRwPs (Chem. News,60, 236).-In reference to the iodine absorption of essential oils,attention is called to the importance of time and temperature in thesereactions; the latter has already been recognised by both R. H.Davies and H. W. Snow (preceding page), but disregarded by R,Williams (precedicg abstract). The author now compares theresults obtained by Barenthin, Davies, Snow, and Williams; thereare discrepancies which are probably due to want of uniformity asregards the two factors mentioned above. H. W. Snow, in a letter(Chew. News, 60, 245), points out that he found the iodine absorptionextremely useful in connection with the examination of oil of pepper-milit f u r adulteration with oil of turpentine ; he also gives referenceshis own contributions and to the work of others on the subject.D. A. L.Tests for Fixed Oils. By P. X. MGRK (Pharnz. J. Trans. [3],19, i85).-A reaction proposed by Hirschsohn (Abstr., 1889, 658) forthe detection OF cotton-seed in other fixed oils was to mix 5 C.C. of theoil with 10 drops of a. chloroform solution of gold chloride (1 gramin 200 c.c.), and to htbat to 100”. The red coloration produced infrom three to five minutes is found by the author not to be character-istic of cotton-seed oil, for he has obtained the like result with theoils of arachis, ben, poppy, sesame, walnut-kernel, &c. The papercontains extended lists of the gold chloride, and also of the silvernitrate reactions with these and many other kinds of fixed oils-pure,doubtful, and comniercial. R. R.Estimation of Neutral Fats. By M. GR~GER (&it. arcg. Cheni.,1889, 61-62).--1n the saponification of a neutral fat by alcoholicpotash, it does not. suffice to boil for half an hour with a bare excessof the alkali, but it is necessary that the excess should not be lessthan a certain amount. For 5 grams of fat, the residual alkali oughtto consume a t least 5 C.C. of semi-normal acid, otherwise saponificationis very liable to be incomplete. This may account for many of therecorded wwiatiolis in the saponification equivalents of fats.M. J. S

ISSN:0368-1769    

DOI:10.1039/CA8905800193

出版商:RSC    

年代:1890

数据来源: RSC

摘要:

201 General and P h y s i c a l Chemistry. Phosphorescence of Copper, Bismuth, and Manganese in the Sulphides of the Alkaline Earth Metals. By V. KLATr and 1'. LENARD (Ann. Phys. Chenz. [2], 38, 90--107).--The difference in the colour of the light emitted by the phosphorescent sulphides of metals of the alkaline earths when prepared by different methods, has hitherto been attributed to a difference in physical structure. The authors find, however, that the difference is really a chemical one, the above sulphides being, when pure, practically without phos- phorescence, and only exhibiting this phenomenon when containing traces of the sulphides of copper, bismuth, manganese, or some fourth metal not yet identified, the colour of the phosphorescence varying with the nature and proportions of the active sulphides present, The presence or absence of any of the above metals can readily be ascer- tained, as each gives rise to a characteristic band i n the spectrum of the phosphorescent materisl, the position of which is always the same.The intensity of the phosphorescence increases with t,he amount of active sulphide present, up to a certain point, but, when a, maximum is reached, any further addition causes a decrease in the intensity, and ultimately destroys the phosphorescence. The quantities OE active sulphide necessary to produce the above maxi- mnm are very small. I n order to produce the brightest phosphores- cence, a third substance should be present in addition to the above. This consists of some colourlsss salt which is fusible at the tempera- ture required for the preparation of the phosphorescent sulphides. It will therefore form a thin layer on t'he surface of the sulphide, to which the active metal imparts a faint coloration, essential to the productiou of phosphorescence.H. C. Refractive Indices of Gases. By T. P. DALE (Phil. Mag. [ 5 ] , 28, 268--271).-The author has observed certain empirical relations between the specific refractive energies of gaseous elements and between the logarithms of these values. Thus the logarithms of the specific refractive energies of nitrogen, chlorine, and phosphorus are identical, as also are those of sulphur and oxygen. The logarithms of the first three are double, and those of sulphur and oxygen 16 times that of hydrogen. The logarithm of the specific refractive energy of mercury is 8 times, and that of arsenic 9 times this quantity. Again, the specific refractive energy of oxygen is nearly double that of hydrogen, that of mercury 4 times, of arsenic 8 times, of sulphur 12 times that of hydrogen.Amongst compounds, the log. specitic refractive energy of nitrous oxide is half that of carbonic oxide, whilst that of cyanogen is 6 times that of hydrogen. The author is engaged on the relations between the molecular weight a.ud refraction of gases. H. I(. 1'. FOL. LTIII. 1)202 ABSTRACTS OF CE-IMICAL PAPERS. Refractive Indices of Salt Solutions. By B. WALTER (Ann,. Plrys. Clzem. [Z], 38, 107--118j.-The author tinds from his own observations and those of othws that the refraction of salt solutions is subject t o laws similar to t,hose for the reduction of the freezing point.Thus the index of refraction of a salt solution is proportional to the amount, of' salt dissolved. Solutions containing equal numbers of molecules of salts of monad metals with nionohasic acids have the same refractive index, ot'her similar solutions of salts of monad metals wit.11 bibasic acids have a refractive index which is practically double the above, and those of salts of diad metals hare a refractive index which is three times that of the first. These laws hold even for concentrated solutions, and there is nothing t.0 indicate the forma- tion of hydrntes in any of the solutions exarnincd. The behaviour of cupric chloride in solutions containing more than 12 per cent. of'the salt is abnormal, as the refraction of such solutions is greater than i t should be according to the above rules, and points to the existence of molecules of greater complexity in the more concenhted solutions.This is supported by the well-known difference in colonr of t,lie con- centrated and dilute solutions. A similar change is exhibited by potassium ferricyanide solutions at a concentration of 4 per cent. Fluorescein solutions were also examined u p to a concentration of 40 per cent., in order to ascertain if any other molecuIar change, than that already recorded (hbstr., 1889, 553) at 2 per cent., could be detected, but with negative result. H. C. A Standard Clark Cell. By H. S. CARHART (Phil. Mug. [ 5 ] , 28, 420-423) -The author 6nds that local action takes place in Clark cells owing to contact between the zinc and the mercurous sulphnte, the temperature coefficient being thereby a1 tered.He has con- structed a cell in which contact is prevented. The new cell has A tempemture coefflcient less than that of' Lord Rnyleigh's cell ; more- over its tcmperxture coefficientl decreases wibh rise of temperature. The polarisatiou is negligible for external resistances greater than 10,OcjO ohms. H. K. T. Electromotive Forces of Cells containing Mixed Salt Solu- tions. By G. F. R. BLOCHMANN (Ann. Phys. Chew. [dj, 37,564-575). --The l3.M.l'. of the standard Clark cell, Hg 1 Hg.,SO, I ZnSO, [ Z L ~ , decreases with rise of temperature, whereas that o f the Helmholtz cell, Hg I H&lZ I ZnC1, I Zn, increases. By mixing the chlorides and sulpliates of the metals, the author hoped to obtain a cell that would remain unaffected by chaiige of temperature, but a cell corrtain- ing mixtures in the proportions calculat~d to effect this result was found to differ but slightly f r o m the chloride cell in its behaviour with re*pect to temperature.The author was therefore led to further investigate the E.M.P. of cells cmtaining mixed salt solutions. Copper and zinc were selected as electrodes, the copper being im- niersed in a solution of two copper salts contairied in a porous pot, surrounded by a solution of two similar zinc salts in which tho zinc electrode is placed. The salts used were the sulphates,GENERAL AND PHYSICAL CHEMISTRY. 203 chlorides, and nitrates of the metals, in solutions containing 1 mol.of salt to 50 mols. O C water, and the acetates dissolved in the proportion 1 to 250. The results obtained with the various mixtures are tabulated and given in curve form. Cells containing the sulphates and chlorides, sulphates and acetates, and the chlorides and acetates give electromotive forces which practically correspond with the mean of those of cells containing the unmixed solutions, taken in the ratio in which the salts are mixed. The E.M.F. of the other cells containing the nitrates is usually below that thus calculated ; but in the case of mixtures of nitrates and acetates containing a large excess of nitrate, the E.M.F. is greater t'han the theoretical. The exceptions in these latter cases are probably due to the fact that the salts have some chemical action one on another, which may in some way be connected with the partial dissociation which such salts undergo in aqueous solction.By E. COHN (Ann. Phys.Chem. [a], 38,42--52).--The author confirms the former result obtained by himself m d Arons (Abstr., 1888, 394) for the sp. ind. cap. of water, in this case using the method originally ernployed for liquids of low conductivity (Ann. Phys. Chem. [el, 28, 454). H. C. Specific Inductive Capacity of Water. H. C. Variations in the Electrical Resistance of Nitrogen Peroxide with a Rise of Temperature. By J. J. BOGUSKI (Compt. r e d . , 109, 804--806).--Nitrocren peroxide has a very hiph resistance, but t,he coi1ductivit.y becomes recogtiisable and measurable in presence of 0.01 to 0.1 per cent. of water.No absolute measurements were made, Imt the relative resistances at different temperatures were determined. Concordant results were obtained with diEerentl methods o l measure- men t. The resistance increases as the temperature rises, and above 7d0 t.he peroxide is an almost perfect insulator. Abrupt variations are observed between 0" and I f " . Although a rise of temperature is a.ccompanied by a definite and static increase in resistance, t!lis is preceded hg a temporary dynamic reduction of resistance, which is greater the more suddenly the compound is heated. This temporary vnriation is so considerable that it, can readily be recognised if a lamp, or the body of the observer, is moved tuwards the tube containing t.lie peroxide, provided that the latter is at a lower temperature.The phenomena are doubtless connected with t,he dissociation of the peroxide. Neither NO, nor N20c is decomposed by an eiectric wrrent, and hence they are insuliitors when separate and when mixed. The dissociation produced by heat sets u p atomic movements favour- able t.o the conduction of elect,ricity by convection, and heiicc the i~esistm~ce diminishes. These atomic rnotioiis soon cease, because the atoms form new molecules. A new condition of equilibrium is established, and the resistance acquires it,s normal static value. If the peroxide is cooled suddenly, the variation of the resistance is a.lways in the same direction, aird no oscillations are observed similar to tbose produced by heating. c. 13. B. f 2204 ABSTRACTS OF CHEMICAL PAPERS.Change in Freshly-prepared Solutions. By E. PFEI FFER (Ann. Phys. Chem. [2], 37, 539--563).-The author has noticeti in former experiments (Abstr., 1886,115) that if a solution is allowed to remain for some length of time, the electrical conductivity often undergoes a temporary decrease, and that this continues until a minimum is reached, from which it again increases. The author now finds that this occurs with water which is left freely exposed in the ordinary way, but not with water which has been kept out of contact with the atmosphere or only exposed to purified air. The phenomenon is, therefore, in some manner due t o the impurities OF the atmosphere. The change becomes more pronounced if the solution is acidified slightly, and the more so the greater the amount of acid added, whereas basic substances produce just the opposite effect, and neutral salts are practicallv without action.As carbonic acid is among the acids which have the above effect, and ammonium carbonate is a much better conductor than free ammonia in aqueous solution, the change is in all probability not dne to the ammonia in the atmosphere. It might, however, be due to organic impurities. Electrical Conductivity as a Means of Investigating the Interaction of Acids of Complex Function. By D. BERTHELOT (Compt. rend., 109, 801 -804).-The author has utilised determina- tions of electrical conductiyity in order to determine the conditions of equilibrium between dilute saline solutions and aspartic acid, which combines the functions of a base and an acid. Solutions were em- ployed containing a gram-equivalent of the acid 01- salt in 100 litres.Wit,h this degree of dilution, variations in molecular conductivity with variations in the concentration of the solution, are sufficiently small to be negligible. The conductivity of a mixture of aspartic acid and sodium chloride indicates decomposition to the extent of 4 per cent., and precisely the same final system is obtained by mixing sodium aspartate with hydro- chloric acid, the decomposition in this case amounting to 96 per cent. I n the first case, the addition of a second or third molecule of aspartic acid oi' sodium chloride has no appreciable effect. In the second case, if two molecular proportions of sodium aspartate are inixed with one Ilio~ecular proportion of hydrochloric acid, the observed conductivity IS lower than that calculated on the assumption of complet'e decom- position, a rcsult due to interaction between sodium aspartate and aspartic acid, and, in a much lower degree, between sodium aspartate and sodium chloride.A third molecular proportion of sodiuin aspar- tate exerts a slight but distinct additional influence in the same direct ion. C. H. B. H. C. Electrical Conductivities and Multiple Affinities of Aspartic Acid. By D. BERTHELOT (Compt. rend., 109, 864--867).-1n this paper the author investigates the basic functions of aspartic acid, the methods of measurement being identical with those used in the investigation of its acid functions (preceding ahst,ract,). The addition of an equivalent proportion of hydrochloric acid to aspartic acid pro- duces a very marked diminution in the electrical resistance; thisGENERAL ASI) PHTSICAL CHEJIISTRY.205 indicates a reduction in the number of molecules, owing to cornbina- tion between the two acids. A second equivalent of hydrochloric acid produces about one-fifth of the reduction produced by the first. A second equivalent of aspartic acid produces half the reduction of tlie first, and a third equivalent produces one-fourth of the original reduction. The addition of aspartic acid to sodinm aspartate increases the resistance, owing to the formation of a double salt, but the effect of successive qmntities of aspartic acid gradually diminishes. The addition of an equivalent of sodium hydroxide to sodium aspartate is accompanied by a very considerable increase in resist- ance ; a second eqiiivalent of alkali produces an effect only one-third as great, and this is true also of a third equivalent. A second equi- valent, of aspartate has a comparatively small effect., and a third or fourth equivalent has still less.Sodium chloride and sodinm aspartate, in equivalent proportions, form a small quantitg of a double salt, but a further quantity of either salt has but little influence on the result. C. H. B. Correction of Thermometric Readings for the Column Outside the Heating Medium. By E. RxhiBAca (Ber., 22, 3072 -3075).-The author has made a large number of observations with various therrrlometers of Jena glass, in order to determine the cor- rection which must be made i n the observed reading when only part of the mercurial column is surrounded by the heating vapour.The very numerous observations, which are given in tabular form, show that Kopp’s ( A n d e n , 94) , Holtzmann’s (HundwSrterbuch der Chemie, 7, 368), and Thnrpc’s (Trans., 1880, 160) corrections give results which are too low with long threads, and too high with short ones; the error in the case of loug threads may be more than one degree w-hen Holtzmaun’s or Thorpe’s correction is employed. Mousson’s constant (Ann. Phys. Chem., 133, 311) has not a con- stant value in the case of high-registering thermometers, and the error in determining this constant, as recommended by MOUSSOI~, may amount to 0.7 degree. Wtillner’s value for ,,?-is also variable. F. S . K. Experimental Determination of the Ratio of the Specific Heats in Superheated Steam.By R. COHICN (Ann. P h y s . Chem. [ a ] , 37, 628-633).--From the velocity of sound in superheated steam, the ratio of the specific heats k was determined by a, method similar to that used by Strecaker in the case of chlorine, bromine, and iodine. The mean value for k thns found was 1.287, the temperature varying from 144” to 300” ; betwecn these temperatures no change in the constancy of k being observed. From the equation of Clausius for the relation between volume, pressure, and temperature in any vapour, the values of k for other temperatures can be calculated, and such a calculation giveR a value of 1.333 a t 95”, agreeing with that found by Jaeger (Abstr., 1889, 460) and other observers.The author does not, however, place reliauce in such a calculation, as the206 ABSTRACTS OF CHEMICAL PAPERS. Clausius equation is no longer truly applicable to superheated vapours. H. C. Animal Heat and the Heat of Formation and Combustion of Urea. By BERTHELOT and P. PETIT (Compt. rend., 109,751)-764). -The combustion of urea was readily effected in t h e calorimetric bomb, the heat of combustion for 1 gram being 2530.1 Cals., o r CO(NH2), + 0, = C 0 2 gas + Nz gas + 2H20 liquid, develops + 151.8 Cals. a t constant volume, or + 151.5 Cals. a t constant pres- sure. The forniation of solid urea from carbon (diamond) and its gaseous Constituents liberates + 80.8 Cals. The heat of dissolution at about 11" is -3.58 Cnls., and hence the heat of formation in solu- tion in water (or urine) is +77*2 Cals., and its heat of combustion +l60.9 Cals.The formation of solid urea and liquid water from carbonic anhydride and ammonia would liberate +31.1 Cals., and the forma- tion of the dissolved compound from dissolved carbonic anhydride and dissolved ammonia, would liberate +4*3 Cals. The formaiion of urea from ammoninrn carbonate (both in solution) would absorb -6.4 to -8.0 Cals., and hence this change does not take place directly, but the reverse change liberates + 6.4 to + 8.0 Cals., and hence readily occurs under favourable conditions. The converdion of ammonium cyanate into urea liberates about +7*1 Cals. The com- plete combustion of urea liberates 11.8 Cals. less than the combustion of its constituents, if they were in the free state, but this complete oxidation only takes place under exceptional conditions.It seems, in fact, that nitrogen in the form of amido-compounds oxidises with much greater difficulty than carbon and hydrogen, is capable of being converted into ammonia, and when introduced into the organism in the form of food, is excreted again with a very small loss of its energy. C. H. B. Specific Gravity Apparatus. By BAILHACHE and COMMELIN (Bull. SOC. Chim. [3], 2, 196--198).--This apparatus is intended for the determination of the volume of vegetable products, such as fruits, rootls, &c. By means of an iron plunger, the substance is kept ini- mersed under the surface of mercury, contained in a vessel communi- cating by a U-tube with a cylinder containing t.he same metal above the surface of which is placed coloured alcohol ; any displacement of mercury in the former vessel causes the alcohol to enter an upright narrow, calibrated tube, and thus the volume of the mercury displaced, and consequently that of the substance, is determinable.T. G. N. Dissociation of Salts containing Water, and the Constitution of the Combined Water. By W. MULLER-EERZBACH (Bw., 22, 3181--3182).-The author gives a list of salts containing water of crystallisation ; those molecules of water which show a greater tension being placed in the table to the right and separated by a + sign.GENERAL AND PEYSICAL CHEMISTRY. 207 Na2HP04 + 2H20 + 5H,O + 5H20, NaLCO, + H?O + 9H20, N%B,O, + 5H20 + 5H20, MgSO, + HZ0 + 5H2O + HZO, COSO, + H,O + 5H20 + HzO, Na,SO, + 1OH,O, NiSO, + H20 + 5H20 + H20, FeSO, + H20 + 3H,O + 3H,O, ZnSO, + H,O + H 2 0 + 5H,O, MnSO, + HpO + H,O + 3H,O, CaClz + H20 + HzO + 2H20 + 2H20, MgC12 + 4H20 + 2H,O,* XaBr + 4HF,0, CUSO, + HzO + H2O + H20 i- 2H20, COC1, + 2H20 + 4H20, MnC12 + H20 + H20, BaCI, + HzO + H20, NtlS203 + 2H20 + 3H20, XaC2H302 + 3H@, CaN206 + 2H20 + H20 (?), CaN,O, + 4H20, CaN206 + 2H20 + H20, ZnN,O, + 3H20 + H20 + H,O, PbC'(fd604 + 3H?O, AlK(S04)2 + 3H2O + 9H20, AI(NH4)(S04)2 + 3H10 + 9H20, AlNa(SO,), + 6H20 + 6H20, CrK(SO,), + 6H20 + 6H,O, BaHzOz + H20 + H20 + 5H,O + H,O, SrH202 + H20 + 6H20 + H,O.* Only decomposed to MgC1, + 4HzO. In the case of copper sulphate, the second and third molecules of water cannot be separated in this way a t temperatures above 40".E. S. R. Osmosis with Living and Dead Membranes. By %. W. REID Specific Volume of Aqueous Vapour. By C. DIETERICI (AWL Yhys. Ckem. "23, 38, 1-26).-This paper deals with the deter- mination of the specific volume of water vapour satmated a t 0". The author has previously determined the heat of vaporisation of water a t O", which is 596.8 cnl. per gram, and now employs this quantity to determine the weight of water converted into vapour at 0", and occnpying a certain known volume. With the ice calori- meter, as small a quautity of heat as 0.03 cal. is still measurable, and therefore, although a t 0" a volume of 5 litres would only con- tain 25 milligrams of saturated water vapour, this weight can be determined by the above method to within 0.2 per cent., the error of a direct weighing being about 4 per cent.The only other serious source of error is in the condensation which takes place on the surface of the glass, which is particularly marked if the vessel which is to contain the vapour is exhausted as far as possible. This error is very materially reduced by selecting a glass of as insoluble a variety as possible, boiling well with water to remove alkali, and allowing a &mall quantity of air to remain in the exhausted vessel. The results show that water vapour saturated a t 0" obeys Gay- Lussac's law for perfect gases down to the saturation point. The density of the vapour is 0.0048856 milligram / c.c., and therefore the specific volume a t 0 "is 20468 C.C. / milligram. Since water vapour saturated at Oo behaves like a perfect gas, the density corresponds with that which might be deduced from Avogndro's law.The pressure which it exercises may, therefore, be calculated, and is found to be 4.619 mm. (Brit. Med. J., 1890, i, 165--167).-See this vol., p. 277. The above numbers are correct to within 0.5 per cent. H. C. Molecular Constitution of Isomeric Solutions. By G. GORE (Phil. Mug. [ 5 ] , 28,289-303 ; compare Abstr., 1889,90,200,201,665, and 810).-The author examines by means of the voltaic balance the208 ABSTRACTS OF CHEMICAL PAPERS. dishibu tion of base when equivalent quant'ities of sulphuric and nitric acids and sodium hydroxide are brought together. According to the researches of J. Thomsen, the final result is the same whether sodium sulphate is added t o nitric acid or sodium nitrate to sulphuric acid, or sodium hydroxide to mixed nitric and sulphuric acids.The author has examined the voltaic energies of two mixtures, one A, consisting of NazSOa + 2HNO3, the other B, consisting of 2NaN03 + H2S0,. The general results of the investigation are that the solution B pro- ceeds at, once t o the filial distribution of soda between the acids (grds of the soda to the nitric acid and i r d to the sulphuric acid), whilst the solutim A, if very dilute or mixed a t a low temperature, shows a voltaic energy approaching that of its separate constituents, and that i t is only after a very considerable lapse of time or after a short ebulli- tion that it approximates to the value found f o r B. Further, it has becn found that a number of molecular compounds of the acids and salts with one another are formed when A is first prepared.Hence the order o€ mixing has a considerable influence on the voltaic energy of the freshly prepared solution. I n the solution B, the evolved nitric acid probably unites wit.h an equivalent quantity of the free snlphuric acid. Loss of voltaic energy does not necessarily involve loss of thermal energy, since the solution A absorbs heat when mixed, whilst B develops heat (Thomsen), both changes being accompanied by loss of voltaic energy. H. K. T.201General and P h y s i c a l Chemistry.Phosphorescence of Copper, Bismuth, and Manganese in theSulphides of the Alkaline Earth Metals. By V. KLATr and1'. LENARD (Ann. Phys. Chenz. [2], 38, 90--107).--The difference inthe colour of the light emitted by the phosphorescent sulphides ofmetals of the alkaline earths when prepared by different methods,has hitherto been attributed to a difference in physical structure.The authors find, however, that the difference is really a chemicalone, the above sulphides being, when pure, practically without phos-phorescence, and only exhibiting this phenomenon when containingtraces of the sulphides of copper, bismuth, manganese, or some fourthmetal not yet identified, the colour of the phosphorescence varyingwith the nature and proportions of the active sulphides present, Thepresence or absence of any of the above metals can readily be ascer-tained, as each gives rise to a characteristic band i n the spectrum ofthe phosphorescent materisl, the position of which is always thesame.The intensity of the phosphorescence increases with t,heamount of active sulphide present, up to a certain point, but, when a,maximum is reached, any further addition causes a decrease in theintensity, and ultimately destroys the phosphorescence. Thequantities OE active sulphide necessary to produce the above maxi-mnm are very small. I n order to produce the brightest phosphores-cence, a third substance should be present in addition to the above.This consists of some colourlsss salt which is fusible at the tempera-ture required for the preparation of the phosphorescent sulphides.It will therefore form a thin layer on t'he surface of the sulphide, towhich the active metal imparts a faint coloration, essential to theproductiou of phosphorescence.H. C.Refractive Indices of Gases. By T. P. DALE (Phil. Mag. [ 5 ] ,28, 268--271).-The author has observed certain empirical relationsbetween the specific refractive energies of gaseous elements andbetween the logarithms of these values. Thus the logarithms of thespecific refractive energies of nitrogen, chlorine, and phosphorus areidentical, as also are those of sulphur and oxygen. The logarithmsof the first three are double, and those of sulphur and oxygen 16 timesthat of hydrogen. The logarithm of the specific refractive energy ofmercury is 8 times, and that of arsenic 9 times this quantity. Again,the specific refractive energy of oxygen is nearly double that ofhydrogen, that of mercury 4 times, of arsenic 8 times, of sulphur12 times that of hydrogen.Amongst compounds, the log. speciticrefractive energy of nitrous oxide is half that of carbonic oxide,whilst that of cyanogen is 6 times that of hydrogen. The author isengaged on the relations between the molecular weight a.ud refractionof gases. H. I(. 1'.FOL. LTIII. 1202 ABSTRACTS OF CE-IMICAL PAPERS.Refractive Indices of Salt Solutions. By B. WALTER (Ann,.Plrys. Clzem. [Z], 38, 107--118j.-The author tinds from his ownobservations and those of othws that the refraction of salt solutionsis subject t o laws similar to t,hose for the reduction of the freezingpoint. Thus the index of refraction of a salt solution is proportionalto the amount, of' salt dissolved.Solutions containing equal numbersof molecules of salts of monad metals with nionohasic acids have thesame refractive index, ot'her similar solutions of salts of monadmetals wit.11 bibasic acids have a refractive index which is practicallydouble the above, and those of salts of diad metals hare a refractiveindex which is three times that of the first. These laws hold evenfor concentrated solutions, and there is nothing t.0 indicate the forma-tion of hydrntes in any of the solutions exarnincd. The behaviour ofcupric chloride in solutions containing more than 12 per cent. of'thesalt is abnormal, as the refraction of such solutions is greater than i tshould be according to the above rules, and points to the existence ofmolecules of greater complexity in the more concenhted solutions.This is supported by the well-known difference in colonr of t,lie con-centrated and dilute solutions. A similar change is exhibited bypotassium ferricyanide solutions at a concentration of 4 per cent.Fluorescein solutions were also examined u p to a concentration of40 per cent., in order to ascertain if any other molecuIar change,than that already recorded (hbstr., 1889, 553) at 2 per cent., couldbe detected, but with negative result.H. C.A Standard Clark Cell. By H. S. CARHART (Phil. Mug. [ 5 ] , 28,420-423) -The author 6nds that local action takes place in Clarkcells owing to contact between the zinc and the mercurous sulphnte,the temperature coefficient being thereby a1 tered. He has con-structed a cell in which contact is prevented.The new cell has Atempemture coefflcient less than that of' Lord Rnyleigh's cell ; more-over its tcmperxture coefficientl decreases wibh rise of temperature.The polarisatiou is negligible for external resistances greater than10,OcjO ohms. H. K. T.Electromotive Forces of Cells containing Mixed Salt Solu-tions. By G. F. R. BLOCHMANN (Ann. Phys. Chew. [dj, 37,564-575).--The l3.M.l'. of the standard Clark cell, Hg 1 Hg.,SO, I ZnSO, [ Z L ~ ,decreases with rise of temperature, whereas that o f the Helmholtzcell, Hg I H&lZ I ZnC1, I Zn, increases. By mixing the chloridesand sulpliates of the metals, the author hoped to obtain a cell thatwould remain unaffected by chaiige of temperature, but a cell corrtain-ing mixtures in the proportions calculat~d to effect this result wasfound to differ but slightly f r o m the chloride cell in its behaviourwith re*pect to temperature.The author was therefore led to furtherinvestigate the E.M.P. of cells cmtaining mixed salt solutions.Copper and zinc were selected as electrodes, the copper being im-niersed in a solution of two copper salts contairied in a porous pot,surrounded by a solution of two similar zinc salts in which thozinc electrode is placed. The salts used were the sulphatesGENERAL AND PHYSICAL CHEMISTRY. 203chlorides, and nitrates of the metals, in solutions containing 1 mol.of salt to 50 mols. O C water, and the acetates dissolved in theproportion 1 to 250. The results obtained with the various mixturesare tabulated and given in curve form.Cells containing the sulphatesand chlorides, sulphates and acetates, and the chlorides and acetatesgive electromotive forces which practically correspond with themean of those of cells containing the unmixed solutions, taken in theratio in which the salts are mixed. The E.M.F. of the other cellscontaining the nitrates is usually below that thus calculated ; but inthe case of mixtures of nitrates and acetates containing a largeexcess of nitrate, the E.M.F. is greater t'han the theoretical. Theexceptions in these latter cases are probably due to the fact that thesalts have some chemical action one on another, which may in someway be connected with the partial dissociation which such saltsundergo in aqueous solction.By E.COHN (Ann.Phys.Chem. [a], 38,42--52).--The author confirms the former resultobtained by himself m d Arons (Abstr., 1888, 394) for the sp. ind.cap. of water, in this case using the method originally ernployed forliquids of low conductivity (Ann. Phys. Chem. [el, 28, 454).H. C.Specific Inductive Capacity of Water.H. C.Variations in the Electrical Resistance of Nitrogen Peroxidewith a Rise of Temperature. By J. J. BOGUSKI (Compt. r e d . ,109, 804--806).--Nitrocren peroxide has a very hiph resistance, butt,he coi1ductivit.y becomes recogtiisable and measurable in presence of0.01 to 0.1 per cent. of water. No absolute measurements were made,Imt the relative resistances at different temperatures were determined.Concordant results were obtained with diEerentl methods o l measure-men t.The resistance increases as the temperature rises, and above 7d0t.he peroxide is an almost perfect insulator.Abrupt variations areobserved between 0" and I f " . Although a rise of temperature isa.ccompanied by a definite and static increase in resistance, t!lis ispreceded hg a temporary dynamic reduction of resistance, which isgreater the more suddenly the compound is heated. This temporaryvnriation is so considerable that it, can readily be recognised if a lamp,or the body of the observer, is moved tuwards the tube containingt.lie peroxide, provided that the latter is at a lower temperature.The phenomena are doubtless connected with t,he dissociation ofthe peroxide.Neither NO, nor N20c is decomposed by an eiectricwrrent, and hence they are insuliitors when separate and when mixed.The dissociation produced by heat sets u p atomic movements favour-able t.o the conduction of elect,ricity by convection, and heiicc thei~esistm~ce diminishes. These atomic rnotioiis soon cease, because theatoms form new molecules. A new condition of equilibrium isestablished, and the resistance acquires it,s normal static value.If the peroxide is cooled suddenly, the variation of the resistanceis a.lways in the same direction, aird no oscillations are observedsimilar to tbose produced by heating. c. 13. B.f 204 ABSTRACTS OF CHEMICAL PAPERS.Change in Freshly-prepared Solutions. By E. PFEI FFER(Ann. Phys.Chem. [2], 37, 539--563).-The author has noticeti informer experiments (Abstr., 1886,115) that if a solution is allowed toremain for some length of time, the electrical conductivity oftenundergoes a temporary decrease, and that this continues until aminimum is reached, from which it again increases. The author nowfinds that this occurs with water which is left freely exposed in theordinary way, but not with water which has been kept out of contactwith the atmosphere or only exposed to purified air. The phenomenonis, therefore, in some manner due t o the impurities OF the atmosphere.The change becomes more pronounced if the solution is acidifiedslightly, and the more so the greater the amount of acid added,whereas basic substances produce just the opposite effect, and neutralsalts are practicallv without action.As carbonic acid is among theacids which have the above effect, and ammonium carbonate is a muchbetter conductor than free ammonia in aqueous solution, the changeis in all probability not dne to the ammonia in the atmosphere. Itmight, however, be due to organic impurities.Electrical Conductivity as a Means of Investigating theInteraction of Acids of Complex Function. By D. BERTHELOT(Compt. rend., 109, 801 -804).-The author has utilised determina-tions of electrical conductiyity in order to determine the conditions ofequilibrium between dilute saline solutions and aspartic acid, whichcombines the functions of a base and an acid. Solutions were em-ployed containing a gram-equivalent of the acid 01- salt in 100 litres.Wit,h this degree of dilution, variations in molecular conductivitywith variations in the concentration of the solution, are sufficientlysmall to be negligible.The conductivity of a mixture of aspartic acid and sodium chlorideindicates decomposition to the extent of 4 per cent., and precisely thesame final system is obtained by mixing sodium aspartate with hydro-chloric acid, the decomposition in this case amounting to 96 per cent.I n the first case, the addition of a second or third molecule of asparticacid oi' sodium chloride has no appreciable effect.In the second case,if two molecular proportions of sodium aspartate are inixed with oneIlio~ecular proportion of hydrochloric acid, the observed conductivityIS lower than that calculated on the assumption of complet'e decom-position, a rcsult due to interaction between sodium aspartate andaspartic acid, and, in a much lower degree, between sodium aspartateand sodium chloride.A third molecular proportion of sodiuin aspar-tate exerts a slight but distinct additional influence in the samedirect ion. C. H. B.H. C.Electrical Conductivities and Multiple Affinities of AsparticAcid. By D. BERTHELOT (Compt. rend., 109, 864--867).-1n thispaper the author investigates the basic functions of aspartic acid, themethods of measurement being identical with those used in theinvestigation of its acid functions (preceding ahst,ract,). The additionof an equivalent proportion of hydrochloric acid to aspartic acid pro-duces a very marked diminution in the electrical resistance; thiGENERAL ASI) PHTSICAL CHEJIISTRY.205indicates a reduction in the number of molecules, owing to cornbina-tion between the two acids. A second equivalent of hydrochloricacid produces about one-fifth of the reduction produced by the first.A second equivalent of aspartic acid produces half the reduction oftlie first, and a third equivalent produces one-fourth of the originalreduction.The addition of aspartic acid to sodinm aspartate increases theresistance, owing to the formation of a double salt, but the effect ofsuccessive qmntities of aspartic acid gradually diminishes.The addition of an equivalent of sodium hydroxide to sodiumaspartate is accompanied by a very considerable increase in resist-ance ; a second eqiiivalent of alkali produces an effect only one-thirdas great, and this is true also of a third equivalent.A second equi-valent, of aspartate has a comparatively small effect., and a third orfourth equivalent has still less.Sodium chloride and sodinm aspartate, in equivalent proportions,form a small quantitg of a double salt, but a further quantity of eithersalt has but little influence on the result. C. H. B.Correction of Thermometric Readings for the ColumnOutside the Heating Medium. By E. RxhiBAca (Ber., 22, 3072-3075).-The author has made a large number of observations withvarious therrrlometers of Jena glass, in order to determine the cor-rection which must be made i n the observed reading when only partof the mercurial column is surrounded by the heating vapour. Thevery numerous observations, which are given in tabular form, showthat Kopp’s ( A n d e n , 94) , Holtzmann’s (HundwSrterbuch der Chemie,7, 368), and Thnrpc’s (Trans., 1880, 160) corrections give resultswhich are too low with long threads, and too high with short ones;the error in the case of loug threads may be more than one degreew-hen Holtzmaun’s or Thorpe’s correction is employed.Mousson’s constant (Ann.Phys. Chem., 133, 311) has not a con-stant value in the case of high-registering thermometers, and the errorin determining this constant, as recommended by MOUSSOI~, mayamount to 0.7 degree. Wtillner’s value for ,,?-is also variable.F. S . K.Experimental Determination of the Ratio of the SpecificHeats in Superheated Steam.By R. COHICN (Ann. P h y s . Chem.[ a ] , 37, 628-633).--From the velocity of sound in superheatedsteam, the ratio of the specific heats k was determined by a, methodsimilar to that used by Strecaker in the case of chlorine, bromine, andiodine. The mean value for k thns found was 1.287, the temperaturevarying from 144” to 300” ; betwecn these temperatures no change inthe constancy of k being observed. From the equation of Clausiusfor the relation between volume, pressure, and temperature in anyvapour, the values of k for other temperatures can be calculated, andsuch a calculation giveR a value of 1.333 a t 95”, agreeing with thatfound by Jaeger (Abstr., 1889, 460) and other observers. Theauthor does not, however, place reliauce in such a calculation, as th206 ABSTRACTS OF CHEMICAL PAPERS.Clausius equation is no longer truly applicable to superheatedvapours.H. C.Animal Heat and the Heat of Formation and Combustionof Urea. By BERTHELOT and P. PETIT (Compt. rend., 109,751)-764).-The combustion of urea was readily effected in t h e calorimetricbomb, the heat of combustion for 1 gram being 2530.1 Cals., o rCO(NH2), + 0, = C 0 2 gas + Nz gas + 2H20 liquid, develops + 151.8 Cals. a t constant volume, or + 151.5 Cals. a t constant pres-sure. The forniation of solid urea from carbon (diamond) and itsgaseous Constituents liberates + 80.8 Cals. The heat of dissolutionat about 11" is -3.58 Cnls., and hence the heat of formation in solu-tion in water (or urine) is +77*2 Cals., and its heat of combustion+l60.9 Cals.The formation of solid urea and liquid water from carbonicanhydride and ammonia would liberate +31.1 Cals., and the forma-tion of the dissolved compound from dissolved carbonic anhydrideand dissolved ammonia, would liberate +4*3 Cals.The formaiion ofurea from ammoninrn carbonate (both in solution) would absorb-6.4 to -8.0 Cals., and hence this change does not take placedirectly, but the reverse change liberates + 6.4 to + 8.0 Cals., andhence readily occurs under favourable conditions. The converdion ofammonium cyanate into urea liberates about +7*1 Cals. The com-plete combustion of urea liberates 11.8 Cals. less than the combustionof its constituents, if they were in the free state, but this completeoxidation only takes place under exceptional conditions.It seems,in fact, that nitrogen in the form of amido-compounds oxidises withmuch greater difficulty than carbon and hydrogen, is capable of beingconverted into ammonia, and when introduced into the organism inthe form of food, is excreted again with a very small loss of itsenergy. C. H. B.Specific Gravity Apparatus. By BAILHACHE and COMMELIN(Bull. SOC. Chim. [3], 2, 196--198).--This apparatus is intended forthe determination of the volume of vegetable products, such as fruits,rootls, &c. By means of an iron plunger, the substance is kept ini-mersed under the surface of mercury, contained in a vessel communi-cating by a U-tube with a cylinder containing t.he same metal abovethe surface of which is placed coloured alcohol ; any displacement ofmercury in the former vessel causes the alcohol to enter an uprightnarrow, calibrated tube, and thus the volume of the mercury displaced,and consequently that of the substance, is determinable.T.G. N.Dissociation of Salts containing Water, and the Constitutionof the Combined Water. By W. MULLER-EERZBACH (Bw., 22,3181--3182).-The author gives a list of salts containing water ofcrystallisation ; those molecules of water which show a greatertension being placed in the table to the right and separated by a + signGENERAL AND PEYSICAL CHEMISTRY. 207Na2HP04 + 2H20 + 5H,O + 5H20,NaLCO, + H?O + 9H20,N%B,O, + 5H20 + 5H20,MgSO, + HZ0 + 5H2O + HZO,COSO, + H,O + 5H20 + HzO,Na,SO, + 1OH,O,NiSO, + H20 + 5H20 + H20,FeSO, + H20 + 3H,O + 3H,O,ZnSO, + H,O + H 2 0 + 5H,O,MnSO, + HpO + H,O + 3H,O,CaClz + H20 + HzO + 2H20 + 2H20,MgC12 + 4H20 + 2H,O,*XaBr + 4HF,0,CUSO, + HzO + H2O + H20 i- 2H20,COC1, + 2H20 + 4H20,MnC12 + H20 + H20,BaCI, + HzO + H20,NtlS203 + 2H20 + 3H20,XaC2H302 + 3H@,CaN206 + 2H20 + H20 (?),CaN,O, + 4H20,CaN206 + 2H20 + H20,ZnN,O, + 3H20 + H20 + H,O,PbC'(fd604 + 3H?O,AlK(S04)2 + 3H2O + 9H20,AI(NH4)(S04)2 + 3H10 + 9H20,AlNa(SO,), + 6H20 + 6H20,CrK(SO,), + 6H20 + 6H,O,BaHzOz + H20 + H20 + 5H,O + H,O,SrH202 + H20 + 6H20 + H,O.* Only decomposed to MgC1, + 4HzO.In the case of copper sulphate, the second and third molecules ofwater cannot be separated in this way a t temperatures above 40".E.S. R.Osmosis with Living and Dead Membranes. By %. W. REIDSpecific Volume of Aqueous Vapour. By C. DIETERICI (AWLYhys. Ckem. "23, 38, 1-26).-This paper deals with the deter-mination of the specific volume of water vapour satmated a t 0".The author has previously determined the heat of vaporisation ofwater a t O", which is 596.8 cnl. per gram, and now employs thisquantity to determine the weight of water converted into vapourat 0", and occnpying a certain known volume. With the ice calori-meter, as small a quautity of heat as 0.03 cal. is still measurable,and therefore, although a t 0" a volume of 5 litres would only con-tain 25 milligrams of saturated water vapour, this weight can bedetermined by the above method to within 0.2 per cent., the error ofa direct weighing being about 4 per cent. The only other serioussource of error is in the condensation which takes place on the surfaceof the glass, which is particularly marked if the vessel which is tocontain the vapour is exhausted as far as possible.This error is verymaterially reduced by selecting a glass of as insoluble a variety aspossible, boiling well with water to remove alkali, and allowing a&mall quantity of air to remain in the exhausted vessel.The results show that water vapour saturated a t 0" obeys Gay-Lussac's law for perfect gases down to the saturation point. Thedensity of the vapour is 0.0048856 milligram / c.c., and therefore thespecific volume a t 0 "is 20468 C.C. / milligram. Since water vapoursaturated at Oo behaves like a perfect gas, the density corresponds withthat which might be deduced from Avogndro's law. The pressurewhich it exercises may, therefore, be calculated, and is found to be4.619 mm.(Brit. Med. J., 1890, i, 165--167).-See this vol., p. 277.The above numbers are correct to within 0.5 per cent.H. C.Molecular Constitution of Isomeric Solutions. By G. GORE(Phil. Mug. [ 5 ] , 28,289-303 ; compare Abstr., 1889,90,200,201,665,and 810).-The author examines by means of the voltaic balance th208 ABSTRACTS OF CHEMICAL PAPERS.dishibu tion of base when equivalent quant'ities of sulphuric and nitricacids and sodium hydroxide are brought together. According to theresearches of J. Thomsen, the final result is the same whether sodiumsulphate is added t o nitric acid or sodium nitrate to sulphuric acid, orsodium hydroxide to mixed nitric and sulphuric acids. The authorhas examined the voltaic energies of two mixtures, one A, consistingof NazSOa + 2HNO3, the other B, consisting of 2NaN03 + H2S0,.The general results of the investigation are that the solution B pro-ceeds at, once t o the filial distribution of soda between the acids (grdsof the soda to the nitric acid and i r d to the sulphuric acid), whilstthe solutim A, if very dilute or mixed a t a low temperature, shows avoltaic energy approaching that of its separate constituents, and thati t is only after a very considerable lapse of time or after a short ebulli-tion that it approximates to the value found f o r B. Further, it hasbecn found that a number of molecular compounds of the acids and saltswith one another are formed when A is first prepared. Hence theorder o€ mixing has a considerable influence on the voltaic energy ofthe freshly prepared solution. I n the solution B, the evolved nitricacid probably unites wit.h an equivalent quantity of the free snlphuricacid. Loss of voltaic energy does not necessarily involve loss of thermalenergy, since the solution A absorbs heat when mixed, whilst Bdevelops heat (Thomsen), both changes being accompanied by loss ofvoltaic energy. H. K. T

ISSN:0368-1769    

DOI:10.1039/CA8905800201

出版商:RSC    

年代:1890

数据来源: RSC

摘要:

208 ABSTRACTS OF CHEMICAL PAPERS. I n o r g a n i c Chemistry. Density of Fluorine. By He. MOISSAN (Con$. rend., 109, 86 I--864).--Fluorine was obtained by electrolysis, as before, but a larger apparatus was used, and in order to purify the gas completely from hydrogen fluoride, it was passed through a platinum wcrm cooled to -550" by nieans of methyl chloride, and then through a platinum tube contaiuing anhydrous sodium fluoride, which combines with hydrogen fluoride with great energy. The sodium salt is far prefer~ble to the potassium salt, because it is not hygroscopic. The pure fluoi'ine was collected in platinum flasks of about 100 C.C. capacity, which had been previously filled with nitrogen. After being weighed, the fluorine was brought in contact with water, and the evolved gases were measnred and analysed, a correction being made for any nitrogen which had not been displaced.The mean sp, gr. found was 1.265, whilst the value calculated from F = 19 is 1.316. C. H. B. Autoxidation. By M. TRAUHE (Bey., 22, 30.57-3062 ; compare Abstr., 1889, 937).-A reply to Hoppe-Seyler (Abstr., 1889, 1106). The author is satisfied that he has proved that nascent hydrogen in presence of oxygen molecules has not a powerful oxidising action, as stated by Hoppe-Seyler, and also that the oxidising action of palladiumIN0 RQANIC CHEMISTRY. 209 hgdride cannot be attributed to nascent hydrogen. R e criticises Hoppe- Sey ler's remarks very severely, and concludes by expressing the hope that his part in the discussion on autoxidation with Hoppe- Seyler may be ended.Hydrogen Arsenide and Antimonide. By 0. BRUNN (Be?-., 22, 3202-320i) .-Hydrogen arsenide and hydrogen sulphide do not act on one another in absence of air a t the ordinary temperature, either in the gaseous condition or in aqueous solution, even on ex- posure to direct sunlight. The admission of air quickly causes i n both cases a precipitate of arsenious sulphide. It has been previously observed that hydrogen arsenide is itself acted on by air or oxygen, with formation of a black powder. An examination of this product has shown that its composition varies with the amount of air present, the gas being first oxidised to solid hydrogen arsenide, and then, if there be sufficient oxygen, to metallic arsenic. The above-mentioned formation of arsenious sulphide is, therefore, probably preceded by the formation of arsenic.If the mixture of hydrogen arsenide and sulphide is heated, sepa- ration of arsenious sulphide commences at about 230". Separate ex- periments with hydrogen arsenide show that the latter commences to dissociate a t 2:30°, and that in this case also the formation of arsenious sulphide is a secondary reaction. Hydrogen antimonide is a t once decomposed by hydrogen sulphide, even in absence of air and light. On heating the former gas alone, dissociation commences a t about 150". The author proposes to make use of this fact for the detection of traces of ant[iniony occurrirtq together with arsenic, in other gases, such as hydrogen. For this purpose thegases are passed through a tube 0.8-1.0 metre in length, and heated by a liquid boiling a t 208-210".No arsenic whatever is deposited, and the antimony mirror may be further examined by the usual methods. H. G. C. Combination of Sodium and Potassium with Ammonia. By A . JOANNIS (Compt. rend., 109, 900--902).-When one equivalent of the alkali metal is brought in contact with 20 equivalents of liquid ammonia, and the ammonia gas is afterwards removed, its pressure rapidly diminishes. At a, certain point, the pressure becomes constant ; in the case of sodium the pressure was 1700 mm. a t 0", and the com- position of the mixture Na + 5.3NHj. The exact composition varies with the temperature, notwithstanding the constancy of the pressure, and hence the product in the tube is riot a definite compound. When a further quantity of the gas is removed, a solid substance with an intense copper-red colour is left, and the constant pressure observed niny be regarded as the vapour pressure of liquid ammonia saturated with this solid.When only one molecule of ammonia is present, €or each atom of metal, no trace of liquid remains, and if still more ammonia is removed, the free sodium o r potassium alone remains, and as this decomposition takes place at a constant pressure, it may be re- garded as true dissociation. Careful experiments gave 0.99 equivalent as the inferior limit, and 1.1 equivalent as the superior limit of the quantity of ammonia combined with one atom of the alkali metal, and F. S. I(.2 10 ABSTRACTS OF CHEMICAL PAPERS. it may therefore be taken that the solid residue, which the author calls potassammonium or sodumnaonium, has the composition NHJK or NH,Na.C. H. B. Thiosulphates. By A. FOCK and K. K~iiss (Ber., 22,3096-3101). -Potassium t,hiosnlphate, 3K2S203 + €LO, separates in colourless, prismatic crystals wben an aqueous solution of the salt is evaporated over sulphuric acid, and when the mother liquors are kept over sul- phuric acid for some time longer the salt separates in large, rhombic crystals, with 5 niols. H20 ; these results agree with those previously obtained by Rammelsberg, Kessler, and Dopping. Lithium thaosuijhate, Li,S203 + 3H,O, crystallises in large, colour less, very deliquescent needles, and is soluble in alcohol ; when heated, it is decomposed into lithium sulphrtte and lithium sulphide.Ammonium thiosulphate, (NH4)2S20:3, separates in anhydrous, colourless plates when an aqueoiis solution of the salt is evaporated over sulphuric acid ; Rammelsberg found that the salt crystallised with 1 mol. H,O. F. S. K. Allotropic Forms of Silver. Ry M. C. LEA (Amer. J. Sci. [3], 37,476-491 ; and 38,47--50, and l29).-The author considers that his own researches have established the existence of silver sub- chloride, although the experiments of Newbury, Muthmann, v. Pfordten, and others, have shown that there is a t present no evi- dence of the existence of a silver sub-oxide, Ag,O. He points out that the fact that a substance will not pass through a dialyser merely proves that it is colloidal and not that it is not in solution. Further, many substrnces which undoubtedly form true solutions are carried down by gum when the latter is added to the liquid and then pre- cipitated by addition of alcohol.The products described in these papers differ from those obtained by v. Pfordten in that they readily amalgamate with mercury and evolve no gas wheu treated with dilute sulphuric acid. Silver can exist in three allotropic forms, or more probably in three modifications of the same form, the differences between the three being less than their differences from normal silver. They differ in colour and other physical properties, and in chemical activity ; they probably represent an active condition of silver of which the ordinary metal is a polymeride. A. Soluble allotropic silver, which forms a deep-red solution, is mrttt black, blue, or green, when solid and moist, and brilliant metallic bluish-green when dry.B. Insoluble allotropic silver, derired from the preceding modifica- tion, dark reddish-brown when moist, and brilliant metallic bluish- green, like A, when dry. C. Gold-like allotropic silver, dark-bronze coloured when moist, but like burnished gold when dry. No soluble modification of this form seems to exist, but a copper-coloured variety is produced under certain conditions. When dry they are very friable and are readily reduced to an impalpable The three modifications are as follows :- All three modifications have certain properties in common.INORQANIC CHEMISTRY. 211 powder, differing markedly in this respect from normal silver. Their most striking property, however, is their power of drying with their particles in optical contact, and if spread while moist on paper or glass, they form mirrors of great perfection and beauty when dry.If these films are treated with solutions of the haloids, ferric chloride, or, hest of all, sodium hypochlorite, very beautiful interference colonrs are obtained. The phenomena are quite different from those obtained with normal silver leaf under the same conditions. Very dilute mineral acids and moderately dilute acetic acid immediately convert allotropic silver into grey normal silver without the evolution of any trace of gas. A. Soluble allotropic silver is obtained by the action of con- centrated solutions of ferrous citrate or a mixture of ferrous sulphnte and sodium citrate on a concentrated solution of a silver sait.If the solutions are not very concentrated, a deep-red liquid is formed which may remain transparent for some time or may gradually deposit a black precipitate. Concentrated solutions should be used, the fol- lowing proportions being found to give the best results. A mixture of ~ ( J O C.C. of a 30 per cent. solution of ferrous sulphate and 280 C.C. of n 40 per cent. solution of sodium citrate was added a t once to 200 C.C. of a 10 per cent. solution of silver nitrate. The liquid, which immediately becomes black, is viporously agitated for several minutes, allowed to remain for 10 to 15 minutes, and the liquid then decanted. A large quantity of a lilac-coloured precipitate remains, but alters slowly even in contact with the mother liquor, and when it is drained the colour changes almost immediately to deep blue.It may be washed with a solution of sodium or ammonium citrate, sulphate, or nitrate, preferably ammonium nitrate, because, although completely soluble in pure water, it is quite insoluble in presence of 5 to 10 per cent. of these salts. A good plan is to add sufficient water to dis- solve nearly the whole of the precipitate and then sufficient am- monium nitrate to reprecitate it. The substance gradually changes whilst being washed and becomes less and Iess soluble. After wash- ing seven or eight times in the manner described, it was washed with alcohol of 95 per cent'. to remove ammonium nitrate and then analysed : it contained 97-27 per cent. of silver and the filtrate from the silver chloride precipitate contained only ferric citrate.It retains water even after prolonged exposure in a dry vacuum. but becomes anhydrous atl 100" ; a t low redness i t gives off smal I quanti- ties of carbonic anhydride, but. no trace of either hydrogen or oxygen. These determinations were made after the substance had become insoluble, and hence it seemed possible that while in solution it might be combined with citric acid. Determinations of the silver and citric acid in a solution of the purified substance (which was proved by optical examination to form a true solution) gave the ratio of silver to citric acid in one case as 55.63 : 1 and in another 193.7 : 1, results which show that the proportion of citric acid is variable and is always very small. Some of the purified precipitate was dried a t loo", inixed with water, and again evaporated to dryness; all the silver separated as grey normal silver and the liquid was quite neutral.If a perfectly neutral iron solution is used in the prepara-212 ABSTRACTS OF CHEMICAL PAPERS. tion of the substance, the liquid after reduction is either nentrsl or very faintly acid. If a solution of the purified lilac precipitate is mixed with a neutral solution of magnesium sulphate, tshe iusoluble form, which consists of almost pure silver, is thrown down, but the liquid remains quite neutral. Possibly the silver is in combination with some neutral substance derived from citric acid, but if so, i t must be some entirely new compound. Ballo has observed that the action of ferrous salts on tartaric acid produces a neutral substance of the same composition as arabin, CsH,,O5. The change which the lilac precipitate undergoes during purification and washing is indi- c a t d by changes of colour, and the constitution of the lilac pre- cipitate whilst under the mother liquor is still doubtful.If the precipitate is spread on paper, it is blood red while moist, blue with metallic lustre when half dry, and matt blue when quite dry. If dried in lumps, the colour and lustre vary considerably. B. Insolzc,ble allotropic silver is obtained from the preceding form by spontaneous change or by the action of certain salts. Alkaline sulphates, nitrates, and citrates precipitate soluble allotropic silver from its solutions, but it still remains soluble.Magnesium, copper, iron, and nickel sulphates, potassium dichromate, potassium ferrocya- nide, barium nitrate, and silver nitrate all precipitate it i n an insoluble form. The soluble precipitate is blue or bluish-black ; the insoluble form is brown and continually darkens while being washed. Am- monia dissolves the insoluble modification ; sodium borate and alkaline sulphates reconvert i t into a soluble form, different however from the original. With a dilute solution of sodium borate, a brown soln- tion is obtained ; with sodium or pot.assium sulphate, a yellow-red solution ; with ammonium sulphate, a red solution. If concentrated fiolutions of these salts are used, the change into the soluble form takes place, but the substance does not dissolve until the salt has been washed away b7 pure water.Sodium nitrite added to a solu- tion of the soluble form partially converts it into normal silver and renders it quite insoluble even in ammonia. I n one case the insoluble variet,y became spontaneously soluble and formed a rose-red solution. I n another case it separated very slowly and spontaneously from a solution in the form of short, black needles and thin prisms, which lost their crystalline form i n contact with pure water but did not dissolve; it dried with a green, metallic lustre. It seems that pure water tends to produce a colloidal form, whether soluble or insoluble, whilst, salts tend to produce a crystalline form. Analysis showed that the insoluble allotropic silver contained 97.96 per cent. of the metal, the remainder being ferric citrate.I t retains water in a vacuum but becomes anhydrous a t 100". When spread in the moist state over paper, it forms a green film with a brilliant metallic liistre. The green is a mixture of blue and yellow, one or the other predominating according to the direction of the illumination. The yellow is polarised in the plane of incidence, and the blue in a direction normal to that plane. All the products were more or less yellow, but the proportion of blue light varied con- siderably and is less the more prolonged the washing of the pre- cipitate. If some of the substance is precipitated by means ofINORGANIC CHEMISTRT. 213 magnesium or aluminium sulphate and is sprea4 on paper without washing, the dry film has the appearance of it highly lustrous, bright- blue metal.When the moist substance is spread on glass, it forms very perfect mirrors when dry. C. Gold-like allotropic silver is obtained by the reduction of silver tartrate by ferrous tartrate in dilute soliitions, but the permanency of tlie product depends on the details of the preparation and is greater the more completely air and light are excluded from the dry sub- stance. The following method gives a permanent product :-a mixture of 107 C.C. of a 30 per cent. solution of ferrous sulphate, 200 C.C. of a 20 per cent. solution of sodium-potassium tartnte, and 800 C.C. of water is added gradually, and with constant stirring, to a mixture of 200 c c. of a 10 per cent. solution of silver nitrate, 200 C.C. of the solution of the alkaline tartrate, and 800 C.C.of water. The precipitate is a t first red, but changes to black, and when washed on the filter becomes bronze-colonred. If dried in lumps or in films on paper or glass, it has the colour and lustre of burnished gold. It is very permanent when dry, but more liable to change while moist, an({ forms a copper-coloured variety, which however is still bright mld peimanent,. While washing, it is important to keep the filter full of water. This modification contains 57.8 to 98.75 per cent. of silver, the remainder being ferric tartrate. The specific gravities of €3 and C were determined after they bad been left under water in a vacuum for a, long time; sp. gr. of in- soluble allotropic silver = 9 58 ; sp. gr. of gold-like a:lotropic silver = 8.51.The sp. gr. of normal silver is 10.5, and that of fiuely divided precipitated silver 10.62. At looo, a bluish-green film of B acquired a superficial bright- yellow colour, and x film of C under the same coilditions became superficially blue, but these changes were confined t,o the surfaces. All three modifications are affected by light; A and B become brown after some hours, and the coppery modification of C becomes bright-yellow. A very bright bluish-green modification of B ob- tained by rapid and short washing acquired the colour of gold after one day's exposure to sunlight, ; samples which have been well washed yield a matt film on paper and become brown when exposed to light. The gold-like moditication acquires a somewhat purer yellow colour when exposed to light in absence of moisture, but in presence of moisture 3 or 4 days exposure to sunlight changes it into white normal silver of great beauty. Moisture alone t.euds to darken its colour.It is interesting to note that organic compounds of silrer always yield grey or black, lustreless products when exposed to light. The modifications A and B are obtained by the reduction of silver citrate by ferrous citrate, and C by the reduction of silver tartrate by ferrous tartrate. No similar results are obtained by the action of ferrous oxalate on silver oxalate. On glass i t forms very perfect mirrors. C. H. B. Action of Ljght on Silver Chloride. By R. HITCFICOCK (Amer. C'hem. J., 11, 474--480).-FineIy divided precipitated silver chloride was allowed to ssttle on microscopic cover glasses,214 ABSTRACTS OF CHEMICAL PAPERS.carefully washed, and dried in a desiccator. I n this way the thin glass slips are obtained covered with a very thin, semi-trans- parent layer of silver chloride. They were then weighed, placed in a tube through which a current of pure hydrogen was passing, and exposed to sunlight, the chlorine which was liberated being absorbed in silver nitrate solution and afterwards weighed. The glass slips with the silver chloride were weighed after the experi- ment. per gram of silver chloride ; the chlorine absorbed by the silver nitrate was very slightly smaller in quantity than the loss in weight of the silver chloride. In one case the product gave np a considerable pro- portinn of silver when heated with dilute nitric acid, aiid hence it wonld seem that decomposition had gone so f a r that the protective action of the unaltered silver chloride had to a great extent been eliminated.C. H. B. Zinc Hydrosulphide. By V. v. ZOTTA (Monatsl~., 10, 807-812). -The author finds, contrary to the statement of Thomsen (Abstr., 1879, 206), that when equivalent quantities cf zinc sulphate and an alkaline h-j-drosulphide are mixed, the precipitate obtained has not the formula Zn(SH)2, but must be regarded as having the composi- tion Zn,H,S4, = Zn(SH)2,2ZnS. The production of this corn- round explains the evolution of hydrogen sulphide which takes place on adding an alkaline hydrosulphide to zinc sulphate ; for the com- pound Zn3H2SI may be regarded as being formed from 3 mols. of the hydrosulphide by loss of 2 mols.of hydrogen sulphide. Thomsen further says (Zoc. cit.) that if zinc sulphate is treated with two equiva- lents of sodium hydrosulphide, no precipitate is produced, but the resulting solution is slightly opalescent ; and concludes that sodium hydrosulphide behaves towards zinc sulphate in precisely the same way as sodium hydroxide. The author in repeating this experiment fincis that about, 20 per cent. of the sulphur present is evolved a~ hydrogen sulphide, but that long continued boiling does not cause the formation of a precipitate. If, however, a mixture of zinc sul- phate with four times its equivalent of sodium hydrosulphide is made, the slightly opalescent solution obLained is rendered turbid on boiling for a few minutes, or on treatment with acids, alkalis, or certain salts, and the precipitate is identical with the sulphide Zn,H2S4, mentioned above.Crystalline Anhydrous Zinc Phosphate and Zinc Arsenate. By A. DE SCHULTKX (&ill. Soc. C h i m [3], 2, 300--302).-Zinc chlorophosphata did not separate from the solution of nnrmal tetra- hydrated zinc phosphate in fused zinc chloride, but rbombic prisms of anhydrous zinc phosphate were obtained from the melt; these liave a sp. gr. of 3.998 a t 15', and melt at, a red heat. The same sub- stance is produced by heating the hydrated salt with a colrcentrated solution of zinc chloride in sealed tubes a t 2.50". On evaporating to dryness arsenic acid solution containing excess of zinc chloride, and subsequently fusing tlie product, prismatic crystals of anhydrous zinc arsenate were obtained having B sp.gr. of 4.913 a t 15". The loss of weight varied from 0.042 to 0.049 gram G. T. M.INORGANIC CHEMISTRY. 215 Hence, zinc differs from magnesium and cadmium in not forming chlorophosphates and chlorarsekates (compare Abstr., 1890, 11). - T. G. N. Egyptian Blue. By 0. MGHLHACSER (Dingl. polyt. J., 272, 144). --This blue pigment was used by the R?omans in the first few centuries of the Christian era. It is said to have been discovered hy Vitruvius in Alexandria, who prepared it by intimately mixing finely divided sand with sodium carbonate, adding copper filings to the mixture, moistening with water, moulding into balls, drying, and heating in clay pots until the blue colour was produced. Pouqud has recently examined this colouring matter, and finds that its composition is t h a t of a double silicate of calcium and copper, Ca0,Cu0,4Si02.I t has a sp. gr. of 3.04, and crystallises in lamitie belonging to the dimetric system. The crystals exhibit dichroism, showing a pale-red colour when viewed by reflected light, and a blue colour when the light is transmitted. The hlue substance resists the action of most chemical agents, and this fact explains the perfect state of its preservation in the wall paintings executed about I900 pears ago. Accoi-ding to Fouquk, its preparation may be effected at a bright red heat from materials devoid even of traces of alkali. A t R hirrher tpmperature the blue is decomposed into cuprous oxide, wollnstonit e and a light-green, vitreous mass ; the higher the tempe- rature, the more of the latter is formed, until eventually wollastonite disappears entirely.The same author finds the method described by Vitruvius applicable, but prefers the use of potassium sulphate as flux. The brightness and fastness of this pigment, the fact that it; resists atmospheric influences and is not affected by most chemical agents, as well as the facility and cheapness of production, render i t desirable that its manufacture should be again taken up. D. B. Nature of Steel. By KOSMANN (Dingl. po7yt. J., 270, 190-1 92). The author reviews the theories of Rinmitn, Osmond and Werth, Miillcr, Ledebur, and Baedeker, respecting the state in which carbon exists in steel. He does not agree with the assumption that carbon e x i s t s evenly alloyed with iron only in bardened steel, whilst in slowly-cooled steel i t is dissolved by the iron i n the form of the com- pound Fe,C, but considers that in rapidly-cooled steel the carbon is also chemically combined with the iron.D. B. Synthesis of Double Sulphides of the Alkali Metals and the Heavy Metals. By H. BRUNNER (Chenz. Cewtr., 1849, ii, 554-555 ; from Arch. sci. phys. nut. Genkve, 22, 6849).-The author has suc- ceeded i n preparing the double sulphides of sodium and the metals of the iron-group by heating the oxalate of the heavy metal with sodium ttiiosulphate. S o d i u m i r o n sdphide crystallises i n beautiful, bronze- red prisrns : chrnnziuiiz sodium sulphide is a reddish-brown mass ; whilst manganese sodium. cobalt sodium, and niclcel sodauna sulphides form lustrous, yellow, crjstalline masses.readily oxidised on exposure to the air. These double sulphides are also formed when the alkaline carbonatee are calcined with sulpliur and the oxalate of the heavy216 ABSTRACTS OF CHEMICAL PAPERS. metal. the double oxalate with sulphur. J. W. L. The chromium sodium sulphide is also obtained by heating Nickeloxydiamine Nitrite. By L. SORET and F. ROBINEAU (BUZZ. SOC. Chinz. [3], 2, l%).--To prepare this salt, ammonia solution of sp. gr. 0.924 (3 kilos.) and sodium nitrite (1 kilo.) are added to nickel sulphate (1 kilo.) dissolved in boiling distilled water (1 litre) ; the mixture is placed aside for 4-5 days, and the resulting crop of crystals, after washing, is recrptallised from a hot ammoiiiacal solution.Although the nickel salt used contained 3 per cent. of cobalt, the crystals of nickeloxydiamine nitrite produced were absc- iutely pure. T. G. N. Double Fluorides of Antimony. By G. STEIN (Chem. Zeit., 13, 357). - By evaporating solutions of antimonious fluoride with lithium chloride or fluoride, the respective double salts S bF3,LiC1 o r SbFs,LiF are obtained ; they crystallise in hexagonal tables ; both arc readily soluble in water without decomposition, the former being the more soluble ; the solutions have R slightly acid reaction. Am- monia precipitates flocculent, gelatinous antimonious oxide from these sclutions ; whereas the known double fluorides of antimony yield heavy precipitates. I n mordanting experiments with tannin-aniline colours, 100 grams of potassium antimony tartrate, or 60 grams of lithium antimony fluoride, or 65 gmms of lithium antimonr chloride were employed, and the results obtained as regards the purity and beauty of colour were of equal value.Antimony fluoride does not form any useful double salts with potassium, sodium, or ammonium thiocyamte ; in f'act, the thio- cyanate decomposes, and especially with ammonium thiocyanate the solution of the double salt, when strongly evapurated, gives a pre- cipitate of antimony sulphide. Antimonates. By F. EBEL (Ber., 22, 3044--3045).-The Ruthor has prepared the following compounds by adding excess of a concentrated solution of the metallic salt to a boiling aqueous solution of sodium antimonate (Na2H2Sb20: + i'H,O) :--Barium antimonate, B;tSbd& + 5H,O ; Beryllium antimonate, BeSb?06 + 6H,O ; silver antimonate, Ag2Sb206 + 3H20 ; copper xntimonato, CuSb& f 5H20; cadmium antimonate, CdSbzO, + 6H,O; lead nntimonate, PbSb2(& + 5H20 ; zinc antirnonate, ZnSb,06 + 5HL0 ; manganese antimonate, MnSb206 + 5 H 2 0 ; amorphous cobalt anti- monate, CoSb,06 + 6H20 ; the crystalline salt, CoSb,06 + 12H,O; amorphous nickel antimonate, NiSb,O, + 6H20 ; the crystalline Falt, NiSb206 + 12H20; the ferric salt, FezO3,Sb,O5 + 7&O; and the aluminium salt, A1203,Sb205 + 9H20.Behaviour of Bismuth with Sulphur and Selenium. By P. A . v. SCHERPKXUERG (Chem. Centr., 1889, ii, 643-644; from Mitt. pltarrn. Inst. Erlnngen, 2 Heft, 1-1 2). -The author has not succeeded in preparing a higher sulphide of bismuth than the trisulphide, D.A. L. F. S. K.MINERALOGICAL CHEMISTRY. 217 although an oxysulphide, Bi203S, is formed when bismuth pent- oxide, suspended in boiling benzene, is treated with dry hydrogen sulphide. Attempts to prepare double snlphides, similar to those described by Schneider (Ann. Y h y s . Chem.. 91, 404), but with a larger proportion of sulphur, by heating the pentovide with conceiitrated potassium hydrosulphide solution in a sealed tube, only resulted in the formation of the lower oxide. If, however, the pentoxide is fused with potassium polysulphide, the compoiind Bi-S,.K2S remains as a crystallirie mass. With selenium, the double salt Bi,Se,,K,Se may be prepared in like manner. J. W. L. Platinum Tetrafluoride. By H. MO~SSAN (Compt. rend., 109, 807--809).--Flnorine, free from hydrogen fluoride, does not attack pla- tinum below loo", acd combination does not take place readily below .500-600". In presence of hydrogen fluoride, the reaction takes place far more easily, even in the case of liquid hydrogen fluoride saturated with fluorine.Platinum tetrafluoride is obtained by heating a bundle of platinum wire to dull redness in a thick platinum tube or a fluor-spar tube through which a current of fluorine is passed. As soon as eombiiiation is complete, the product is transferred to a perfectly dry tube. It forms a deep-red, fused mass or chamois-yellow crystals resembling anhydrons platinum tetrachloride, is extremely hygro- scopic, and cannot be kept for a long time even in a well-corktd and carefully-dried tube.When thrown into a small quantity of water, a tawny coloration is first produccd, then heat is rapidly developed, and decomposition takes place with formation of hydrogen fluoride and hydrated platinum dioxide. Very dilute solutions are more stable, but the same change takes place inimediately if the liquid is heated. This reaction explains E'remy's failure to obtain platinum tetra- flnoride by the action of hydrofluoric acid on hydrated platinum dioxide. When platinum fluoride is heated, it yields fluorine and metallic platinum, the latter being left in a crystalline form, a result which buyports DaubrBe's views on the mineralising effect of fluorine. C H. B.208 ABSTRACTS OF CHEMICAL PAPERS.I n o r g a n i c Chemistry.Density of Fluorine.By He. MOISSAN (Con$. rend., 109,86 I--864).--Fluorine was obtained by electrolysis, as before, but alarger apparatus was used, and in order to purify the gas completelyfrom hydrogen fluoride, it was passed through a platinum wcrmcooled to -550" by nieans of methyl chloride, and then through aplatinum tube contaiuing anhydrous sodium fluoride, which combineswith hydrogen fluoride with great energy. The sodium salt is farprefer~ble to the potassium salt, because it is not hygroscopic.The pure fluoi'ine was collected in platinum flasks of about 100 C.C.capacity, which had been previously filled with nitrogen. After beingweighed, the fluorine was brought in contact with water, and theevolved gases were measnred and analysed, a correction being madefor any nitrogen which had not been displaced.The mean sp, gr.found was 1.265, whilst the value calculated fromF = 19 is 1.316. C. H. B.Autoxidation. By M. TRAUHE (Bey., 22, 30.57-3062 ; compareAbstr., 1889, 937).-A reply to Hoppe-Seyler (Abstr., 1889, 1106).The author is satisfied that he has proved that nascent hydrogen inpresence of oxygen molecules has not a powerful oxidising action, asstated by Hoppe-Seyler, and also that the oxidising action of palladiuIN0 RQANIC CHEMISTRY. 209hgdride cannot be attributed to nascent hydrogen. R e criticisesHoppe- Sey ler's remarks very severely, and concludes by expressingthe hope that his part in the discussion on autoxidation with Hoppe-Seyler may be ended.Hydrogen Arsenide and Antimonide.By 0. BRUNN (Be?-.,22, 3202-320i) .-Hydrogen arsenide and hydrogen sulphide do notact on one another in absence of air a t the ordinary temperature,either in the gaseous condition or in aqueous solution, even on ex-posure to direct sunlight. The admission of air quickly causes i n bothcases a precipitate of arsenious sulphide. It has been previouslyobserved that hydrogen arsenide is itself acted on by air or oxygen,with formation of a black powder. An examination of this producthas shown that its composition varies with the amount of air present,the gas being first oxidised to solid hydrogen arsenide, and then, ifthere be sufficient oxygen, to metallic arsenic. The above-mentionedformation of arsenious sulphide is, therefore, probably preceded bythe formation of arsenic.If the mixture of hydrogen arsenide and sulphide is heated, sepa-ration of arsenious sulphide commences at about 230".Separate ex-periments with hydrogen arsenide show that the latter commences todissociate a t 2:30°, and that in this case also the formation of arsenioussulphide is a secondary reaction.Hydrogen antimonide is a t once decomposed by hydrogen sulphide,even in absence of air and light. On heating the former gas alone,dissociation commences a t about 150". The author proposes to makeuse of this fact for the detection of traces of ant[iniony occurrirtqtogether with arsenic, in other gases, such as hydrogen. For thispurpose thegases are passed through a tube 0.8-1.0 metre in length,and heated by a liquid boiling a t 208-210".No arsenic whateveris deposited, and the antimony mirror may be further examined bythe usual methods. H. G. C.Combination of Sodium and Potassium with Ammonia.By A . JOANNIS (Compt. rend., 109, 900--902).-When one equivalentof the alkali metal is brought in contact with 20 equivalents of liquidammonia, and the ammonia gas is afterwards removed, its pressurerapidly diminishes. At a, certain point, the pressure becomes constant ;in the case of sodium the pressure was 1700 mm. a t 0", and the com-position of the mixture Na + 5.3NHj. The exact composition varieswith the temperature, notwithstanding the constancy of the pressure,and hence the product in the tube is riot a definite compound. Whena further quantity of the gas is removed, a solid substance with anintense copper-red colour is left, and the constant pressure observedniny be regarded as the vapour pressure of liquid ammonia saturatedwith this solid. When only one molecule of ammonia is present, €oreach atom of metal, no trace of liquid remains, and if still moreammonia is removed, the free sodium o r potassium alone remains, andas this decomposition takes place at a constant pressure, it may be re-garded as true dissociation.Careful experiments gave 0.99 equivalentas the inferior limit, and 1.1 equivalent as the superior limit of thequantity of ammonia combined with one atom of the alkali metal, andF. S. I(2 10 ABSTRACTS OF CHEMICAL PAPERS.it may therefore be taken that the solid residue, which the authorcalls potassammonium or sodumnaonium, has the composition NHJK orNH,Na.C. H. B.Thiosulphates. By A. FOCK and K. K~iiss (Ber., 22,3096-3101).-Potassium t,hiosnlphate, 3K2S203 + €LO, separates in colourless,prismatic crystals wben an aqueous solution of the salt is evaporatedover sulphuric acid, and when the mother liquors are kept over sul-phuric acid for some time longer the salt separates in large, rhombiccrystals, with 5 niols. H20 ; these results agree with those previouslyobtained by Rammelsberg, Kessler, and Dopping.Lithium thaosuijhate, Li,S203 + 3H,O, crystallises in large, colourless, very deliquescent needles, and is soluble in alcohol ; when heated,it is decomposed into lithium sulphrtte and lithium sulphide.Ammonium thiosulphate, (NH4)2S20:3, separates in anhydrous,colourless plates when an aqueoiis solution of the salt is evaporatedover sulphuric acid ; Rammelsberg found that the salt crystallisedwith 1 mol.H,O. F. S. K.Allotropic Forms of Silver. Ry M. C. LEA (Amer. J. Sci. [3],37,476-491 ; and 38,47--50, and l29).-The author considers thathis own researches have established the existence of silver sub-chloride, although the experiments of Newbury, Muthmann,v. Pfordten, and others, have shown that there is a t present no evi-dence of the existence of a silver sub-oxide, Ag,O. He points outthat the fact that a substance will not pass through a dialyser merelyproves that it is colloidal and not that it is not in solution. Further,many substrnces which undoubtedly form true solutions are carrieddown by gum when the latter is added to the liquid and then pre-cipitated by addition of alcohol.The products described in thesepapers differ from those obtained by v. Pfordten in that they readilyamalgamate with mercury and evolve no gas wheu treated withdilute sulphuric acid.Silver can exist in three allotropic forms, or more probably inthree modifications of the same form, the differences between the threebeing less than their differences from normal silver. They differ incolour and other physical properties, and in chemical activity ; theyprobably represent an active condition of silver of which the ordinarymetal is a polymeride.A. Soluble allotropic silver, which forms a deep-red solution, is mrtttblack, blue, or green, when solid and moist, and brilliant metallicbluish-green when dry.B.Insoluble allotropic silver, derired from the preceding modifica-tion, dark reddish-brown when moist, and brilliant metallic bluish-green, like A, when dry.C. Gold-like allotropic silver, dark-bronze coloured when moist, butlike burnished gold when dry. No soluble modification of this formseems to exist, but a copper-coloured variety is produced undercertain conditions.Whendry they are very friable and are readily reduced to an impalpableThe three modifications are as follows :-All three modifications have certain properties in commonINORQANIC CHEMISTRY. 211powder, differing markedly in this respect from normal silver.Theirmost striking property, however, is their power of drying with theirparticles in optical contact, and if spread while moist on paper orglass, they form mirrors of great perfection and beauty when dry.If these films are treated with solutions of the haloids, ferric chloride,or, hest of all, sodium hypochlorite, very beautiful interferencecolonrs are obtained. The phenomena are quite different from thoseobtained with normal silver leaf under the same conditions. Verydilute mineral acids and moderately dilute acetic acid immediatelyconvert allotropic silver into grey normal silver without the evolutionof any trace of gas.A. Soluble allotropic silver is obtained by the action of con-centrated solutions of ferrous citrate or a mixture of ferrous sulphnteand sodium citrate on a concentrated solution of a silver sait.If thesolutions are not very concentrated, a deep-red liquid is formed whichmay remain transparent for some time or may gradually deposit ablack precipitate. Concentrated solutions should be used, the fol-lowing proportions being found to give the best results. A mixtureof ~ ( J O C.C. of a 30 per cent. solution of ferrous sulphate and 280 C.C.of n 40 per cent. solution of sodium citrate was added a t once to200 C.C. of a 10 per cent. solution of silver nitrate. The liquid, whichimmediately becomes black, is viporously agitated for several minutes,allowed to remain for 10 to 15 minutes, and the liquid then decanted.A large quantity of a lilac-coloured precipitate remains, but altersslowly even in contact with the mother liquor, and when it is drainedthe colour changes almost immediately to deep blue.It may bewashed with a solution of sodium or ammonium citrate, sulphate, ornitrate, preferably ammonium nitrate, because, although completelysoluble in pure water, it is quite insoluble in presence of 5 to 10 percent. of these salts. A good plan is to add sufficient water to dis-solve nearly the whole of the precipitate and then sufficient am-monium nitrate to reprecitate it. The substance gradually changeswhilst being washed and becomes less and Iess soluble. After wash-ing seven or eight times in the manner described, it was washed withalcohol of 95 per cent'. to remove ammonium nitrate and thenanalysed : it contained 97-27 per cent.of silver and the filtrate fromthe silver chloride precipitate contained only ferric citrate. Itretains water even after prolonged exposure in a dry vacuum. butbecomes anhydrous atl 100" ; a t low redness i t gives off smal I quanti-ties of carbonic anhydride, but. no trace of either hydrogen or oxygen.These determinations were made after the substance had becomeinsoluble, and hence it seemed possible that while in solution itmight be combined with citric acid. Determinations of the silverand citric acid in a solution of the purified substance (which wasproved by optical examination to form a true solution) gave the ratioof silver to citric acid in one case as 55.63 : 1 and in another 193.7 : 1,results which show that the proportion of citric acid is variable andis always very small.Some of the purified precipitate was dried a t loo", inixed with water, and again evaporated to dryness; all thesilver separated as grey normal silver and the liquid was quiteneutral. If a perfectly neutral iron solution is used in the prepara212 ABSTRACTS OF CHEMICAL PAPERS.tion of the substance, the liquid after reduction is either nentrsl orvery faintly acid. If a solution of the purified lilac precipitate ismixed with a neutral solution of magnesium sulphate, tshe iusolubleform, which consists of almost pure silver, is thrown down, but theliquid remains quite neutral. Possibly the silver is in combinationwith some neutral substance derived from citric acid, but if so, i tmust be some entirely new compound. Ballo has observed that theaction of ferrous salts on tartaric acid produces a neutral substanceof the same composition as arabin, CsH,,O5.The change which thelilac precipitate undergoes during purification and washing is indi-c a t d by changes of colour, and the constitution of the lilac pre-cipitate whilst under the mother liquor is still doubtful. If theprecipitate is spread on paper, it is blood red while moist, blue withmetallic lustre when half dry, and matt blue when quite dry. Ifdried in lumps, the colour and lustre vary considerably.B. Insolzc,ble allotropic silver is obtained from the preceding formby spontaneous change or by the action of certain salts. Alkalinesulphates, nitrates, and citrates precipitate soluble allotropic silverfrom its solutions, but it still remains soluble.Magnesium, copper,iron, and nickel sulphates, potassium dichromate, potassium ferrocya-nide, barium nitrate, and silver nitrate all precipitate it i n an insolubleform. The soluble precipitate is blue or bluish-black ; the insolubleform is brown and continually darkens while being washed. Am-monia dissolves the insoluble modification ; sodium borate and alkalinesulphates reconvert i t into a soluble form, different however fromthe original. With a dilute solution of sodium borate, a brown soln-tion is obtained ; with sodium or pot.assium sulphate, a yellow-redsolution ; with ammonium sulphate, a red solution. If concentratedfiolutions of these salts are used, the change into the soluble formtakes place, but the substance does not dissolve until the salt hasbeen washed away b7 pure water.Sodium nitrite added to a solu-tion of the soluble form partially converts it into normal silver andrenders it quite insoluble even in ammonia. I n one case the insolublevariet,y became spontaneously soluble and formed a rose-red solution.I n another case it separated very slowly and spontaneously from asolution in the form of short, black needles and thin prisms, whichlost their crystalline form i n contact with pure water but did notdissolve; it dried with a green, metallic lustre. It seems that purewater tends to produce a colloidal form, whether soluble or insoluble,whilst, salts tend to produce a crystalline form.Analysis showed that the insoluble allotropic silver contained 97.96per cent.of the metal, the remainder being ferric citrate. I t retainswater in a vacuum but becomes anhydrous a t 100".When spread in the moist state over paper, it forms a green filmwith a brilliant metallic liistre. The green is a mixture of blue andyellow, one or the other predominating according to the direction ofthe illumination. The yellow is polarised in the plane of incidence,and the blue in a direction normal to that plane. All the productswere more or less yellow, but the proportion of blue light varied con-siderably and is less the more prolonged the washing of the pre-cipitate. If some of the substance is precipitated by means oINORGANIC CHEMISTRT.213magnesium or aluminium sulphate and is sprea4 on paper withoutwashing, the dry film has the appearance of it highly lustrous, bright-blue metal. When the moist substance is spread on glass, it formsvery perfect mirrors when dry.C. Gold-like allotropic silver is obtained by the reduction of silvertartrate by ferrous tartrate in dilute soliitions, but the permanency oftlie product depends on the details of the preparation and is greaterthe more completely air and light are excluded from the dry sub-stance. The following method gives a permanent product :-amixture of 107 C.C. of a 30 per cent. solution of ferrous sulphate,200 C.C. of a 20 per cent. solution of sodium-potassium tartnte,and 800 C.C. of water is added gradually, and with constantstirring, to a mixture of 200 c c.of a 10 per cent. solution of silvernitrate, 200 C.C. of the solution of the alkaline tartrate, and 800 C.C.of water. The precipitate is a t first red, but changes to black, andwhen washed on the filter becomes bronze-colonred. If dried inlumps or in films on paper or glass, it has the colour and lustre ofburnished gold. It is verypermanent when dry, but more liable to change while moist, an({forms a copper-coloured variety, which however is still bright mldpeimanent,. While washing, it is important to keep the filter full ofwater. This modification contains 57.8 to 98.75 per cent. of silver,the remainder being ferric tartrate.The specific gravities of €3 and C were determined after they badbeen left under water in a vacuum for a, long time; sp.gr. of in-soluble allotropic silver = 9 58 ; sp. gr. of gold-like a:lotropic silver= 8.51. The sp. gr. of normal silver is 10.5, and that of fiuely dividedprecipitated silver 10.62.At looo, a bluish-green film of B acquired a superficial bright-yellow colour, and x film of C under the same coilditions becamesuperficially blue, but these changes were confined t,o the surfaces.All three modifications are affected by light; A and B becomebrown after some hours, and the coppery modification of C becomesbright-yellow. A very bright bluish-green modification of B ob-tained by rapid and short washing acquired the colour of gold afterone day's exposure to sunlight, ; samples which have been well washedyield a matt film on paper and become brown when exposed to light.The gold-like moditication acquires a somewhat purer yellowcolour when exposed to light in absence of moisture, but in presenceof moisture 3 or 4 days exposure to sunlight changes it into whitenormal silver of great beauty.Moisture alone t.euds to darken itscolour. It is interesting to note that organic compounds of silreralways yield grey or black, lustreless products when exposed to light.The modifications A and B are obtained by the reduction of silvercitrate by ferrous citrate, and C by the reduction of silver tartrate byferrous tartrate. No similar results are obtained by the action offerrous oxalate on silver oxalate.On glass i t forms very perfect mirrors.C.H. B.Action of Ljght on Silver Chloride. By R. HITCFICOCK(Amer. C'hem. J., 11, 474--480).-FineIy divided precipitated silverchloride was allowed to ssttle on microscopic cover glasses214 ABSTRACTS OF CHEMICAL PAPERS.carefully washed, and dried in a desiccator. I n this way thethin glass slips are obtained covered with a very thin, semi-trans-parent layer of silver chloride. They were then weighed, placed ina tube through which a current of pure hydrogen was passing, andexposed to sunlight, the chlorine which was liberated beingabsorbed in silver nitrate solution and afterwards weighed. Theglass slips with the silver chloride were weighed after the experi-ment. pergram of silver chloride ; the chlorine absorbed by the silver nitratewas very slightly smaller in quantity than the loss in weight of thesilver chloride.In one case the product gave np a considerable pro-portinn of silver when heated with dilute nitric acid, aiid hence itwonld seem that decomposition had gone so f a r that the protectiveaction of the unaltered silver chloride had to a great extent beeneliminated. C. H. B.Zinc Hydrosulphide. By V. v. ZOTTA (Monatsl~., 10, 807-812).-The author finds, contrary to the statement of Thomsen (Abstr.,1879, 206), that when equivalent quantities cf zinc sulphate andan alkaline h-j-drosulphide are mixed, the precipitate obtained has notthe formula Zn(SH)2, but must be regarded as having the composi-tion Zn,H,S4, = Zn(SH)2,2ZnS. The production of this corn-round explains the evolution of hydrogen sulphide which takes placeon adding an alkaline hydrosulphide to zinc sulphate ; for the com-pound Zn3H2SI may be regarded as being formed from 3 mols. of thehydrosulphide by loss of 2 mols.of hydrogen sulphide. Thomsenfurther says (Zoc. cit.) that if zinc sulphate is treated with two equiva-lents of sodium hydrosulphide, no precipitate is produced, but theresulting solution is slightly opalescent ; and concludes that sodiumhydrosulphide behaves towards zinc sulphate in precisely the sameway as sodium hydroxide. The author in repeating this experimentfincis that about, 20 per cent. of the sulphur present is evolved a~hydrogen sulphide, but that long continued boiling does not causethe formation of a precipitate.If, however, a mixture of zinc sul-phate with four times its equivalent of sodium hydrosulphide ismade, the slightly opalescent solution obLained is rendered turbid onboiling for a few minutes, or on treatment with acids, alkalis, orcertain salts, and the precipitate is identical with the sulphideZn,H2S4, mentioned above.Crystalline Anhydrous Zinc Phosphate and Zinc Arsenate.By A. DE SCHULTKX (&ill. Soc. C h i m [3], 2, 300--302).-Zincchlorophosphata did not separate from the solution of nnrmal tetra-hydrated zinc phosphate in fused zinc chloride, but rbombic prismsof anhydrous zinc phosphate were obtained from the melt; theseliave a sp. gr. of 3.998 a t 15', and melt at, a red heat. The same sub-stance is produced by heating the hydrated salt with a colrcentratedsolution of zinc chloride in sealed tubes a t 2.50".On evaporating to dryness arsenic acid solution containing excessof zinc chloride, and subsequently fusing tlie product, prismaticcrystals of anhydrous zinc arsenate were obtained having B sp.gr. of4.913 a t 15".The loss of weight varied from 0.042 to 0.049 gramG. T. MINORGANIC CHEMISTRY. 215Hence, zinc differs from magnesium and cadmium in not formingchlorophosphates and chlorarsekates (compare Abstr., 1890, 11).-T. G. N.Egyptian Blue. By 0. MGHLHACSER (Dingl. polyt. J., 272, 144).--This blue pigment was used by the R?omans in the first fewcenturies of the Christian era. It is said to have been discoveredhy Vitruvius in Alexandria, who prepared it by intimately mixingfinely divided sand with sodium carbonate, adding copper filings tothe mixture, moistening with water, moulding into balls, drying, andheating in clay pots until the blue colour was produced.Pouqud has recently examined this colouring matter, and finds thatits composition is t h a t of a double silicate of calcium and copper,Ca0,Cu0,4Si02. I t has a sp.gr. of 3.04, and crystallises in lamitiebelonging to the dimetric system. The crystals exhibit dichroism,showing a pale-red colour when viewed by reflected light, and a bluecolour when the light is transmitted. The hlue substance resists theaction of most chemical agents, and this fact explains the perfectstate of its preservation in the wall paintings executed about I900pears ago.Accoi-ding to Fouquk, its preparation may be effected at abright red heat from materials devoid even of traces of alkali. A t Rhirrher tpmperature the blue is decomposed into cuprous oxide,wollnstonit e and a light-green, vitreous mass ; the higher the tempe-rature, the more of the latter is formed, until eventually wollastonitedisappears entirely. The same author finds the method described byVitruvius applicable, but prefers the use of potassium sulphate asflux.The brightness and fastness of this pigment, the fact that it; resistsatmospheric influences and is not affected by most chemical agents, aswell as the facility and cheapness of production, render i t desirablethat its manufacture should be again taken up. D. B.Nature of Steel.By KOSMANN (Dingl. po7yt. J., 270, 190-1 92).The author reviews the theories of Rinmitn, Osmond and Werth,Miillcr, Ledebur, and Baedeker, respecting the state in which carbonexists in steel. He does not agree with the assumption that carbone x i s t s evenly alloyed with iron only in bardened steel, whilst inslowly-cooled steel i t is dissolved by the iron i n the form of the com-pound Fe,C, but considers that in rapidly-cooled steel the carbon isalso chemically combined with the iron. D. B.Synthesis of Double Sulphides of the Alkali Metals and theHeavy Metals. By H. BRUNNER (Chenz. Cewtr., 1849, ii, 554-555 ;from Arch. sci. phys. nut. Genkve, 22, 6849).-The author has suc-ceeded i n preparing the double sulphides of sodium and the metals ofthe iron-group by heating the oxalate of the heavy metal with sodiumttiiosulphate.S o d i u m i r o n sdphide crystallises i n beautiful, bronze-red prisrns : chrnnziuiiz sodium sulphide is a reddish-brown mass ;whilst manganese sodium. cobalt sodium, and niclcel sodauna sulphidesform lustrous, yellow, crjstalline masses. readily oxidised on exposureto the air. These double sulphides are also formed when the alkalinecarbonatee are calcined with sulpliur and the oxalate of the heav216 ABSTRACTS OF CHEMICAL PAPERS.metal.the double oxalate with sulphur. J. W. L.The chromium sodium sulphide is also obtained by heatingNickeloxydiamine Nitrite. By L. SORET and F. ROBINEAU (BUZZ.SOC. Chinz. [3], 2, l%).--To prepare this salt, ammonia solution ofsp.gr. 0.924 (3 kilos.) and sodium nitrite (1 kilo.) are added tonickel sulphate (1 kilo.) dissolved in boiling distilled water (1 litre) ;the mixture is placed aside for 4-5 days, and the resulting crop ofcrystals, after washing, is recrptallised from a hot ammoiiiacalsolution. Although the nickel salt used contained 3 per cent. ofcobalt, the crystals of nickeloxydiamine nitrite produced were absc-iutely pure. T. G. N.Double Fluorides of Antimony. By G. STEIN (Chem. Zeit., 13,357). - By evaporating solutions of antimonious fluoride withlithium chloride or fluoride, the respective double salts S bF3,LiC1o r SbFs,LiF are obtained ; they crystallise in hexagonal tables ; botharc readily soluble in water without decomposition, the former beingthe more soluble ; the solutions have R slightly acid reaction.Am-monia precipitates flocculent, gelatinous antimonious oxide from thesesclutions ; whereas the known double fluorides of antimony yieldheavy precipitates.I n mordanting experiments with tannin-aniline colours, 100 gramsof potassium antimony tartrate, or 60 grams of lithium antimonyfluoride, or 65 gmms of lithium antimonr chloride were employed,and the results obtained as regards the purity and beauty of colourwere of equal value.Antimony fluoride does not form any useful double salts withpotassium, sodium, or ammonium thiocyamte ; in f'act, the thio-cyanate decomposes, and especially with ammonium thiocyanate thesolution of the double salt, when strongly evapurated, gives a pre-cipitate of antimony sulphide.Antimonates.By F. EBEL (Ber., 22, 3044--3045).-TheRuthor has prepared the following compounds by adding excess ofa concentrated solution of the metallic salt to a boiling aqueoussolution of sodium antimonate (Na2H2Sb20: + i'H,O) :--Bariumantimonate, B;tSbd& + 5H,O ; Beryllium antimonate, BeSb?06 +6H,O ; silver antimonate, Ag2Sb206 + 3H20 ; copper xntimonato,CuSb& f 5H20; cadmium antimonate, CdSbzO, + 6H,O; leadnntimonate, PbSb2(& + 5H20 ; zinc antirnonate, ZnSb,06 + 5HL0 ;manganese antimonate, MnSb206 + 5 H 2 0 ; amorphous cobalt anti-monate, CoSb,06 + 6H20 ; the crystalline salt, CoSb,06 + 12H,O;amorphous nickel antimonate, NiSb,O, + 6H20 ; the crystalline Falt,NiSb206 + 12H20; the ferric salt, FezO3,Sb,O5 + 7&O; and thealuminium salt, A1203,Sb205 + 9H20.Behaviour of Bismuth with Sulphur and Selenium. By P.A . v. SCHERPKXUERG (Chem. Centr., 1889, ii, 643-644; from Mitt.pltarrn. Inst. Erlnngen, 2 Heft, 1-1 2). -The author has not succeededin preparing a higher sulphide of bismuth than the trisulphide,D. A. L.F. S. KMINERALOGICAL CHEMISTRY. 217although an oxysulphide, Bi203S, is formed when bismuth pent-oxide, suspended in boiling benzene, is treated with dry hydrogensulphide.Attempts to prepare double snlphides, similar to those described bySchneider (Ann. Y h y s . Chem.. 91, 404), but with a larger proportionof sulphur, by heating the pentovide with conceiitrated potassiumhydrosulphide solution in a sealed tube, only resulted in the formationof the lower oxide. If, however, the pentoxide is fused with potassiumpolysulphide, the compoiind Bi-S,.K2S remains as a crystallirie mass.With selenium, the double salt Bi,Se,,K,Se may be prepared in likemanner. J. W. L.Platinum Tetrafluoride. By H. MO~SSAN (Compt. rend., 109,807--809).--Flnorine, free from hydrogen fluoride, does not attack pla-tinum below loo", acd combination does not take place readily below.500-600". In presence of hydrogen fluoride, the reaction takes placefar more easily, even in the case of liquid hydrogen fluoride saturatedwith fluorine. Platinum tetrafluoride is obtained by heating a bundle ofplatinum wire to dull redness in a thick platinum tube or a fluor-spartube through which a current of fluorine is passed. As soon aseombiiiation is complete, the product is transferred to a perfectly drytube. It forms a deep-red, fused mass or chamois-yellow crystalsresembling anhydrons platinum tetrachloride, is extremely hygro-scopic, and cannot be kept for a long time even in a well-corktd andcarefully-dried tube. When thrown into a small quantity of water, atawny coloration is first produccd, then heat is rapidly developed, anddecomposition takes place with formation of hydrogen fluoride andhydrated platinum dioxide. Very dilute solutions are more stable,but the same change takes place inimediately if the liquid is heated.This reaction explains E'remy's failure to obtain platinum tetra-flnoride by the action of hydrofluoric acid on hydrated platinumdioxide.When platinum fluoride is heated, it yields fluorine and metallicplatinum, the latter being left in a crystalline form, a result whichbuyports DaubrBe's views on the mineralising effect of fluorine.C H. B

ISSN:0368-1769    

DOI:10.1039/CA8905800208

出版商:RSC    

年代:1890

数据来源: RSC

摘要:

MINERALOGICAL CHEMISTRY. M i n e r a l o g i c a l Chemistry. 217 Composition of Roumanian Rock-salt. By ISTRATI (BUZZ. SOC. China. [3], 2, 4-88).-l’his mineral, which is mined in the Carpa- thians, contains 98-99.8 per cent. of sodium chloride. Some varieties have a definite odonr of pet,roleum, which in some cases is contained in the mineral to such an extent that explosions have occurred. The variety known as ‘‘ puturosa” coni.ains as much as 117 C.C. of gases per kilo.; the gas obtained from Dolftana salt yielded on analysis 25 per cent of unsaturated hydrocarbons and 19.6 per cent,. of oxygen, but no carbonic anhydride. T. G. N. VOIA. LVIIL. !I218 ABSTRACTS OF CHEMICAL PAPERS. Kobellite from Colorado. By H. F. EELLER (Zeit. Kryst. Min., 17, 67--72).-This mineral, from the Silver Bell mine, Oumy, is fine-grained, somewh:Lt fibrous, and exhihits no crystalline form.It has a sp. gr. of 6.334. The analyses lead to the formula 2(PbAg$ii,)S, (SbBi),S:,. This does not agree with Rammelsberg’s formula, Pb3BiSbSs. 18-39 28.40 7-55 36-16 3-31 2-59 1.50 0.39 0.45 98.74 The mean of four analyses was as follows :- 5. Bi. Sb. Pb. Ag. Cu. Fe. Zn. Gangue. Total. B. H. B. Aurichalcite. By A. BELAR (Zpit. Kryst. Min., 17, 113-127).- In the aurichalcite of Temperino, Delesse detected the presence of calcium. Other chemists regard this a s merely a mechanical im- purity in hhe material anal-ysed, and believe that aurichalcite is nothing more than R compound of copper and zinc hydrated carbon- ates. Analyses were made of aurichalcite (1 and 2) from Moravicza,, (3j from Campiglia, and (4) from Sardina, with the following re- sults :- CuO.ZnO. FezO,. R,O. cop 1 ...... 20.39 54.70 - 13-53 11.X3 2 ...... 21.43 53.57 - 26.78 3 ...... 20.20 55.51 - 26.F)O 4 ...... 15-58 58.72 2.17 22.97 \- All four analyses lead to the formula CuCO, + 3Z1i(Ho)~. I n concliision, the author gives the results of experimenh made with the view of preparing aurichalcite art,ificially. He finds that tlhe statenient of Delesse, that aurictinlcibe re-crystallism out from solu- tions of the mineral in ammonium carbonate, is not correct. B. H. B. Messelite, a New Mineral. BJ- W. MUTHMANN (Zeit. Kryst. Min., 17, 93-94) .-This mineral forms radiated masses of brown or colourless tablets in a bituminous shale embedded in the lignite of the Messel mine in Hesse-Darmstadt.The crystals were found optically to be triclinic. Analysis gave the following results :- P&. CaO. FeO. MgO. MnO. HzO. Insol. Total. 37.72 31-11 15.63 1.45 trace 12.15 1-40 99-46 These results correspond with the formula (CaFeMg)3(P04)2 + Messelite differs from fairfieldite by the absence 0: man- 24H,O. ganese and by the different proportion of water. B. H. B. Mazapilite, Anhydrite, Eleonorite, &c., from North America,. By G. A. K ~ N J G (Zeit. Kryst. Mln., 17, &4---92).-1. iVuzapilite is the name given by the author to an extremely rare mineral from the Jesus Maria Mine, Mazapil, Mexico. The crystals belong to the rhombic system, the axial ratio being a : b : c = 0-8616: : 1 : 9.9969. Analysis gave-MINERALOGICAL CHEMISTRY. 219 AS,^,.Sb20,. P205. Fe,O,. CaO. HzO. Total. Sp. gr. 43-60 0.25 0.14 30.53 14-82 9*83 99.17 3.582 Formula : Ca3Fe2 (As04)4(OFe.0H)2 + 5H20. 2. Anhydrite.-This mineral was found at the Darby tunnel, seven miles from Philadelphia, in the unusual form of crusts consisting of parallel prisms on the plagioclnse and augite of a diabrtse. The sili- cates of the rock exhibited no trace of decomposition. 3. Eleonorate from Arkansas.-A strongly dichroic crystal in a geode of dufrenite, from Sevier Co., Arkansas, was identified by the author as Streng's eleonorite. As all the water was driven off at 280°, Streng's formula, FesP4OI9 + 8H20, is preferable to that of Groth, Fe,(OH),(PO,), + 2QH20. 4. Minerals from Frariklin., New Jersey.-At this well-known locality the following minerals have recently been met with :- Chloanthite, arsenic-nickel, fluorspar, apatite, and hydrated nickel silicate ; the latter on analysis gal-e- SiO,. NiO.CaO. MgO. ZnO. FeO. HQO. As205. Total. 31.02 38.82 0.70 0.42 4.00 2% 16.58 4.77 97.96 R. H. B. Pseudobrookite, from Havredal, Norway. By A. CEDERSTROM (Zeit. Kr!yst. Min., 17, 133-1 36).-This mineral was first analysed by Koch and Lattermann. Owing t o want of material, the analysis could not be made with accnrecy. The discovery of large crystals at Hnvrednl has enabled the author to mike an analysis of carefully selected material, the results beiug as follows :- Author. Koch. Lattermann. Calculated. - - Ignition.. . - 0-69 Pez03. . . . . 56-42 42-29 48.64 56.54 TiO,. . . . .. 44.26 62.74 46-79 43 -46 MgO .. . . . - 4.28 4-53 - Total .. .. 100.68 100.00 99.96 100.00 The last column gives the percentage composition calculatJed from Chemical-mineralogical Theories. By V. GOLDSCHMIDT (Zeit. Kr!pt. Min., 17, 25--tj6).-This memoir is divided into three sec- tions: (1) on the varieties of isomorphism, (2) on symbols and formulq and (3) on the formula of the silicsates. The two first sec- tions serve as an introduction to the views propounded in the third. By the introduction of letters, the author encteavours to simplify the formulae of silicates. E for R',02 or R",O,, representing SiO,, A for R'2Rvi604, representing Si204, R2 for Rvi206, representing Si,06, Si for SiOz, Sizfor Si201, &c., the formula Fed( Ti04)3. B. H. B. Thus he employs the symbols- 9 2220 ABSTRACTS OF CHEMICAL PAPERS.so that, for example, would be the abbreviated formula for albite. Further, he employs symbols for the silicate molecules of more frequent occurrence; thm the hornblende molecule is H = ASi = "'$} O,, and the nepheline molecule N = ASi,. B. H. B. Artificial Preparation of Wollastonite, By E. HUSSAK (Zeit. Kryst. Min., 17, lOl).-In these experiments, a glass composed of J(N&O,SiO,) + 2(Cs0,B203) was melted, and, on cooling, was found to be free from bubbles, crystals, and crystallites. Mixed with CaSi03 (1 mol.), the mass on cooling was found to be full of bubbles and fissures, and on the sides of the crucible there were a few im- perfect, columnar, colourless, minute crystals. When more CaSiO,% (2 mols.) was added, the colourless columns increased in number, and formed into a radiated globule.The mixture of the glass and 3 mols. of CaSi03 on cooling became completely crystalline. A number of hex- agonal tablets were present, but the minute columns still predominated. The tablets belong to the hexagonal, optically positive calcium sili- cate, whilst the columns are crystals of wollastonite est,ended in the direction of the axis of symmetry. B. H. B. Leucitophyre from Persia. By V. STEINECKE (Zeit. Kryst. M ~ K , 17, 110-1 11 ; from Zeit. Naturwiss., 60, 4).-At Koschkserwi Maraud, in a magma of orthoclase, plagioclase, nepheline, augite, leucite, and magnetiie, there are found crystah of lencite, augite, olivine, sanidine, and nepheline. The leucite gave on analysis- SiO* CaO.MgO. MnO. 8 1 2 0 3 . Fe20,. K20. Na,O. Ignition. 54.54, 0.99 0.25 trace 22-18 1.74 19.83 0.71 1.33 An analysis of the augite is also given. B. H. B. Nosean-bearing Ejections from the Laacher See. By L. L. HUBBARD (Zeit. Kryst. Min., 17, 208 : from Tschermak's min. Jlifth., 8, 356--399).--In the ejections found a t the Laacher See, nosean is principally confined to geodes, and in its formation in a t,rrachytic rock, sanidine has, in many cases, been produced. The latter occurs in radiated masses, and gave on analysis the following results :- Si02. Al?O,. Fe203. CaO. MgO. Na20. K20. Total, Sp. gr. 65.36 21.19 0-45 0.56 trace 6.77 5.72 100.05 2.556 B. H. B. Wiluite. By R. PRENDEL (Zeit. Krys. Min., 17, 9&-97).-The author has made an exhaustive investigation of the physical pro- perties of the idocrase of Wilui, and proves that this so-called wiluite cliff ers considerably from idocrase proper.By A. BECKER (Zeit. Kryst. Min., 17, 128--132).-'l'he author has analysed (1) biotite aiid (2) muscovite of remarkable purity, carefully isolated from the gneiss, ,338 metres B. H. B. Two Analyses of Mica.MINERALOOICAL CHEMISTRY. 221 1-53 2-94 0.83 0.62 17'51 17.12 35.561 34.35 trace I trace 0 02 0.36 0'81 0.2'3 2 61 2.99 00 -51 100 '81 1 3-82 3-56 trace trace below the surface, at a mine at Halsbriicke, near Freiberg, in Saxony. The analytical results were as follow :- SiOz. TiO:. Al,O,. Fe,O,. FeO. MnO. MgO. KzO. 3 . . .. 34.70 4.58 17.17 2-11 19.05 0.50 9.52 8-91 2.. .. 46.74 1.52 32.56 1.55 0.92 - 1-18 10.37 1 ........1.24 3.56 0.20 101.54 2 ........ 1.02 3.s5 - 99.41 Na,O. HIO. P. Total. The formult~ of the two minerals are- - 3-85 4-68 2-62 2.43 2.79 3-46 3-92 1.23 1-09 2-76 2-47' 3-08 1-51 2-21 16.31 14.74, 16.70 16.18' 16.03 15.43 16.25 36-01 35'43 34.97 35.11 33.84 35.81 35.48 - trace I trace trace 0.37 trace 0.14 0.23 0.66 0.25 0.12 0.16 0.18 0-16 1.36 0'18 1'18 1.25 1.83 0.81 0.52 trace trace 1.32 1.70 1-92 1.35 1.36 3'41 2-78 1-15 0.861 1.25 0.87 0.98 101 *39 100 -67 100 -55 101 * 10 100 -89 100 -34 100 '84 2.70 2 42 2-51 2-67 2-13 3-04 2-72 - ~ ~ - - - ~ - - - --._ I (1) 5 [KNaH),SiO4 + 8( FeMn%Ig),SiO, + 3(A1,Fe2)2( SiO,),. (2) 2(KNaH)2Si03 + (A12Fe2)2(Si0d)3. B. H. B. Chemical Composition of Vesuvian. By J. H. VOGEL (Zsit. Kryst. Min., 17, 21 5--216).--The author gives the results of analyses of nine specimens of vesuvian from different localities :--1.Cziklowa, yellowish-green crystals, sp. gr. 3.38, directly determined water 1.53 per cent. ; 2. Becco della Corbassera, Ala, yellowish-green masses, sp. gr. 3*586, HzO 1.11 ; 3. Canzocoli, near Predazzo, large, yellowish- brown crystals, sp. gr. 3.404, HzO 1.57; 4. Zermatt, dark-brown crystals, sp. gr. 3.488, H,O 1.05; 5. Egg, sp. gr. 3.406; 6. Haslau, dark-brown masses, sp. gr. 3.419 ; 7. Sandford, brown crystals, sp. gr. 3.419 ; 8. Eker, sp. gr. 3.328 ; 9. Arendal, large, dark-brown crystals, sp. gr. 3.38. -- Si02 ......... Y'i02. ......... Fe2O3 ........ FeO .......... Al,O, ........ CaO ......... MnO ......... bi g o ......... K,O ......... 3 +o ........F ............ Ignition ...... Total .... --- B. H. B. Petrography of South-West Africa. By H. WULF (Zeit. Kryst. Xin., 17, 199-200 ; from Tscherwiak's wiiia. Mitth., 8, 193-238).-- The author gives analyses of scapolite from the scapolite-gneiss of the copper mine, and of Husab on the Tsoachaub, to the east of Wall- fisch Bay. Analyses are also given of augite from the same rock, of wullastonite from the wollastonite-augite-gneiss of Reed, and from222 ABSTRACTS OF CHEMICAL PAPERS. the wollastonite-diopside rock of the copper mine. Epidote from Diepdal gave on analysis the following results :- SiO,. Al,03. Fe203. MnO. CaO. Ignition. Total. Sp. gr. 37-04 22.99 14.19 trace 24.09 2.16 100.47 3.4.0 €3. H. B. Meteorite from Phu-Hong. By S. MEUNIER (Compt. rend., 109, 875--878).--This meteorite fell on September 22nd, 1887, a t Phu- Hone;, in Cochin China.It has a granular and even oolitic fracture, which is of a violet-grey colour, and the polished surface gives Wid- mannstatt's figures. Under the microscope, i t is seen to consist of a transpai ent matrix, with opaque ramifying filaments and irregular granules. The transparent portion consists of peridote and magne- sium pyroxene ; the needles are arranged in very numerous spheroidal masses or chondrites. The sp. gr. of the meteorite at 12" is 3.601; 35.37 per cent. is magnetic; 29-62 per cent. is soluble in hydrochloric acid, and 35.12 is notl attacked by the acid. The magnetic portion contains 91.22 per ceut. of iron and 9.05 per cent. of nickel, with distinct traces of cobalt.The compositioh of the soluble and insoluble non-magnetic portions are given in the following table :- SiO,. MgO. CaO. N%O. FeO. Al,03. CrzO,. Mn. Insoluble.. 63.60 28.48 1.91 0.87 4.10 1-22 0.92 trace Soluble ... 40.09 45.97 - - 14.00 - - - The meteorite belongs to the type Zim.erickite, and the author discusses the claims of certain other meteorites and terrestrial rocks to be included in the same type. Analysis of Water from the Roundwood Colliery. By J. F. CLEEVES and J. C:PLATTS (J. Soc. Chern. Ind., 7, 7d9).-The sample was taken at a depth of 500 yards from the surface, and at a distalice of l,SOC, yards from the bottom of the shaft. The temperature was 19", and the sp. gr. 1.0622. Analysis gave the following results expressed in grams per litre :- SiO,.Al,03 and Fe,03. BaC1,. MgBr,. MgClf. CaC1,. NaC1. Totals. 0.129 0.019 0.292 0.413 5.087 22.850 67.351 96.141 Chlorine required.. ............ 59.38 Chlorine found.. .............. 59.50 C. R. B. The water contains a large amount of gases dissolved in it, prominent among them being marsh gas. D. B.MINERALOGICAL CHEMISTRY.M i n e r a l o g i c a l Chemistry.217Composition of Roumanian Rock-salt. By ISTRATI (BUZZ. SOC.China. [3], 2, 4-88).-l’his mineral, which is mined in the Carpa-thians, contains 98-99.8 per cent. of sodium chloride. Some varietieshave a definite odonr of pet,roleum, which in some cases is containedin the mineral to such an extent that explosions have occurred. Thevariety known as ‘‘ puturosa” coni.ains as much as 117 C.C.of gasesper kilo.; the gas obtained from Dolftana salt yielded on analysis25 per cent of unsaturated hydrocarbons and 19.6 per cent,. of oxygen,but no carbonic anhydride. T. G. N.VOIA. LVIIL. !218 ABSTRACTS OF CHEMICAL PAPERS.Kobellite from Colorado. By H. F. EELLER (Zeit. Kryst. Min.,17, 67--72).-This mineral, from the Silver Bell mine, Oumy, isfine-grained, somewh:Lt fibrous, and exhihits no crystalline form.It has a sp. gr. of 6.334. The analyses lead to the formula2(PbAg$ii,)S, (SbBi),S:,. This does not agree with Rammelsberg’sformula, Pb3BiSbSs.18-39 28.40 7-55 36-16 3-31 2-59 1.50 0.39 0.45 98.74The mean of four analyses was as follows :-5. Bi. Sb. Pb. Ag. Cu. Fe. Zn. Gangue. Total.B. H. B.Aurichalcite. By A. BELAR (Zpit.Kryst. Min., 17, 113-127).-In the aurichalcite of Temperino, Delesse detected the presence ofcalcium. Other chemists regard this a s merely a mechanical im-purity in hhe material anal-ysed, and believe that aurichalcite isnothing more than R compound of copper and zinc hydrated carbon-ates. Analyses were made of aurichalcite (1 and 2) from Moravicza,,(3j from Campiglia, and (4) from Sardina, with the following re-sults :-CuO. ZnO. FezO,. R,O. cop1 ...... 20.39 54.70 - 13-53 11.X32 ...... 21.43 53.57 - 26.783 ...... 20.20 55.51 - 26.F)O4 ...... 15-58 58.72 2.17 22.97\-All four analyses lead to the formula CuCO, + 3Z1i(Ho)~.I n concliision, the author gives the results of experimenh madewith the view of preparing aurichalcite art,ificially.He finds that tlhestatenient of Delesse, that aurictinlcibe re-crystallism out from solu-tions of the mineral in ammonium carbonate, is not correct.B. H. B.Messelite, a New Mineral. BJ- W. MUTHMANN (Zeit. Kryst.Min., 17, 93-94) .-This mineral forms radiated masses of brown orcolourless tablets in a bituminous shale embedded in the lignite ofthe Messel mine in Hesse-Darmstadt. The crystals were foundoptically to be triclinic. Analysis gave the following results :-P&. CaO. FeO. MgO. MnO. HzO. Insol. Total.37.72 31-11 15.63 1.45 trace 12.15 1-40 99-46These results correspond with the formula (CaFeMg)3(P04)2 +Messelite differs from fairfieldite by the absence 0: man- 24H,O.ganese and by the different proportion of water.B. H. B.Mazapilite, Anhydrite, Eleonorite, &c., from North America,.By G. A. K ~ N J G (Zeit. Kryst. Mln., 17, &4---92).-1. iVuzapilite isthe name given by the author to an extremely rare mineral from theJesus Maria Mine, Mazapil, Mexico. The crystals belong to therhombic system, the axial ratio being a : b : c = 0-8616: : 1 : 9.9969.Analysis gaveMINERALOGICAL CHEMISTRY. 219AS,^,. Sb20,. P205. Fe,O,. CaO. HzO. Total. Sp. gr.43-60 0.25 0.14 30.53 14-82 9*83 99.17 3.582Formula : Ca3Fe2 (As04)4(OFe.0H)2 + 5H20.2. Anhydrite.-This mineral was found at the Darby tunnel, sevenmiles from Philadelphia, in the unusual form of crusts consisting ofparallel prisms on the plagioclnse and augite of a diabrtse. The sili-cates of the rock exhibited no trace of decomposition.3.Eleonorate from Arkansas.-A strongly dichroic crystal in ageode of dufrenite, from Sevier Co., Arkansas, was identified by theauthor as Streng's eleonorite. As all the water was driven off at 280°,Streng's formula, FesP4OI9 + 8H20, is preferable to that of Groth,Fe,(OH),(PO,), + 2QH20.4. Minerals from Frariklin., New Jersey.-At this well-knownlocality the following minerals have recently been met with :-Chloanthite, arsenic-nickel, fluorspar, apatite, and hydrated nickelsilicate ; the latter on analysis gal-e-SiO,. NiO. CaO. MgO. ZnO. FeO. HQO. As205. Total.31.02 38.82 0.70 0.42 4.00 2% 16.58 4.77 97.96R. H. B.Pseudobrookite, from Havredal, Norway. By A. CEDERSTROM(Zeit. Kr!yst. Min., 17, 133-1 36).-This mineral was first analysed byKoch and Lattermann.Owing t o want of material, the analysiscould not be made with accnrecy. The discovery of large crystals atHnvrednl has enabled the author to mike an analysis of carefullyselected material, the results beiug as follows :-Author. Koch. Lattermann. Calculated.- - Ignition.. . - 0-69Pez03. . . . . 56-42 42-29 48.64 56.54TiO,. . . . . . 44.26 62.74 46-79 43 -46MgO .. . . . - 4.28 4-53 -Total .. .. 100.68 100.00 99.96 100.00The last column gives the percentage composition calculatJed fromChemical-mineralogical Theories. By V. GOLDSCHMIDT (Zeit.Kr!pt. Min., 17, 25--tj6).-This memoir is divided into three sec-tions: (1) on the varieties of isomorphism, (2) on symbols andformulq and (3) on the formula of the silicsates.The two first sec-tions serve as an introduction to the views propounded in the third.By the introduction of letters, the author encteavours to simplify theformulae of silicates.E for R',02 or R",O,, representing SiO,,A for R'2Rvi604, representing Si204,R2 for Rvi206, representing Si,06,Si for SiOz,Sizfor Si201, &c.,the formula Fed( Ti04)3. B. H. B.Thus he employs the symbols-9 220 ABSTRACTS OF CHEMICAL PAPERS.so that, for example, would be the abbreviated formula foralbite. Further, he employs symbols for the silicate molecules ofmore frequent occurrence; thm the hornblende molecule is H =ASi = "'$} O,, and the nepheline molecule N = ASi,.B. H. B.Artificial Preparation of Wollastonite, By E. HUSSAK (Zeit.Kryst.Min., 17, lOl).-In these experiments, a glass composed ofJ(N&O,SiO,) + 2(Cs0,B203) was melted, and, on cooling, was foundto be free from bubbles, crystals, and crystallites. Mixed withCaSi03 (1 mol.), the mass on cooling was found to be full of bubblesand fissures, and on the sides of the crucible there were a few im-perfect, columnar, colourless, minute crystals. When more CaSiO,%(2 mols.) was added, the colourless columns increased in number, andformed into a radiated globule. The mixture of the glass and 3 mols. ofCaSi03 on cooling became completely crystalline. A number of hex-agonal tablets were present, but the minute columns still predominated.The tablets belong to the hexagonal, optically positive calcium sili-cate, whilst the columns are crystals of wollastonite est,ended in thedirection of the axis of symmetry.B. H. B.Leucitophyre from Persia. By V. STEINECKE (Zeit. Kryst. M ~ K ,17, 110-1 11 ; from Zeit. Naturwiss., 60, 4).-At KoschkserwiMaraud, in a magma of orthoclase, plagioclase, nepheline, augite,leucite, and magnetiie, there are found crystah of lencite, augite,olivine, sanidine, and nepheline. The leucite gave on analysis-SiO* CaO. MgO. MnO. 8 1 2 0 3 . Fe20,. K20. Na,O. Ignition.54.54, 0.99 0.25 trace 22-18 1.74 19.83 0.71 1.33An analysis of the augite is also given. B. H. B.Nosean-bearing Ejections from the Laacher See. By L. L.HUBBARD (Zeit. Kryst. Min., 17, 208 : from Tschermak's min. Jlifth.,8, 356--399).--In the ejections found a t the Laacher See, nosean isprincipally confined to geodes, and in its formation in a t,rrachyticrock, sanidine has, in many cases, been produced.The latter occursin radiated masses, and gave on analysis the following results :-Si02. Al?O,. Fe203. CaO. MgO. Na20. K20. Total, Sp. gr.65.36 21.19 0-45 0.56 trace 6.77 5.72 100.05 2.556B. H. B.Wiluite. By R. PRENDEL (Zeit. Krys. Min., 17, 9&-97).-Theauthor has made an exhaustive investigation of the physical pro-perties of the idocrase of Wilui, and proves that this so-called wiluitecliff ers considerably from idocrase proper.By A. BECKER (Zeit. Kryst. Min., 17,128--132).-'l'he author has analysed (1) biotite aiid (2) muscoviteof remarkable purity, carefully isolated from the gneiss, ,338 metresB.H. B.Two Analyses of MicaMINERALOOICAL CHEMISTRY. 2211-53 2-940.83 0.6217'51 17.1235.561 34.35trace I trace0 02 0.360'81 0.2'32 61 2.9900 -51 100 '8113-82 3-56trace tracebelow the surface, at a mine at Halsbriicke, near Freiberg, in Saxony.The analytical results were as follow :-SiOz. TiO:. Al,O,. Fe,O,. FeO. MnO. MgO. KzO.3 . . .. 34.70 4.58 17.17 2-11 19.05 0.50 9.52 8-912.. .. 46.74 1.52 32.56 1.55 0.92 - 1-18 10.371 ........ 1.24 3.56 0.20 101.542 ........ 1.02 3.s5 - 99.41Na,O. HIO. P. Total.The formult~ of the two minerals are--3-85 4-68 2-62 2.43 2.79 3-46 3-921.23 1-09 2-76 2-47' 3-08 1-51 2-2116.31 14.74, 16.70 16.18' 16.03 15.43 16.2536-01 35'43 34.97 35.11 33.84 35.81 35.48- trace I trace trace 0.37 trace 0.140.23 0.66 0.25 0.12 0.16 0.18 0-161.36 0'18 1'18 1.25 1.83 0.81 0.52trace trace 1.32 1.70 1-92 1.35 1.363'41 2-78 1-15 0.861 1.25 0.87 0.98101 *39 100 -67 100 -55 101 * 10 100 -89 100 -34 100 '842.70 2 42 2-51 2-67 2-13 3-04 2-72- ~ ~ - - - ~ - - - --._I(1) 5 [KNaH),SiO4 + 8( FeMn%Ig),SiO, + 3(A1,Fe2)2( SiO,),.(2) 2(KNaH)2Si03 + (A12Fe2)2(Si0d)3.B. H. B.Chemical Composition of Vesuvian. By J. H. VOGEL (Zsit.Kryst. Min., 17, 21 5--216).--The author gives the results of analysesof nine specimens of vesuvian from different localities :--1. Cziklowa,yellowish-green crystals, sp. gr. 3.38, directly determined water 1.53per cent. ; 2. Becco della Corbassera, Ala, yellowish-green masses,sp. gr. 3*586, HzO 1.11 ; 3.Canzocoli, near Predazzo, large, yellowish-brown crystals, sp. gr. 3.404, HzO 1.57; 4. Zermatt, dark-browncrystals, sp. gr. 3.488, H,O 1.05; 5. Egg, sp. gr. 3.406; 6. Haslau,dark-brown masses, sp. gr. 3.419 ; 7. Sandford, brown crystals,sp. gr. 3.419 ; 8. Eker, sp. gr. 3.328 ; 9. Arendal, large, dark-browncrystals, sp. gr. 3.38.--Si02 .........Y'i02. .........Fe2O3 ........FeO ..........Al,O, ........CaO .........MnO .........bi g o .........K,O .........3 +o ........F ............Ignition ......Total ....---B. H. B.Petrography of South-West Africa. By H. WULF (Zeit. Kryst.Xin., 17, 199-200 ; from Tscherwiak's wiiia. Mitth., 8, 193-238).--The author gives analyses of scapolite from the scapolite-gneiss ofthe copper mine, and of Husab on the Tsoachaub, to the east of Wall-fisch Bay.Analyses are also given of augite from the same rock, ofwullastonite from the wollastonite-augite-gneiss of Reed, and fro222 ABSTRACTS OF CHEMICAL PAPERS.the wollastonite-diopside rock of the copper mine. Epidote fromDiepdal gave on analysis the following results :-SiO,. Al,03. Fe203. MnO. CaO. Ignition. Total. Sp. gr.37-04 22.99 14.19 trace 24.09 2.16 100.47 3.4.0€3. H. B.Meteorite from Phu-Hong. By S. MEUNIER (Compt. rend., 109,875--878).--This meteorite fell on September 22nd, 1887, a t Phu-Hone;, in Cochin China. It has a granular and even oolitic fracture,which is of a violet-grey colour, and the polished surface gives Wid-mannstatt's figures. Under the microscope, i t is seen to consist of atranspai ent matrix, with opaque ramifying filaments and irregulargranules. The transparent portion consists of peridote and magne-sium pyroxene ; the needles are arranged in very numerous spheroidalmasses or chondrites.The sp. gr. of the meteorite at 12" is 3.601; 35.37 per cent. ismagnetic; 29-62 per cent. is soluble in hydrochloric acid, and 35.12is notl attacked by the acid. The magnetic portion contains 91.22per ceut. of iron and 9.05 per cent. of nickel, with distinct traces ofcobalt. The compositioh of the soluble and insoluble non-magneticportions are given in the following table :-SiO,. MgO. CaO. N%O. FeO. Al,03. CrzO,. Mn.Insoluble.. 63.60 28.48 1.91 0.87 4.10 1-22 0.92 traceSoluble ... 40.09 45.97 - - 14.00 - - -The meteorite belongs to the type Zim.erickite, and the authordiscusses the claims of certain other meteorites and terrestrial rocksto be included in the same type.Analysis of Water from the Roundwood Colliery. By J. F.CLEEVES and J. C:PLATTS (J. Soc. Chern. Ind., 7, 7d9).-The samplewas taken at a depth of 500 yards from the surface, and at a distaliceof l,SOC, yards from the bottom of the shaft. The temperature was19", and the sp. gr. 1.0622. Analysis gave the following resultsexpressed in grams per litre :-SiO,. Al,03 and Fe,03. BaC1,. MgBr,. MgClf. CaC1,. NaC1. Totals.0.129 0.019 0.292 0.413 5.087 22.850 67.351 96.141Chlorine required.. ............ 59.38Chlorine found.. .............. 59.50C. R. B.The water contains a large amount of gases dissolved in it, prominentamong them being marsh gas. D. B

ISSN:0368-1769    

DOI:10.1039/CA8905800217

出版商:RSC    

年代:1890

数据来源: RSC

摘要:

ORGANIC CHEN ISTRT. 223 0 r g anic C hem i s t ry. Constitution of Petroleum. By J. A. LE BEL (BUZZ. SOC. Ghim. [3] 2,305-307).-The author considered that normal paraffins might alone be present in petroleum the occurrence of the secondary paraffins being due to isomeric change occurring dnring its manipulation. He found however after isolation of the amylenes from natural petr- oleum and subsequent treatment with concentrated hydrochloric acid in the cold that dimet.hylethy1 chloride boiling a t 86" was obtained which proves the occurrence of other than normal paraffins in petroleum and according to him negatives the fermentation theory of petroleum formation since no fermentation is known which produces both classes of compounds a t a time. Diallyl Tetrabromides. By G.WAGNER (Ber. 22 3056-3057). -The author has previously stated that diallyl is probably a mixture of two isomerides (compare Abstr. 18813 226) a view which if correct would explain the existence of the two tetrabromides C,H,,Br,. Ciamician and Anderlini (this vol. p. ZO) in assnming that these two bromides are geometrically isomeric have probably overlooked the author's previous paper. T. 0. N. F. S. K. Action of Hydrocyanic Acid on Calomel. By FouQuEr (J. Yharm. [ 5 ] 20 397-400).-The statement that corrosive sublimate is produced by the action of hydrocyanic acid on calomel is incorrect. Mercury is set free with the formation of mercuric cyanide and hydrochloric acid in equivalent quantities. The reaction is almost always incomplete; bnt it may be started again by neutralising the free hydrochloric acid.Ammoniomercuric Cyanides. By R. VARET (Compt. revd. 109 903-904).-Alcoholic ammonia is saturated with mercuric cyanide a current of ammonia gas being passed through the liquid while solution is taking place. The solution is heated a t 50" to 60° again saturated with dry ammonia and allowed to cool. After some time it deposits trmispareiit prismatic needltbs of the compound HgCy2,2NH3 which become opaque and rapidly lose ammonia when exposed to the air. At loo" it loses the whole of the ammonia in a few hours If concentrated aqueous ammonia is saturated with mercuric cyanide mixed with more ammonia and cooled it yields long white prismatic needles of the compound HgCy2,2NH3,+H20 ; this readily loses water and ammonia on exposure to air although it is more stable than the preceding compound.A t IGO" it decomposes com- plet,ely and mercuric cyanide is left. The compound HgCy2,NH3 is obtained in small hard transparent crystals by heating aqueous ammonia with a large excess of mercuric cyanide in a closed vessel a t 40". It dissolves in ammonia alters when exposed to air and loses all its ammonia a t 100". The action J. T.224 ABSTRACTS OF CHEMKCAL PAPERS. of dry ammonia on finely-powdered mercuric cyxnide yields a yellowish-white product of the composition 10HgCp2,NH,. If ordinary ammonia is saturated with mercuric cyanide mixed with one-tenth its volume of ammonia solution and cooled to 0" i t yields small white crystals of the compound HgCy2,NH,,$H20 very soluble in aqueous or alcoholic ammoilia very unstihle when exposed to air.At looo it loses the whoIe of its water and ammonia. C. H. B. Interaction of Haloi'd Salts of Mercury and Zinc. By R. VARET (C~mpt. rend. 109 809-812).-A concentrated solution of zinc bromide is added drop by drop to a boiling saturated solution of mercuric cyanide with vigorous agitation. The greater part of the precipitate redissolves but the liquid remains turbid. It is filtered and allowed to cool when it deposits white crystals of the compound Hg?ZnBrzCy4 + 8Hz0 which alters little if a t all on exposure t o air is somewhat soluble in water and becomes anhydrons a t 100" or in zt vacuum. When the hydrated compound is heated it loses water blackens and decomposes in to mercury cyanogen mercuric bromide and zinc carbonate.Nitric acid converts it into zinc nitrate mercuric cyanide and mercuric bromide hydrocyanic acid being evolved. Dry ammonia expels the combined water and forms a compound HgpZnBrzCy4 + 2NH3 which loses ammonia when exposed to air and is decomposed by water. That this compound has the constitution ZnCyz,HgC'y2,HgBr + 8H20 and is not a compound of mercuric cyanide with zinc bromide is proved by the following facts. Potassium iodide added to the aqueous solution produces at first a precipitate of zinc cyanide fol- lowed by a precipitate of mercuric iodide ; and Berthelot has shown that potassium iodide combines with merciiric cyanide with liberation of heat but has no action on zinc cyanide. Cupric sulphate liberates cyanogen and produces a peach- blossom coloured precipitate of mercuric cupric bromo-cyanide.The addition of zinc cyanide to a boiling concentrated solution of mercuric bromide yields the same compound and i t is evident that its formation limits the action between mercuric bromide and cyanide and zinc cyanide and bromide whatever may be the arrange- ment of the atoms in the initial system. C. H. B. Mannose. By E. FISCHER and J. HIRSCHBERGER (Ber. 22 3218-3224).-The mannose employed in these experiments was obtained from vegetable ivory nuts by a niodification of Reiss' method (Abstr. 1889 687) instead of by the oxidation of mannitol. Com- parative experiments made with mannose from thc latter source showed the complete identity of the two sugars. The method of preparation was as follows Sifted ivory-nut shavings (1 part) were digested with 6 per cent.hydrochloric acid (2 parts) on the water- bath for six honrs filtered hot the residue pressed and again ex- tracted with water. The brown solution after treatment with animal charcoal was neutralised with caustic soda solution and an excess of phenylhydrazine acetate added. The resulting hydrazone was pnri-ORGANIC CHEMISTRY. 225 fied and converted into mannose by the method previously described (Abstr. 1839 481). Mu,nnonic Acid.-For the preparation of this acid a solution of mannose (1 part) in water (5 parts) is mixed with bromine (2 parts) at the ordinary temperature frequently shaken and allowed to remain 24 hours after the bromine has dissolved. The latter is then eliminated in the usual manner and the resulting solution of man- nonic acid converted into the phenylhydrazide C12H18N20fi by Fischer and Passmore's method (this vol.p. 152) ; this forms small colour- less brilliant prisms which melt at 214-216" with decomposition are soluble in hot water but sparingly in cold wa'ter or alcohol. It may also be obtained directly from ivory nuts in the following manner The ivory-nut shavings are heated with 6 per cent. hydrochloric acid and the solution treated with animal charcoal as previously described. The quantity of mannose in solution is determined by precipitating a known quantity with phenylhydrazine and for every part of sugar found 2 parts of bromine added to the solution. The whole is frequently shaken until all the bromine has dissolved and then allowed to remain.After evaporating off the free bromine the solu- tion is nearly neutralised with lead carbonate filtered precipitated with lead acetate solntion and again filtered. The filtrate may be then converted into the hydrazide as before. The latter after re- crystallisation is decomposed by boiling baryta-water the liberated phenylhydrazine extracted with ether. and the boiling liquid exactly precipitated with sulphuric acid. Tho filtrate on evaporation leaves a syrup which solidifiev to a slightly brown crystalline mass. This is extracted twice with a little alcohol and the residual white com- pound recrystallised from this solvent. The crystals obtained form stellate groups of colourless needles and hare the composition C6H1006 and are therefore tlhe Zactone of mannonic acid ; this melts at 149-153" is readily soluble in water but less so in alcohol.Its aqueous solution is dextrorotatory [a]= = 53.81 and has a neutral reaction but quickly dissolves carbonates on boiling forming salts of mannonic acid. The ccxlciiim salt (C6H1107)2Ca + 2H& forms microscopic prisms. The strontium salt with 3 mols. H20 crystallises from alcohol in small prisms. The barium salt has not yet been obtained crystalline. Mannonic acid is oxidised by nitric acid to a bibasic acid which differs from saccharic and metasaccharic acids and seemingly also from isosaccharic acid. This compound is undergoing further exami- nation. The authors have previously stated that mannose undergoes fer- mentation with yeast and they have been able to confirm t h i s by a repetition of the experiment with larger quantities.A 5 per cent. solution when mixcd with fresh yeast at the ordinary temperature evolves carbonic anhydride in 10-15 minutes and in 24 hours the reaction is complete. Prom the filtered solution ethyl alcohol can be separated by fractional distillation the yield seemingly being the same as that from dextrose. The liquid obtained by boiling ivory nuts with 6 per cent. hydrochloric acid also ferments after neutra- lisation with lime although more slowly. As fkom 900-1001) tons226 ABSTRACTS OF OHEMICAL PAPERS. of such shavings are obtained yearly and these yield 33 per cent. of their weight of sugar it would seem that a commercial process for the preparation of alcohol from this source might be successfully founded.Marinose is acted on by acetic chloride in exactly the same manner as dextrose. The acetochloromunnose obtained likewise forms a syrup which is sparingly soluble in water but is decomposed by long-con- tinued boiling with the latter into mannose and acetic and hydro- chloric acids. H. G. C. Sugar from the Quebracho. By C. TANRET (Compt. rend. 109 908-910).-The bark of the quebracho (Aspidosperwm qwbracho) yields a sugar quebrachite of the composition C7HI4O6 which crystal- lises from alcohol in anhydrous rhomboidal prisms with a very sweet taste. It is very soluble in water and somewhat soluble in boiling alcohol but insoluble in ether. It melts a t 186-187" boils in a vacuum and condenses in beautiful needles ; rotatory power [a!= = -80" ; sp.gr. a t 0' = 1.54. Quebrachite ferments only in contact wit.h beer-yeast and has no action on Fehling's solution but reduces ammoniacal silver nitrate. It is not affected by boiling dilute solu- tions of acids or alkalis and gives no precipitate with basic lead acetate but is precipitated by ammonincal lend acetate provided the solution is not very dilute. Monohydrated sulphuric acid dissolves i t readily especially at loo" with slight discoloration forming que- brachisulphuric m i d a lavogyrate acid which yields soluble non-crjs- tallisable barium and calcium salts. When heated with acetic anhy- dride and zinc chloride it yields a crystalline derivative which melts at 89'. With nitric and sulphuric acids it yields an unstable nitrin and when heated with nitric acid it gives rhodizonic acid.When heated with hydriodic acid quebrachite yields methyl iodide and an inosite which crystallises from alcohol in very brilliant slender efflorescent prismamtic needles soluble in 2.3 parts of water at 12" very slight.ly soluble in I.oiling alcohol and insoluble in ether. It melts at 238" is somewhat less volatile than quehranhihe and has a la?vorotntory power of [ajD = -55". With nitric acid it gives the in osit e react ion. C. H. B. Formation of Rafflnose. By F. HERLRS (Chem. Centr. 1889 ii 421-422 ; from Bohm. Zeit. Zucker-It'd. 13 455).-The author has subjected cane-sugar to the action of calcium hydroxide a t various temperatures but without being able to detect any formation of raffinose a result in agreement with t h a t obtained by Cech (Chem.Centr. 1889 i 682). He draws the conclusion that the formation of rafinose takes place in the beet,root. He also confirms the correct- ness of Herzfeld's statement (ibid. $04)) that it is forrited by freezing the beetroot. The author 6nds that the preservation of the beetroot for too long a time favours the formation of raffinose. J. W. L. Melitriose and Melibiose. By C. SCHEIBLER and H. MITTELMEIER (Ber. 22 3118-3 124 ; compare Abstr. 1589 953).-Melitose prepared from cotton-seed meal exactly as dkscribed by BerthelotORGANIC CHEJIISTRI'. 227 (Compt. rend. 103 533)' iR not changed by boiling baryta-water does not reduce Fehling's solution and crystallises unchanged from alco- hol. Berthelot's statement (Zoc. cit.) that melitose is decomposed by alcohol into raffinose and eucalyn is therefore incorrect and melitose is identical with raffinose.When melitriose is treated with a dilute solution of invertin a t the ordinary temperature for two hours it is decomposed into melibiose and levulose; but when it is kept for 36 hours at 40" with a con- centrated solution of invertin it is decomposed into dextrose galac- tose and levulose ; Berthelot's eucalyn is therefore identical with melibiose. When melibiose is reduced with sodium-amalgam a t the ordinary temperature the solution being kept as neutral as possible i t is con- verted into a substance ( m e l i b i o t i t e ) which does not reduce Fehling's solution but if a little of the solution is boiled for a short time with n few drops of sulphuric acid it acquires powerful reducing proper- ties galactose bc;.ng one of the decomposition-products of meli bio- tite.F. S. K. Molecular Weights of Maltose and of several Inulin-like Substances. By A. G. EKSTHAND and R. MAUZELIUS (Chena. CerLtr. 1889 ii 444 ; from Vetensk. Aknd. Forhandl. 1889 157).-The mole- cular formulte given below were determined by Raoult's method :- Anhydrous maltose C,zH22011. Triticin C:36H6& from the root of Dracmua riibra melts at 140" and has the specific rotation [a]D - -36.61. specific rotation [.In = - 41.07. Graminin C18H800.10 from Trisetulii alpestre melts a t 220" and has the specific rotation [.ID = -44.47. Irisin CssH1600so from Iris pseudo-acorus melts at 160" and has the Rpecific rotation [.ID = -51.20.Phlein from Phleuin pratense melts at 215" arid has the specific rotation [ a ] D = -47.94; the molecular weight could not be determined. Triticin from T r i l i c u m repens melts a t 160" and has the J. W. L. Animal Cellulose. By R. ScHijrrzF (Chem. Centr. 1889 ii 588 ; from Mitt. pharm. Inst. Erhngen 2 Heft 280-281).-The author has examined the mantle of I'hallusia rnammillaris it being purified by boiling first with water shen repeatedly with 20 per cent. potas- sium hydroxide solution and 10 per cent. hydrochloric acid and finally by digestion with hydrofluoric acid and hydrochloric acid. The white cellulose substance contained 43.47 per cent. of carbon and 6-85 per cent. of hydrogen. Solution of cupric oxide in ammonia dissolves the substance and solution of iodine in zinc chloride or sulphuric acid Btairis it variously from red to violet.Nitric and sulphuric acids form an explosive nitrate with it which is somewhat soluble in ether. When heated with 10 per cent. sulphuric acid in a closed flask at loo" a substance is formed which reduces Fehling's solution and which ferments with yeasf with formation of carbonic anhydride. The ether extract of the mantle contained small quantities of cholesterin fat and free fatty acids ole'ic valeric and probably also palmitic and stearic acids.228 BBSTRACTS OF CHEMICAL PAPERS. The mineral matter included in the cuticle freed from fat consisted of Silica 2.76 alumina 9.52 ferric oxide 15.81 phosphoric acid (com- bined with iron and aluminium) 12.72 calcium phosphate 3-91 calcium carbonate 49.22 and magnesium carbonate 6.03 per cent.J. W. L. Lignin. By G. LANGE fZeit. physiol. Chem. 14 217-226).-The investigation of the l i p i n of beech and ash wood previously recorded (Ahstr. 1889,1235) has in the present research been extended to that of pine wood (Pinus d i e s L.). The lignin was prepared from this by the same methods as those previously employed ; it was found to con- sist of 32 to 55 per cent. of cellulose two brown substances called lignic acid ; and as a result of fusing with alkali formic acetic and traces of higher fathy acids oxalic acid catechol prot,ocatechuic acid ammoi,ia and traces of higher bases were obtained. No succinic acid was obtained as Erd.niann stated (Annulen 138 1). The per- centage compositions of the lignic acids obtained from the three varieties of wood were as follows :- Lignic acid soluble in alcohol.C 61.475; H 5.48 Insoluble in alcohol. Beech .... . . C 59.04; H 5.37 Ash .. .. .. . . 61.61 5.47 58.83 5.15 Pine.. .. .. . . 61.28 4.95 60.51 5.22 Experiments designed to ascertain the constitution of these sub- stances were unsuccessful. W. D. H. Gum Tragacanth. By J. OGLE (Pharm. J. Trans. [3] 20 3).- A sample of Syrian tragacanth yielded moisture 18.92 soluble gum 35.94 ash 2.73 and insoluble gum 42.39 per cent. The precipitate produced in the aqueous solution by the addition of alcohol was found not to be identical with arabin and no evidence of the presence of starch could be obtained. R. R. Absence of Rotatory Power in Amine Salts. By J.A. LE BEL (BuZl. SOC. Chirn. [ 3 ] 2 305).-The order in which the substitution of radicles is effected in the NH3 molecule does not in- fluence the nature of the resultin? amine from which it follows that either the molecule alters its confipurstion according to the substitu- tion or that intramolecular migration of the substituted radicles occurs ; if then in the former case the radicles :we definitely located 8 compound of the formula CI*NHR'R2RJ should exhibit rotatory power since R' R2 and R3 cannot be in the same plane. With a view to determine t h i s experimentally the author prepared methylet.hy1- propylamine hydrochloride which he found to be devoid of rotatory power and consequently the first hypothesis is untenable. T. G. N. Propargylamine and Derivatives of Allylamine.By C. PAAL and C. HERMANN (Bey. 22 3076-3085).-I)ibromopropybamine hydrobromide C3H,Br2*NH2,HBr is obtained when an ice-cold aqueous solution of allylamine is slightly acidified with concentrated hydro- bromic acid and then treated with bromine (1 mol.) ; the yield isORGANIC CHEMISTRY. 229 quantitative. It separates from hot water in well-defined transparent crystals melts a t 164" and is only sparingly soluble in hot a,lcohol m d cold water but readily in hot water; i t is not decomposed by mode- rately concentrated sulphuric acid even when boiled therewith for half an hour. The salt ( C3H,Br2*NH.!),,2HBr,PtC14 crystallises in orange-red p1at.es and decomposes at 200° but without melting. The salt C3H,Br,*NH2,HBr,AiiC13 crystallises in dark-red needles me1 ts at 124" and is moderately casily soluble in water.Brornallylamine hydrobromide melts at 175" and not a t 223-22& as previously stated (cornpaye Paal Abstr. 1889 117). In prepa.ring bromallylaniine salts by the method previously de- scribed it is better to neutralise the aqueous distillate containing the base with a dilute mineral acid instead of collectiug the dis- tillate in excess of acid; in this way the formation of additive- compounds is avoided. Tribromopropylarnine hydrobromide CsH4Br3*NH?,HBr prepared by treating bromallylamine hydrobromide with bromine in well-cooled aqueous solution crystnllises from water in large colourless plates containing water of crystallisation ; the crystals effloresce on exposure to the air and melt a t 210" with partial decomposition.It crjstal- lises from alcoholic ether in slender needles and is moderately easily soluble in hot alcohol. A base C3H,BrzN or (C3H,Br2N) is formed when tribromopropyl- amine hydrobromide is treat,ed with alcoholic. potash ; on distilling with steam neutralising the distillate with hydrobromic avid and concentrating t.he solution the hydrobromide C3H5Br,N,HBr is ob- tained in colourless crystals. This salt melts at 214" does not combine with bromine and is readily soluble in water but only spar- ingly in alcohol. The salt ( C3H,Br2N),,2HBr,PtCI crystalliscs in golden scales and decomposes a t 2Y0° but without melting. The salt C3H,Br2N,HBr,AuCl3 forms smaJl yeilow well-defined crystals. The free base is a yellowish unstable oil ; it does not give the carbyl- amine react,ion and it yields an oily nitrosamine which is insoluble in water and dilute mineral acids.Proparg y Eami?ie C H 3*N H 2 is formed when a dibrom opropyl amine salt is heated for 14 hours a t 100" in a sealed tube with an alcoholic solution of sodium ethoxide (4 mols.). The contents of the tube are t,ransferred to a flask and hcated on the water-bath until most of the alcohol has distilled t'he distillate being collected in an alcoholic solution of oxalic acid. The acid oxalate C3H3*NH2,C2H204 separates during the process in slender colourless needles which are perfectly pure i f the above conditions are observed. It is only very sparingly soluble in boiling alcohol b u t readily in water from which i t seprates in large plates melting a t 143" ; its dilute aqueous solution gives a purple-red coloration with auric chloride. The yield of the oxalate is about 51 per cent.of the theoretical; the residue in the flask contains not inconsiderable quantities of a non-volatile base. All attempt,s to isolate propargylamine were unsuccessful ; it seems to be much more readily soluble in water and concentrated alkalis than ammonia or met'hylamine. Propargylatnine silver is precipitated when a solution of silver nitrate in excess of ammonia is added to an ammo-230 ABSTRACTS OF CEEMICAL PAPERS. niacal solution of the oxalate ; it is a colourless compouiid darkens gradually on exposure to the air and explodes when heated. The picrate C,H,*NH2,C6H,N307 prepared by precipitating an alcoholic solution of the base with picric acid ~ryat~allises in large reddish plates melts at 189" and is insoluble in ether.The 7~ydrochloride C3Hl.NH2,HC1 prepared by passing hydrogen chloride into an alco- holic solution of the base crystallises in colourless plates is readily soluble i r i water and alcohol and decomposes on exposure to light. The hydrobromide C,H,*NH,. HBr crystallises in thin colourless plates begins to soften at 130" melts a t l'il" and decomposes on exposure to light. Met h?ylpropargylamine k y d ~ i o d i d e C3H3*NHMe,HI is obtained when an alcoholic solution of propargylamine is treated with methjl iodide ; it crystallises in long colourless very hygroscopic needles melts a t 83" and decomposes on exposure to light. The free base is a yellowish volatile oil of ammoniacal odour. The ozalafe C4H,N,C2H,04 crys- tallises from dilute alcohol in colourless needles melting a t 141".Eth ylpropargy lnmine hydriodide crystallises in long needles ; propyl- prol)argylnmine hydrobromide crystallises in plates melting a t 180". Isoomylp~opargylamie is formed whm isoamyldibromoprnpylRmine hydrobromide is treated with sodium ethoxide as described above ; the contents of the tube are treated with a little water to dissolve the sodium bromide the solution saturated with potassium carbonate the supernatant alcohol separated dried over potash and distilled the distillate being collected in an alcoholic solution of oxalic acid. The oxalate C,H,*NH.C5H,,,C2H20 is thus obtained in small colourless needles melting at 204"; it crystallises from water with 1 mol. H,O.The free base is liquid. The hydrobromide C8H15N,HBr crybtallises in uacreous plates melting a t 186". F. S. K. Action of Heat on Chloral-ammonia. By A. B ~ ~ H A L and CHOAY (Compt. rend. 109 817-820).-Personne showed that when chloral-ammonia is heated at 100" it yields chloroform and formamide but the decomposit,ion is not complete. If chloral-ammonia is heated in a retort at 100" until chloroform ceases to distil orer a black viscous mass with a slightly alliaceous odour is left ; this contains ammonium chloride formamide and some other compounds. If this residue is boiled with strong alcohol the latter on cooling deposits crystals of the chloralim ide described by Pinner and Fnchs the yield being about 5 per cent.of the original chloral- a mmonia. Chloral im ide forms I on g colourless tasteless needles slightly soluble i n water more soluble in alcohol very soluble in ether. It is decomposed by a cold aqueous solution of platinic chloride with formation of chloral and ammonium platinochloride. It is riot affected by water in sealed tubes a t 150° but a t 170" decom- poses completely into chloroform and formamide which undergo partial decomposition and yield some ammonium chloride carbonic anhydride and hydrochloric and formic acids. Chloralimide in doses of 0.25 to 0.50 gram has remarkable antipyretic and analgesic pro- per tie s. If the residue in the retort either before or after extraction w i t hORUANIC OHEMISTRY. 231 alcohol is boiled with a large quantity of water the liquid deposits crystals on cooling and if these are purified by treatment with anim.11 charcoal and recrystallisntion frotn alcohol the compound C,CI,H,N,O is obtained in long colourless tasteless inodorous prisms very slightly soluble even in boiling water more soluhle in alcohol especially if heated and very soluble in ether.It melts at 21 6-217" and almost immedistely decomposes with evolution of gas. It is partially decomposed by platinic chloride and when heated with excess of acetic anhydride i t yields an acetgl-derivative of the composition C,CI,H4AcN2O2 which crystallises in long needles very soluble in acetic acid almost insoluble in water and only slightly soluble in alcohol or benzene. Tbis derivative is not affected by a neutral or acid alcoholic solution of platinic chloride; it is stable even a t a high temperature but does not melt without decomposing.The first compound C4C1?H5N2O2 is prohably didehydrotrichloro- dihydroxypiperazine formed by the condensation of 2 mols. of chloral-ammonia with elimination of 3 mols. of hydrogen chloride but this view requires further investigation. C. H. 13. The Indian Grass Oils. By F. D. DODGE ( A m e r . Chem. J. 11 4.56-469).-These are a t least five in number namely oils of citron- ella lemon-grass Indian or Turkish geranium ginger-grass and vetivert or cus-cus. They are derived from various tropical grasses of the genus Andropogon but there is some confusion as to the particular species from which the individual oils are obtained. The commercial varieties are often adulterated with kerosene ; the pure oil is a clear greenish-yellow liquid with a sharp burning taste and a strong aromatic odour. Its sp.gr. a t 16" is 0.8770 at 26.5" 0.8750. It distils betneen 200" and 240" leaving 10 per cent. of a thickoily residue having a pungent odour. It gives most of the reactions of aldehydes combining with hydrogen sulphites and with phenylhydrazine although not with ammonia; i t also reacts with acetic and benzoic chlorides and gives a mirror with an ammoniacal silver solution. Two litres of the oil were distilled in a current of steam and collected in fractions of 1100 C.C. and 4UO c.c. the residue of 500 C.C. not being readily volatile. The first fraction (1100 c.c.) was treated with a solution of sodium hydrogen sulphite the mixture being kept cool with ice and water.The liquid solidified to a white magma and the sodium hydrogen sulphite compound was then pressed between flannel and washed wit,h ether; the filtrake yielded 3.50 C.C. of residual oil. The sodium hydrogen sulphite compound was mixed with dry sodium carbonate and distilled in a current of steam; about 700 C.C. of aldehyde was thus obtained. This was shown by analyses and a vapour-density determinat,ion to have the formula CloH180 and is thus isomeric with borneol and geraniol. l'he author names it citronellic aldehyde and considers i t t o be 13- met h y 1 - 6 -is o b u t y 1 a.11 y 1 ace t a1 d e h y de C H P,S C H C H Me C H C H 0 since this formula is most in accordance with its reactions. It unites with 2 atoms of bromine and when reduced with sodium amalgam and acetic acid i t yields citronellyl alcohol C,,H,,O boiling a.t 225-230" ; this decolorises bromine solution and has a pleasaut Citronella Oil.232 ABSTRACTS OF CHEMICAL PAPERS. odour of roses.It forms compounds with phenylhydrazine with aniline and paratoluidine and with acetic acid but these products have not yet been isolated. It is dextrorotatory and when oxidised appears to yield fatty acids ; with potassium permanganate it yields a mixture of acids smelling strongly of ordinary valeric acid. When treated with phosphoric anhydride some large colourless plates (melting a t 140") were deposited and two oils formed one boiling a t 175" which was shown by analysis to be an irniiure terpene and one boiliiig above 300° which had a pleasant odour resembling the high- boiling fractions of citronella oil.The 350 C.C. filtered from the sodium hydrogen sulphite compounds yielded (1.) 75 c.c of a light oil boiling a t 177" and having a pleasant citrene-like odour ; this was analysed and its vapour-density deter- mined the results indicating that it was an impure terpene; (2.) 120 C.C. of a thicker oil of rose-like odour boiling a t 222-224" and of sp. gr. = 0.8741 at 2G*5" which appeared to be citronellyl alcohol ; (3.) 100 C.C. boiling above 240" dark brown viscid and having a peculiar odour. The residual 500 C.C. of the original oil not readily volatile in steam was treated with sodium hydrogen sulphite and yielded about 10 C.C. of citronellic aldehyde and a residual 475 c.c.which when distilled behaved like the residue from the other sulphite precipitate but yields a much larger amount of high-boiling products which oxidise readi]~ and are difficult to treat. Citronella oil therefore contains citronellic aldehyde and alcohol together with a terpene and oils boiling above 240". Derivatives of Tetrachlorodiacetyl and of Tetrachloracetone. By S. LEVY F. C. WITTE and A. CURCHOD ( A w d e n 254,83-114; compare Abstr. 1889,1160 and 1136).-The compound C,,H,,Cl,N,O prepared by boiling tetrachlorodiacetyl (Abstr. 1889 390) wit,h excess of phenylhgdrazine in alcoholic solution combiries with phenyl- hydrazine when warmed therewith with evolution of ammonia; i t is decomposed by alcoholic potash with liberation of aniline and when treated with fumingnitric acid i n sulphiiric acid solution i t is converted into a yellow compound which is precipitated on adding water.separates in crystals when tetrach!orodiacetyl (1 mol.) is treated with orthophenyl- enediamine (1 mol.) in hot aqueous solution. It crystallises from alcohol in small colourless nacreous plates and from benzene in large well-defined triclinic plates u b c = 0.8198 1 0.9698 ; a = 92" 4' p = 121" 56' y = 85" 22' ; it melts at 177" and distils at a high temperature with partial decomposition. It is readily soluble in hot chloroform alcohol and benzene but only sparingly in the cold solvents and in ether and is insoluble in water ; it dissolves in concen- trated sulphuric acid with a yellow coloration The compound C2H,(NH.CHCl.CO.CO.CHCI,) can be obtained by gradually adding an aqueous solution of tetrach1orodiacet)pl to an ice-cold aqueous solution of ethylenediamirle but it is best prepared by dissolving the t w o substances in 95 per cent.alcohol The study of these oils is to be continued. C. F. B. N:F-CHCI C6H4<N :C*CHCI,' Tetrach lorodimet? y lquinoxalh2e,OROXNlC CHEMISTRY. 233 and warming until the colour of the solution changes to red. It crystallises f'roni dilute alcohol in colourless slender needles melts a t 222-223" with decomposition and is readily soluble in alcoliol ether chloroform and benzene but only sparingly in light petroleum and almost insoluble in water. Trichlorcmidod;acstyl CHCl:.CO.CO*C HCl*NH prepared by gradu- ally adding ammonia (3-4 c.c.) to a dilute alcoholic soiution of tetra- chlorodiacetyl(2 grams) and heating the mixr;urc to boiling crystallises from benzene in colourless needles melts a t 127" and is readily soluble in alcohol and ether but only moderately in water or benzene and very sparingly in light petroleum.It has feeble basic properties and is decomposed by soda with evolution of ammonia. When treateti with hydrochloric acid it is converted into two substances one of which crystalliscs in large prisms melting a t l57" the other in small colourless needles of lower melting point. TetraclLEo~oiliacet?/~cet~ ldicyadit$r. in C H C=l,*C (OH) (CN ) *C (OH) (CN ) CRC 12. is formed when tetrachlorodiacetyl is heated with excess of concen- trated hydrocyariic acid at 30-40' for 4 to 5 hours.The product is cx- tracted with ether and repeatedly treated with light petroleum to free it from the monocyanhydrin. It separates from a mixture of ether and l i g h t petroleum in spherical aggregates sinters together a t about 110" and melts at about 135-137" with decomposition. It is readily soluble in water ether and alcohol but only sparingly i l l carbon bisulphide chloroform arid benzene and insoluble in light petroleum. It is decomposed when warmed with water a t a tem- perature below 100". The dlacetyl-derivative C,,H,Cl,N,O preparetl by heating the cyanhydrin with acetic chloi-ide crystallises froni dilute alcohol in colourless needles melts at 1 6 3 O decomposes at a higher temperature and is readily soluble iu ether alcohol and chloroform but only spdringly in bemene and boiling water autl insoluble in light petroleuin.crystallises from benzene in which it is readily soluble in co1uurle.-s plates melts at 110-111" and decomposes a t about 153". r i 1 he mo?iocyanhydri?i CHCl,*C(OH)(CN).CO*CHCl (see above) CO-7 (OH)*CHC12 Tetrach lorodiinethy Etartarimide NH<CO.C (OH) .(-H(J2' is Oh- tained together with a small quantity of a ;ellowish acid when the dicyanhydrin (2 grams) is heated a t 110" for two hour with 35 per cent. hydrochloric acid (15 c.c.). It separates from n mixture of benzene and ether in dendritic crusts melts a t 239-240" and is readily soluble in alcohol ether and hot water but almost insolul,le in chloroform benzene and light petroleum. l'he ti.iacetyZ-dei.ivati\ e C,,H,,Cl,N O crptalliseu from dilute alcohol in small colourless prisms or needles melts at 176-177" with decomposition aiid is readily soluble in alcohol and ether but only sparingly in hot arid insoluble in cold water.l't:tradhlorudinzetIiyItartara )wide C H C 12. C (0 H) ( C 0 N H,). C( 0 H) ( C 0 N H 2 ) * J H C12 VOL LTIII. T232 ABSTRACTS OF CHEMICAL PAPERS. is formed when concentrated sulphuric acid is gradually added to a concentrated glacial acetic acid solution of t h e dicyanbydrin and the mixture warmed gently until the crystals which separate from the solution have redissolved. It crystallises from boiling chloroform in slender colourless needles melts at 183' and is readily soluble in water alcohol and ether but only very sparingly in boiling chlom- form and insoluble in light petroleuiri.It is converted into the imide by 35 per cent. hyd-rochloric acid a t 110" or when warmed with sulphuric acid i n glacial acetic acid solution. Tetrachlorhydroxyisobutyramide (m. p. 156") i s best prepared from tetrachloracetonecpnhydriu (Abstr. 1889 1136) by dissolving the latter i n glacial acetic acid adding concentrated sulphuric acid and heating t o boiling for a few minutes. I t crystallises from etlier in four-sided pyramids is readily soluble in alcohol and moderatel!. easily in benzene b u t only sparingly in chloroform and insoluble in light petroleurn. The compound C4H,C13N02 probably the amide of trichloropropyl- enecxidecai boxylic acid is obtained when the preceding compound is treated with sodium carbonate in the cold. It crystallises in needles mclts at l Z " and is readily solnble in ether alcohol chloroform and ben7ene moderately easily i n carbon bisulpbide and sparingly in light petroleuin.TehachlorhydToq isobu tlyric acid 0 Ha C ( CH Cl,) !.C 0 0 H prepared by heating the amide a t 110-120" with hydrochloric acid of sp. gr. 1.16 crystallises from light petroleum in needles melts at 69-71" and is readily soluble in water ether alcohol chlo~oform and benzene but only sparingly in carbon bisulphide and light petroleum. The potassium salt C4H3C140.,K crystallises from water in transparent prisms and is very readily soluble in water but only sparingly in alcohol ; i t is decomposed by hot water. By V. ACCER and A. B ~ ~ H A L ( B u l l . Sor. Chiin. [3] 2 144-145).-To pre- pare acetic chloride sulphur (1 mol.) or sulphur dichloride (1 mol.) is placed in a fiask with glacial acetic acid (2 mols.) and chlorine is passed into the mixture cooled by ice and salt until no fulthvr absorption occurs ; after distillation of the resulting product a t 60" and agitation of t h e distillate with mercury or powdered copper to remove a sulphur compound subsequent fractionation jieltis a pure product; 600 grams of acetic acid gave 500 grams of acetic chloride. Chlorscetic acid is obtained under conditions similar to those above except that the mixture of sulphur and acetic acid is to be boiled chloracetic acid is obtained in a very pure condition only traces of acetic chloride and of acetic. anhydride being produced ; 800 grams of acetic acid yielded after 12 hours' chlorination 1000 grams of the monochlorinated derivative.T. G. N. F. S. K. Preparation of Acetic Chloride and Chloracetic Acid. Action of Triethylamine on Ethyl a-Bromobutyrate and Ethyl a.Bromopropionate. By M. E. DuvrrmEn (Bull. SOC. Chirn. [YJ 2 139-142; compare Abstr. 1888 !249).-'I'he action of tri-OROASIC CHEhl ISTRT. 233 ethylamine (3 mols.) on ethyl a-bromobntyrate (1 mol.) at 100" yielded a considerable amount of a-hydroxybutyric acid and this was accompanied by a sm2ll quantity of butyric and crotonic acids whilst traces of tetrethylammonium hydroxide were produced. The substitution of ethyl a-bromopropionate for ethyl a-bromo- butyrate determines the production of much lactic acid and of small quantities of tetrethylammonium hydroxide and of betaine (1 per cent.) in which latter respect the bromo-derivative differs from the corresponding chloro-compound from which under similar conditions Bruhl could not obtain betiine (this Journal 1576 i 699).T. G. N. Preparation of Alkyl Salts of p-Ketonic Acids. B y J. HAMONET (Bull. SOC. Claim. [3] 2 334-337; compare Abstr. 1888 235).-The product of the action on a normal acid chloride (1 mol.) of sublimed ferric chloride (2 mols.) is poured into cold absolute alcohol and when the reaction is completed the upper layer of liquid which contains the salt of the (%ketonic acid is dried and frac- tionated. Propionic chloride yields by this process ethyl a-propiopropionate a colourless liquid of sp. gr. 0.9987 a t 0" boiling at 196-197". Butyric chloride and heptoic chloride when similarly treated yield respectively ethyl a-butyrobutyrate boiling a t 217 -219' and e t h y l a-hpptohepfoate boiling a t 290-292".As ethyl ,phntyrobutyrate when treated by Ceresole's method yields but yrobutyric acid whose barium salt decomposes on warming into a carbonate and butyrone i t is to be regarded as a P-ketonate. Jsobutyric acid yielded by the author's method valerone and ethyl caZrrocaZPrate boiling at 238-2134" and of sp. gr. 0.9492 at 0". From a mixture of propionic and butyric chlorides the author ob- tained by this method ethyl propyl ketone boiling a t 1-22' and ethyl a-p?*opiobzityrcrte boiliilg at 207-209" and of sp. gr. 0.9884 a t 0". The theory of the reactions is discussed. T. G. N. Ethylenelactic Acid from Flesh Extract.By E. KLINENRO ( R e r . 22 3182-3183).-The author corrects the statement of Sieg- fried ( B e y . . 22 2711) that he (Klimenko) was unable to isolate an amorphous zinc salt from lactic acid obtained from flesh extract. F. S. I<. Alkyl Hydrogen Oxalates Dichloroglycollates and Chlor- oxalates Tetralkyl Oxalates. By R. ANSCHGTZ (ArtmzZen 254 1-42 ; compare Abstr. 1886 785 and 101 l).-The alkyl hydrogen oxa.lates gradually undergo spontaneous decoiuposi tion into the neutisal s ilt and oxalic acid ; they decompose potassium acetate i n alcoholic solution forming alkyl potassium oxalates. MethyZ phenyloxamate NHPh*CO.CC;OPJe prepared by heating methyl oxalate with aniline crystallises from alcohol in whic-h i t is readily soluble in large yellowish plates and from light petroleum in small colourless needles melting at 114'.'l'he corrcispoilding p~opyl salt NHPh-COCOOPr crystnllises from alcohol i n c,,louI less r 2236 ABSTRACTS OF CHEMICAL PAPERS. needles melts a t 92" and is readily soluble in alcohol but only sparingly in light petroleum. The isopropyl salt crystallises from light petroleum in long white silky needles and melts a t 52". The i s o t u f y l salt forms mall colourless plates melts at 65". and is readily soluble i n alcohol. The an2y1 salt crystallises from light petroleum in needles and m e h - a t 60". Bimethyl dichloroglycollate OMe-CCl,*COOMe prepared by heat iiig methyl oxalate with phoaphoric chloride f o r 1 2 to 18 hours a t 130 -135" and fractionating the crude product under reduced pres- sure is a colouraess liquid boiling at 179-181" (at 72" about 12 mni.).Dli.cobutyZ dicldoroglycollate C,H7g0.CC1z-COOC,H7 is a colourless liquid boiling a t 128" {about 14 mm.). The alkyl cliloroxalates can be obtained by distilling the dislkyl (1 i chlorogl y collat es under the ordinary pressure. Methyl chloroxdlate COCkCOMe is best prepared by heating di- methyl dichloroglycollate at 200-215" for 40 hours ; i t is a colourless liquid boiling at 118-120". The corresponding ethyl salt COCl-COEt boils a t 135-136" (at 30" about 10 mm.) the normal propyl salt a t 153-154" (at 50" about 12 mm.) the i s o h d y l salt a t 163-165" (at S2" about 10 mm.) and the amyl salt a t 183-185" (at 68" about 10 mm.). Tetralkyl-derivatives of oxalie acid can be obtained by treating the dialkyl dichloroglycollates with .sodium compounds of alcohols in alcoholic ethereal solution.Tetramethyl oxaZate C(OMe)&OOMe is acoloudess liquid boiling at 75-76" (ahout 12 mm.). The corresponding ethyZ salt C(OEt),.COOEt boils at 98" (about 12 mm.) the normal propyl salt at 256-257" (at 12!)-1W0 about 12 nim.) the isobutylsalt a t 146" (about 10 mm.) and the amyl salt at 190" (about 10 mm.). Dimethyl diethyl oxalate OMe*C( OEt),*COOMe is formed when d imetliyl dichloroglycollate is treated with sodium ethoxide in ethereal solution ; i t boils at 90-92" (about 13 mm.). If the reaction is carried out in alcoholic ethereal solution a liquid boiling a t 945-965" (about 12 mm.) probably methjl triethyl oxalate is obtained. When dimdhyl dicblorog€ycollate is heahed with oxalic acid at about 50" carbonic oxide carbonic anhydride and hydrogen chloride are evolved and tlie residue consists of methyl oxalate; other di- alkyl dichloroglycollstes could probably be converted into the corre- sponding alkyl oxalate in like manner.When teti ameth.yl oxalate is treated with phosphoric chloride it is converted into methy 1 oxalate with evolution of methyl chloride ; tetrethyl oxalate yields ethjl oxalate u d e r the same conditions. F. S. K. Constitution of Succinic Chloride. By W. 0. EMERY (Bey. 22 3184- ilY6). - Met hgl snccinate prepared by treating succinic chloride with sodium methoxide in ethereal solution is identical with the compound obtained by heating silver succinate with methyl iodide at 100° ; i t melts tit 19" and boik at 8u" (10-11 mm.).F. S. K.ORGA4hrIC CHEYISTRY. 2.3 7 Substituted Succinic Acids. By C. A. BISCHOFF (Be).. 22 31 79-3180) .-The author has hydrolysed a number of ehhereal s Lit's of alkyl- and beczyl-isobu tenylti*icarboxylic acids ; two isomeric acids were obtained in every case. A large number of ethereal salts of other unsaturated tricarboxylic acids will be examined in this direc- tion. F. S. K. Synthesis of Aconitic Acid from Acetylenedicarboxylic Acid. By J. M. LOVBN (Bey. 22 3053-3056).-When dibromo- succinic acid is boiled for a long time with a slight excess of alcoholic yotssh it is converted into oxalic and nconitic acids. Acetylenedicarboxyiic acid under the same conditions gives the same products so that the bromosuccinic acid is first converted into acetylenedicarboxylic acid ; the yield of aconitic acid is 30 per cent,.o r more of the acetylenedicarboxylic acid employed. I?. 8. K. Oxidation of Ketones by Potassium Permanganate in Alkaline Solution. By G. GLUCICSMANN (nlonatsh. 10 7 70-782) .- Potassium perrnanganate has no action on pinncoline in cold or warm neutral solution; but when the ketone (PO parts) suspended in water is gradiinlly treated with a mixture of potassium perniangannte (63 parts) and sodium hydroxide (20 parts) dissolved in water ( 2 litres) oxidation takes place the products being the until now unknown trhnethyZpyruuic acid CGH,,,O and a little trimethyl- acetic! acid. The new acid crystallises in colourless irregular-pointed prisms having a peculiar acid odour is sparingly soluble in cold hut readily soluble in hot water and in ether is fairly soluble in benzene cilrbor1 bisulphide chloroform and carbon tetrachloride is volatile in a current of steam melts a t 90-91" and has the constitu- tion CMe.3.COCOOH. With phenylhydrazine trirnet,hylpyruvic acid forms a compound C,2H,6NL02 which crystdlises from dilute alcohol in long pale- yellow needles and melts a t 157-158" with evolution of carbonic anhydride and formation of aniline. On heating with a 33 per cent. solution of hydrochloric acid trimethylpyruvic actd is not Yegenerated but an aldehyde probably that of trimetliylacetic acid is the product. The calcium salt of trimethylpyruvic acid (C6H903)rCa + 3H,O is very soluble in water; the sodium salt is anhydrous and crystallises in long colourless rhombic plates ; the silver salt which is also anhydrous in gleaming scales.Trimethylpyruvic acid is converted into trimethylacetic acid when oxidised with silver oxide or with potassium dichromate ant1 sulphuric acid. On reduction with eight times its weight of 4 per cent. sodium amnlgam it is converted into trimethyleth~lidenelactil ~ c d CMe.3*CH(OH).COOH in nearly theoretical quantity. This acid forms colourless probably monosymmetric crystals (u b c = 1.45 1 1.10 qprox.) melts a t 87-88° is readily soluble in water and in ether and gives copper silver and zinc salts which are not very characteristic. Thc oxidation of pinacoline to trimethylpyruvic acid is not in238 ABSTRACTS OF CHEMICAL PAPERS. accordance with Popow's rule for the oxidation of ketones and bhe author to explain the reaction supposes that in the operatmion an intermediat,e condensation-product CMe3.CO*C tl :CMe*CMe is formed with elimination of 1 niol.of water and that this condensation-pro- duct on oxidation with 3 atoms of oxygen is converted into tri- methylpyruvic acid aad pinacoline the latter again undergoing thc condensation and oxidation processes. The author has also succeeded in obtaining pyruvic acid by the oxidation of acetone with perniangnnste i n alkaline solution and suggests tha,t the formation of trimethylp~ruvic acid from pinacoline may perhaps be a typical reaction. G. T. 31. Isomeride of Tricarballylic Acid. By E. GUINOCHET (Compt. q-end. 109 906-908).-The action of sodium amalgam on the tri- bromotricarballylic acid formed by the action of bromine on aconit,ic acid yields an isomeride of tricarballylic acid.It crystallises in con- fused almost opaque macled prisms and melts at 181" ; carballylic acid melts at 15$" and crystallises in large perfectly transparent prisms. It is only slightly soluble in water whilst carballylic acid is very soluble. Its barium salt is cr.ystallisable anhydrous and some- what soluble in water; the calcium salt crystallises with 12 mols. H?O in long hard trmsparent efflorescent prisms. C. H. B. Fucusol. By K. BIELER and B. TOLLENS (Bey. 22 3062-3063). Constitution of the Aromatic Nucleus. By S. A. SWORN (€'Ail. Mag. [ 5 ] 28 4 0 2 4 1 5 and 443-451).-Arguments are brought forward in favour of Thomsen's octahedral formula for benzene (Abstr. 1887 362) these being chiefly based on the evidence of direct linkage between symmetrically disposed carbon-atoms (para-linkage).In some cases arguments derived from the study of pyridine-derivatives are applied by analogy to the derivatives of benzene the author considering that this is justified by the result of recent researches. It is first shown that the central nucleus of ant)hra- cene is truly aromatic and that in t h i s nucleus the carbon-atoms are directly linked to one another. The abnormally low molecular volume and absorption of ultra-violet rays by anthracene the oxida- tion of anthracene to a substance of the yuinone type and the oxidation of acridine t'o a quinoline-derivative are all advanced in favour of the above views.The diketonic nature of quiiione and its behaviour on reduction are best explained on the assumption of a para-linkage the author being of opinion that when a para-linkage is broken tbe nmdeus opens out into a hexagonal ring and the remaining para- linkages are se-c-ered with the formation of olefinic bonds this view being supported by Baeyer's work on the additive compounds of tere- phthalic acid. The fwmulae of Meyer and Ladenburg represent benzene a s containing para-linkages but the optically active conine would have no asymmetric carbon-atom in the symbol derived from these formule a requirement which is however satisfied by that of 'l'homsen. In the same \my symbols for naphthalene and fluorent -A claim for priority. (Compare Illaquenne this vol. p.33.)ORGANlC CHENISTRT. 239 cannot be satisfactorily derived from the formulae of Meyer and Ladenburg but can be readily deduced from the Tbomsen formula. An objection to the Thomsen formula which the author himself raises is tlhat were the configuration of the benzene-molecule as a whole oct,ahedral we should expect the crystals of benzene t o belong to the regular system whereas they are rhombic. It is considered therefore that the above formula requires still further deveiopment before it caii be brought into accordance with all the facts. H. C. Paracyanobeneyl Chloride and its Derivatives. By W. MELLINGHOFF (Ber. 22 3207-321f).-Paracyunobenzl/l chloride CN*C6H,*CHzC1 is obtained in a similar manner to orthocyanobenzyl chloride (Gabriel and Otto Abstr. 1887 lo%) b,y passing chlorine into paracyanotolnene nearly at its boiling point until the weight has increased 30 per cent.allowing to cool and recrystnllising the solid portion from alcohol. It forms colourless well-developed rhomblc prisms a b c = 0.7495 1 0.4314 melts a t 79*5" boils at 263" (uncorr.) and is sparingly soluble in hot water more easily in alcohol ether chloroform and benzene. Paracyitnobenxyl cyanide CN*C6EL4.CH2*CN is formed when the above compound is treated with potassium cyanide. It crystallises from alcohol in needles melts a t loo" boils above 360" and is slightly soluble i n hot water more readily in alcohol ether and chloroform. It is the dinitrile of homoterephthalic acid into which it may be con- verted in the manner shown below. There are seven possible inter- mediate products all of which have been prepared.Paracyanophetzylacetamide CN*C6H4.CHz-COXHP is prepared by warming the dry powdered dinitrile with 38 per cent. hydrochloric acid (15 parts) until effervescence commences. It separates from dilute alcohol in crystals which melt at 196.5 (uncorr.) and is soluble in hot water and alcohol. In addition to this compound para- cyanophenylacetic acid and a substance of unknown consfitution CnH,,N are also formed. w- ChZoroparatoZuamicle CONH2*CGH4*CHzCI is obtained by allowing paxacyanobenzyl chloride to remain with concen trahed sulphuric acid in the cold for 12 hours. It is a white crystalline precipitate melts at 173" (uncorr.) and is soluble in the common solvents. w-Cyarzopal.atoluat,Licle CO NH2.C6H4.CH2*CN is formed by heating the foi egoing compound with potassium cyanide.It crystallises from alcohol in small colourless plates melts a t 182" (uncorr.) and is readily distinguished from the isomeric paracyanophenylacet,amide by its appearance. Paracy anophen y lacetic acid CN* C,j€€:1*CH2* C 0 0 H is prepared by heating paracyariobenzyl cyanide with fuming hydrocliloric acid until the temperature has reached 105" and then almost neutralising with ammonia. It forms prismatic crystals melting a t 152' (uncorr.) and forms an emerald-green copper salt. w-Chloroparatoluic acid COOH*C6H4*CH2C1 is formed when w-chloro- paratoluamide is heated with 25 times its weight of officinal hydro- chloric acid for la hours. It crystallises from alcohol in microscopic210 ABSTRACTS OF CHEBI[CAL PAPERS.needles melts a t 199" (uncorr.) and yields a light-brown precipitate with solutions of copper salts. w-Cyanoparafolziic acid COOE€*CsH4.CH,*CN is formed from the compound just described by acting on its potassium salt with potassium cyanide. I t melts a t 201" (uncorr.) and is readily so- luble in hot water alcohol and ether less so in cold water. Homoterephthalamide C:ONH2*C~H,*CH,.CONH2.-To prepare this substance paracyanobenzyl cyanide is dissolved in 8 parts of cold concentrated sulphnric acid and allowed t o remain for 12 hours; water is then added and the acid neutrdised with ammonia. The amide forms a white precipitiite or nodules of crystals and melts a t 235" (uncorr.). It is very sparingly soluble in indifferent sol- \Tents but dissolves readily in concentrated hydroch:oric acid. Womoterephthalamic acid COOH*C,H,.CH,*CONB is obtained from w-cyanoparatoluic acid by the action of cold Concentrated sulphuric acid and may be purified by crystallisation from alcohol in which i t is sparingly soluble.It melts at 261" (uncorr.) and forms a light- blue copper salt. Homoterepht ha Zisoamic acid c ON H2*C6H,C H2*COOH is formed in like manner to the foregoing from paracyanophenylacetic acid. It melts at 229" (uncorr.) and is distinguished from its isomeride by greater solubilit'y in alcohol and by forming a malachite-green copper salt. HomoterephthaZ;c acid COOH*C6H**CH,*COOH is best obtained from the diarnide by heating it for 3-4 hours with 20 parts of 25 per cent. hSdrochloric acid and crystallising the product from dilute alcohol Jt dissolves in 7 parts of alcohol a t 30" and in 100 parts of water a t 50" but is almost insoluble in ether and benzene.It melts a t 285-288" (uncorr.) and gives with copper salts a verdigris- like precipitate. The corn pounds described as homoterephthalic acid by Paternb (Gazzetta 7 361) and as insolinic acid by Hofmann (AnnaZen 97 177) probably consist of impure terephthalic acid. H. G. C. Chloraniso'ils. By L. HUGOUWENQ (BUZZ. Xoc. Chim. [3] 2 273- 2@0).-Chlorine is passed into cold anisoi'l (432 grams) in the dark until the weight increases t o 680 grams ; after washing and subsequent steam distillation the portion which fractionates a t 230-237.5" is retained. This liquid resisted crystallisation and not until it had been exposed to the cold of a winter's night were acicular crystals obtained which after removal of the trichlorinnted derivative by pressure were recrystallised from alcohol.As thus obtained dichlor- anisoil melts a t 27-28" but the presence of traces cjf trichloranisoil reduces the melting point to 16". Prom the alcoholic mother liquor large orthorhombic prisms of dichloranisoil separate having the axial ratios a b c = 0.6556 1 0.5231. The substance boils a t 232-239" under a pressure of 743.45 mm. (corr.) ; i t is soluble in alcohol ether benzene and chloroform but is insoluble in water. When heated a t 145" in sealed tubes with hydriodic acid (sp. gr. la?) methyl iodide and dichlorophenol (1 2 4) were obtained. Dichloyonitroanisoi'l is obtained by the action of fuming nitric acidORGAXIC CHEJlISTRY.241 on dichloranisoil ; it crystallises from alcohol in pale yellcwish-green needles melting a t 43.5". Trzchloranisoi'l is formed by passing chlorine into cold aniso'il until the hydrogen chloride evolved and absorbed by cold water equals the weight of aniso'il employed ; the product is washed dis- solved in boiling alcohol and recrgstallised when needles are ob tained which melt a t 60-5" are soluble in benzene chloroform and carbon bisulphide and distil at 240 under a pressure of 738.2 mm. (corr.). When heated a t 180" in sealed tubes with concentrated hydrochloric acid or a t 14O-15OJ with hjdriodic acid trichlorophenol [l 2 4 61 is produced. Trichloronitroanisoi'l [OMe C1 NO = 1 2 4 6 31 forming long nacreous needles melting at 48-50" results from the action of a mixture of sulphuric and fuming nitric acids on the preceding derivative.A trichlorodinitroanisofL [l 2 4 6 3 51 cr~ystallising in prisms which melt a t 90-91" is farmed by the action of nitric and srilphuric acids on trichloroaniso'il at 70-75". Tetrachloranisciil results from the action of chlorine a t 70" on anisojil containing 5 to 6 per cent. of iodine; some pentachloraniso'il is also produced and may be separated by recrystallisation from hot alcohol. Tetrachloraniso'il cr3;stallises in slender needles which are soluble in alcohol ether chloroform benzene and carbon bisulphide ; it is sublimable and boils with partial decomposition a t 278" under a pressure of 745.85 mm.(corr.). When hydrolysed by hydrochloric acid a t 175" or by hydriodic acid a t 150" orthotetrachlorophenol hitherto undescribed is produced ; this substance the author is studying. Pentachlorani#oil crystallises in long hard crystals melts a t 107-108" and is slightly soluble in cold alcohol easily in benzene carbon bisulphide chloroform and boiling alcohol. Under a pressure oC 745.45 mtn. it boils a t 289' with partial decomposition. When heated with hydriodic acid a t 186" it yields pentachlorophenol. T. G. N. Derivatives of Symmetrical. Dinitroresorcinol. By P. KEHR- MANN ( J . pr. Chma. [ 21 40 49$-497).-Chlorodi~iitror~sorcillol [(OH) C1 (NO?) = 1 3 2 4 61 is obtained by suspending finely powdered dinitroresorcinol i n ether and passing chlorine diluted with carbonic anhydride through the liquid.It forms long yellow vitreous prisms melting at 181-182" and soluble in most solvents. The neutral potassium salt was obtained. The chlorodiamidoresorcinol stannoch loride is obtained by reducing the nitro-compound with excess of stannous chloride b u t attempts to isolate the hydrochloride or base result in the formation of ch7or- n?nidohydrox~jquinonrinzide [0 CI OH NH NH2 = 1 2 3 4 61 which is best obtained by treating the stannochloride with ferric chloride in aqueous solution ; it crystallises in violet needles and is converted into chlorodihydroxTquinone (next abstract) by dilute potash solution. A. G. B. Derivatives of Metadichloroquinone. By F. KEHRNANN and W. TIESLER (J. pr. Chem. [2 J 40 480-4!34).-Metadichloroquinone242 ABSTRACTS OH' OHEhlICAL PAPERS.is best prepared as follows :-Commei*cial trichlorophenol(200 grams) is dissolved in sufficient glacial acetic acid at 40-50" and is mixed with a solution of chromic anhydride (120 grams) in sufficient water to dissolve i t and twice that volume of glacial acetic acid. After the mixture has remained a t 30-40" for a quarter of an hour much water is added ; this precipitates the metadichloro- quinone in yellow needles ; it melts a t 121". Metadichloroquinol CsH2C12(0H)2 crystallises in flat long leaflets melting a t 164". The diacetyl-derioative forms slender needles melting at 98" and soluble in the usual solvents. When alcoholic potash (10 per cent.) is dropped into an alcoholic solution of metadichloroquinone the liquid becomes first green and then brownish-red but as soon as hhe potash is in excess the coloui* begins to fade; red crystals of a potassium salt are then deposited the yield being 5-6 per cent.of the quinone. Chlo~odiimidoquinoZ [(N.E3)z (OK) C1 = 1 4 2 5 61 is pre- pared by dropping strong ammonia into a saturated (at 50-60") solu- tion of metadichloroquinone not more animonia than one quarter of the volume of the quinone solution beiiig added in all. After half an hour crystals separate which are washed with alcohol and purified by crystallisation from glacial acetic acid ; they amount to 20-2.5 per cent. of the quinone. Chlorodiimidoquinol forms lustrous bronze- coloured t h i n leafy crystals which sublime without melting but with partial carbonisation at 258-260"; it is insoluble in cold water and alcohol but dissolves partially in hot alcohol with a violet colour ; i t dissolves in strong hydrochloric and sulphuric acid with a blue colour and is precipitated on dilution.When heated with dilute acids it loses nitrogen as ammonia and is converted into a chlorodihydroxyyuinone (see below). When heated with potash solu- tion i t is converted into the red potassiuwz salt obtained above; when this is dissolved in water and a slight excess of strong hydro- chloric acid added large yellow-red leafy crystals of chloropara- rlihydroxyquinone C6HC1O2(OH) gradually separate ; this quinone melts at 240". The ammonizbm salt forms an insoluble brownish- red crystalline precipitate when ammonium chloride is added to the solution of the potassium salt; the salts of most heavy metals give insoluble brown precipitates under the same circumstaLces ; the strontium and silver salts are described.When chlorine diluted with carbonic anhydride is passed througll a dilute acid solution of chloroparadihydroxyquinone cbloranilic acid is obtained ; if bromine be used bromochloranilic acid is formed. Iodochlorodihydroxyquinone [02 (OH) I C1 = 1 4 2 5 3 61 is obtained as a red crystalline powder when a strongly acid solution of the chlorodihydroxyquinone is dropped into the calcu- lated mixture of potassium iodide and iodate ; it is insoluble in cold water and is decomposed by hot water ; it decomposes a t 275" ; hot dilute hydrochloric acid converts it into chloranilic acid with sepa ration of iodine.Nitroso- and nitro-chloranilic acids are obtained respectively when chloroparadihy droxyquinone is treated with nitrous and nitric acids respectively. These acids are still under investigation.OHQANIC CHEMISTRY. 213 Chloi-oyaradiaminoquinol hydrochloride obtained by digesbing chloro- diimidoquinol with stannous chloride and hydrochloric acid crjstal- lises in large colourless rhomloic octahedra or prisms very soluble iu water. The free base has not been obtained. Tetracetylparadiamidochloroquinol [ (OAc) (NHAc)? C1 = 1 4 2 5 61 is obtained by heating the above hydrochloride with acetic anhydride and sodium acetate for half an hour and adding water ; it crystallises from hot glacial acetic acid in lustrous white four-sided tables melting at 255" and sparingly soluble.Chloroparadiacetamidoquinone [O (NHAc)~ C1= 1 4 2 5 61 is formed when the above tetracetyl-compound is dissolved in dilute alkali acidified and ferric chloride added in slight excess. It crystallises in brilliant golden needles melts a t 225--LZb" and is soluble in hot alcohol and glacial acetic acid. When suspended in ether and treated with hydrochloric acid and stannous chloride chloro~aradiacetn?nidop z~inol is formed ; this crystallises in colourless prisms melting a t about 30O0 and soluble in hot water alcohol and ether. A discussion of the constitution of some of the foregoing com- pounds concludes the paper. A. C;. B. Desmotropy in Phenols. By J. HERZTG and S. ZEISEL (Monatslz. 10 735 -769 ; compare Abstr.1888 826 ; and 1889,247 and 966) .- On adding bromine to tetrethylphloroglucinol in molecular propor- tion half the halogen is converted into hydrogen bromide and a mixture of two isomeric bromotetrethylphloroglucinols is formed. In this operation it is necessary to brominate a solution in absolute alco- hol the presence of water in the alcohol leading to the formation of dibromotetrethylphloroglucinol. The two isomeric monobrornotetr- et hylphloroglucinl 1s are best separated by fractional crystallisation from petroleum (b. p. 60-90') in which the a-compound is least soluble and from which it crystallises in thick quadratic plates a b c = 1.0029 1 1.3749) melting at 85-83". The /+compound is more soluble and crystallises in needles melting a t 115-118". If the a-compound is dissolved in cold potash soda or ammonia and after remaining some time precipitated wltti hydrochloric acid i t IS converted into the /%compound ; the pure P-compound is however not always the most stable form for when a solution in acetic acid is pre- cipitated with water a mixture of the a- and /$compounds is obtained.If the acetic acid solution is boiled the coilversion of the /3- into the a-compound takes place completely and the same result is produced on boiling a solution of the @-compound in benzene or some other solvent without chemical action on it. Sodium /3-bromotetrethyl- phloroglucinol C14H20Br03Na is obtained in long colourless crystals readily soluble i n water on dissolving the F-compound in a suall excess of pure caustic soda ; the potassium salt much resembles i t ; the silver salt is crystalline and soluble in water and in alcohol.The a-compound furnishes the same salts. On heating with acetic anhgdride both a- and P-bromot'etrethyl- phloroglucinol gave the same monacetate CI4H,,BrO3Ac which c r j s- tallises in monoclinic prisms (a b c = 1.7 1 x) and melts at214 ABSTRACTS OE' CHEMICAL PAPERS. 66-68'. When @-potassium bromotetrethylphlorogl ricinol is heated with an excess of ethyl iodide for three hours ethyliodotetrethyl- phloroglucinol crystallising from petroleum in asymmetric plates ( a b c = 1 1.0961 0.8947) and melting at 51-53" is formed. Both a- and p-bromotetrethylphloroglucinol give the same tetrethyl- phloroglucinol (m. p. 210-212") on reduction with zinc aud the same dibrornide on bromination in dilute alcoholic solution.The dibromide melts a t 80-82' crystallises from dilute alcohol in flat needles of con- siderable length contains no hydroxyl-group and gives on reduction with zinc and acetic acid tetrethylphloroglucinol (m. p. 209-211°) and on heating with acetic anhydride the above described monacetate. The general beh aviour of the isomeric bromotetrethylp hloro- glucinols leads the authors to attribute the constitution [0 Et2 0 E t 0 H,Rr = 1 2 3 4 5 61 to the a-compound and [OH Et 0 Et 0 Br = 1 2 3 4 5 61 to the P-ccmpound ; the dibromide produced from both being formed by isomeric change and represented by the constitution [ O E h 0 B1-8 0 Et2 = 1 2 3 :4 5 61. (3.T. &I. Constitution of Asarone By J. F. ETKMAN (Rer. 22 3172- 31 76).-The vapour- density of asarone the crystalline constituent of asarum oil determined under reduced pressure was found to be 102.9; an optical examination of a mixture of asarone and Pafrole showed that asarone contains a propenyl- and not an allgl-group. The constitution of asarone is therefore [(OMe)3 C,H = 1 2 5 41 where C3H5 = CECHMe. The liquid constituent of asarum oil is probably a methyl ether of isoeugenol. F. S. K. New Sugar with an Aromatic Nucleus. By MAQUENNE (Corirpt. rend. 109 812-814).-A commercial sugar pinite derived from the resin of the Pirius lambertiana of Nebraska resembles the pinite described by Berthelot which was derived from the same Fource but differs from it in melting point and rotatory power.Both are very soluble in water slightly soluble in alcohoi crystallise i n nodules and have a high rotatory power. Berthelot's pinite has a rot,atory power of [a]j = + 58.6 ; the new sugar which the author distinguishes as P-pinite has a rotatory power [a]n = 65O.51 and melts at 186-187,' (corr.). It has the same melting point and rotatory power as sennite and probably is identical with it. P-Pinite has a composition intermediate between C,H,,Os and CtiH,,07. When boiled for a short time with fuming hydriodic acid it yields methyl iodide and a sugar C6H,,06 which crystallises in small tetrahedra melts a t 245' (corr.) dissolves very readily in water and is almost insoluble in alcohol and quite insoluble in ether. Cryometric estimation of its molecular weight gave the numbers 176-178 so that i t is isomeric with glucose.When heated with llitric acid i t yields rbodizonic acid which can be converted into tetrahydroxyquinone by the action of hydrochloric acid. It followsORGANIC CHEN IST R Y. 245 from these results that 6-pinite is the methyl salt of the sugar C6HI2O6 and the latter is a benzene-derivative isomeric with inosite ; it may be distingnished a s 6-inosite. Berthelot's pinite also yields methyl iodide and p-inosi te when treated with hydriodic acid. C. H. B. Lactones derived from Glycines. By P. W. ARENIU~ (J. p i * . Clrem. [el 40 498-504 compare Abstr. 1888 825).-GZycoZyZ- pheTbyZgZycine OH.CH,.CO*KPh*CH,.COOH is prepared by heating chloracetophenyl~lycocine with aqueous soda for half an hour adding excess of hydrochloric acid and extracting with ether by distilling the ether arid crjstallisinp the residue from a mixture of benzene and alcohol the new plycine is obtained in large transparent rhombic tables melting a t 127-128° soluble in water and alcobol and sparingly in ether and benzene.The caZcium salt (with 6 mols. H20) and the barium salt (with 7 mols. H,O) are described. Anlaydroglycol~ZpJ~en~lgl~icir~e NPh<CH2:CO> 0 (compare Knori*'s phenylmorpholine Ahstr. 1889 l219) is obtained by heating gly- colylphenylglycine a t 160" ; it crystallises from hot alcohol in silky needles which melt a t 1G9" and dissolve with difficultv. GZycoZyZpheszyZgZ?lcin mnide OH*CH,~CO*NPh-CB2*CONH obtained by passing dry ammonia throiiqh an alcoholic solution of the la3t- mentioned compound crjstallises in lustrous leaflets melts a t 1.23-129" and dissolves easily in water and alcohol but only sparingly in benzene.Gl~coly lorthotolyl glycine and anh yd roglycolylorthotolylgl yc'ne have been described before (Abstr. 1888 825) ; the pottrssium scr Zt (with 1 mol. H,O) the silver salt and the barium salt (with 7 mols. HzO) of the former are here described. GZ?/coZyZo~thotoZylgZyc~nall ide OH*CH,.@O*N( CGH,Me)*CH2*CONH obtained from the latter i n like mantier to ~lycolylphen~lglgcinamicle crystallises in rhombic tables and melts a t 152". !IO*CH A. G. B. Metaphenylenediamine from Resorcinol. By A. SEYEWITZ (Conipt. rend. 109 814-817) -Resorcinol is heated i n sealed f u l m at 280-300" for three hours with four times its weight of anhydroiis (but not fused) calcium chloride previously saturated with dry ammonia.The product is agitated with twenty times its weight of cold water for ten minutes filtered the amine extracted with ether after addition of a slight excess of potassium hydroxide and the ethereal solution saturated with dry hydrogen chloride which pre- cipitates crystals of metaphenrlenediamine hydrochloride in quantity amounting to about 60 per cent. of the resorcinol taken. No un- altered resorcinol is left in t'he tube. The amine is not formed l d o w 200" and even a t 250" some resorcinol remains unaltered. Direct experiments show t'hat t8he maximum yield is obtained by heating for three hours at 300" ; longer heating rednces the quantity of diamine obtained.C. H. €3.2-46 ABSTRACTS OF CttEhl'ICAL PAPERS. Condensation-products of Carbodiimides and Orthodi- amines. By I. MOORE (Be].. 22 3186-3201; compare Abstr. 1889 98 3) .-Dimet hy ldip hen y Miamidome th y lsneort h op h pny lenediarnine Cl9Hl6Na&Tez prepared by boiling the phenylene-base with methyl iodide and potash in alcoholic solution crystallises from alcohol in colourless needles or prisms and decomposes a t about 200° but without melting ; it is readily soluble in hot benzene and hot alcohol but only sparingly in boiling water and almost insoluble in ether. The tetranitmso- compound C19H14N4(NO)4 separates in slender needles when the base is treated with sodium nitrite in well-cooled glacial acetic acid solution; it gradually decomposes at about 110" melts a t about 137-138" and is readily soluble in ether glacial acetic acid hot benzene and alcohol but insoluble in water.It dissolves freely in warm dilute hydrochloric acid and dilute sulphuric acid and it gives Liebermann's nitroso-reaction. Diacet y 1 dipamtol y 1 diumidoineth y leneort hop hcn y lenediamine prepared by warming the paratolyl-base (Zoc. cit.) witlh acetic an- hyd ride crvstallises from wai-m dilute alcohol in colourless needles melts a t 142-143" and is readily soluble in alcohol benzene and ether but almost insoluble in light petroleum. The dibenzoy7- derivative C21Hz,,0N4B~2 is obtained when the base is heated with benzoic anhydride a t 130-140" for an hour ; it crystallises from boiling alcohol in colourless needles or slender prisms melts a t 184 -185" and is readily soluble in hot alcohol and hot benzene biit only sparingly in ether and almost insoluble in light petroleum.The tetrabenzoyl-derivat ive CzlHIBNIBzI prepared by heating the base with benzoic anhydride at 240-250" for 2 i hours crystallises from boiling alcohol in colourless slender needles melts a t 273-5274" and is readily soluble in boiling climene moderately easily in hot alcohol and benzene and almost insoluble in light petroleum. The tetranitroso-derivative C,lH,8N1(NO)a crystallises in slender yellow needles gradually decomposes a t about 120" and inelts at about 130" ; it is readily soluble in alcohol ether and warm benzene but almost insoluble in liqht petroleurn. I t gives Liebermann's nitroso- reaction.T ~ ~ t r a p h e n y Z d i a m i ~ ~ ~ ~ m ~ t ~ ~ ~ l e n e o r ~ h ~ p ~ ~ ~ y Z ~ n e c Z i a m i n e C,,H,,N is obtained when diphenyldiamidomet byleneorthophenylenedianiine is heit ted at 200" with carbodiphenylimide. It crystallises in colourless well-defined rhombic prisms a b c = 0.6633 I 0.5685 melts at 138-139" and is readily soluble in alcohol ether and benzene but almost insoluble in light petroleum. When distilled it is de- composed into aniline and diphenyldiamidomethyleneorthophenylene- ciiarnine; it is also decomposed by 20 per cent. hydrochloric acid a t 1.50" yielding diphenylcarbamitle and phenylenediamine. The hydrochloride (C,,H28N6)2,SHCl crystallises in thiti colourless plates and is readily soluble in alcohol and hot water. The pZatino- chloride ( C32H28N6)4,3 H,PtC16 which crystallises in oranqe-red plates is only sparingly soluble in hot alcohol and insoluble in water and ether.The szrlphate CaH28N6,2H2S04 crystallises from alcoholORGANIC CHEMISTRY. 247 in colourless prismatic needles and is readily soluble in hot alcohol and hot water but insoluble in ether. The tatramethyl-deriva- tive C32H24N6Me4 crystal1 ises from warm benzene in colourless prismatic needles melts at 181-182" and is readily soluble in warm alcohol. ether and benzene and in mineral acids. The tetracetyl- derivative CSzETz4N,Ac crystallises from a mixture of benzene and light petroleum in colourless well-defined prismq melts at 125-126" a n d is readily soluble in alcohol ether and benzene but only sparingly in light petroleum.The tetrabelzzoyl-derivative C32H?4NSB~4 crystallisw from hot alcohol in small colourless needles o r prisms melts a t 181-182" and is readily soluble in hot alcohol and benzene but only sparingly in ether and almost insoluble in light petroleum. Tetraparatolylcxmidodimeth~ylen~ol-thophenylenediamine C36H761J6 can be prepared by heating orthophenylenediamine (1 mol.) with carbo- diparatolylimide (1 mol.) a t 130-140" aud then adding a further quantity (1 mol.) of the imide and heating again for 3-4 hours a t %OOo. It crystallises from hot alcohol in colourless needles melts a t 115-116" and is readily soluble in hot alcohol and benzene but only very sparingly in ether and light petroleum. It dissolves in con- centrated sulphuric acid yielding a colourless solution and it is decom- posed by 30 per cent.hydrochloric acid a t 150" yielding ortho- phenylenediamiiie and diparatolylcarbamide. The hydrochloride ( C3,&,N6),,3HC1 crystallises from dilute hydrochloric acid in colour- less prismatic needles and is readily soluble in alcohol and hot water bnt only verp sparingly i n ether. and iiisoluble in benzene. The plnfinochloride ( C3,H,,N,)4,~H2PtC1 + 15H20 separates in orange-red plates when platinic chloride is added to a dilute hydrochloric acid so- lution of the base ; it loses its water at 100" and is insoluble in water ether and benzene butl readily soluble in warm alcohol. The sulpliate C3fiH36N6,(LH2S04 crvstnllises in colourless needles and is readily soluble in hot alcohol and hot water but almost insoluble in benzene and ether.The fetracetyl-derivative C36H32NSAc4 separates from benzene in small granular crystals melt9 a t 114-11 5 O and is readily soluble in alcohol hot benzene and hot light petroleum but very sparingly in cold ether. The tefi.abeizzoyZ-derivnt ive c3 H32N6Bz1 cryst~llises from alcohol in colourless needles melts at 145-146" and is rendily soluble in hot alcohol ether and benzene but almost in- soluble in light petroleum. Pentamidobenzene. By A. W. PALMER and C. L. JACKSON (Amer. Chein. J. 11 448-456; compare Abstr. 1888 825 and A. Barr ibid. 822) .-Triamidodinitrobe?rzene C6H ( NH2),( SO,) was prepared by heating tribromodinitrobenzeiie melting a t 192" with alcoholic ammonia at 100" under pressure. It mas obtained in two forms-in reddish-yellow needles and in black aniorphoas masses ; it does not melt even above 300" but is decomposed if heated inore intensely and is iiisoluble in most ordinary solvents but dissolves slightly in alcohol and in chloroform from which solutions it crystallises in small yellow plates. When reduced with tin and hydrochloric acid i t yields a trihydrochlovide o~pei?tnmidobenzene CsH(NH2),(NH,Cl) ; this crystallises in small colourless shombic plates turning brown after a F.s. I(.218 ABSTRACTS OF CHEMICAL PAPERS. time and forming a tarry substance when heatad with hot water 01- oxidising agents. This substance is sparingly soluble in alcohol and dissolves easily in water from which it is precipit'ated by passing in hydrogen chloride ; it is insoluble in ether benzene and chloro- form.Evidence was also obtained of the formation of a pentahydrochloride of this base. Tria~LiZidodin;trobpnxene C,H (NBP1i),(N02) was also prepared by heating aniline with tribromodinitrobenzene ; it melts at 179" and crystallises from alcohol in orange-red needles from ether in groups of short prisms ; from solution in benzene or chloroform i t is deposited in an amorphous form. It dissolves readily in benzene chloroform and hot alcohol moderately in ether carbon hisulphide acetic acid and acetone. It is not acted on by hydrochloric acid but dissolves in nitric and sulphuric acids forming yellow solutions. This research has been discontinued owing to the publication of a paper by Barr on the same subject. The free base cannot easily be prepared from it.C. F. B. Action of Carbon Bisulphide on certain Axo-compounds and Hydrazones. By P. JACOBSON and V. SCHENCKE (Ber. 22 3232 -3245).-It has previously been shown by Jacobson (Abstr. 1888 487) that by the action of carbon bisulphide on benzeneazo-/j- naphthol two anhydro-compounds of a-amido-/?-naphthol are formed namely thiocarbamidonaphthol C,,H,< .>C-SH and carbanilamido- naphthol Cl,H6<x>C*NHPh. The authors have examined the action of carbon bisulph id e on benzeneazoparacresol benzeneazopsendo - cnmenol and benzenedifiazoresorcinol and find that in all these cases tfhe reaction proceeds in a manner exactly analogous to that described above. They have also extended their experiments to the hydrazones of P-naph thaquinone and phenanthraquinone and show that the same reaction takes place in these cases also.The results obtained form therefore a further confirmation of the supposition tliat the atoms in the characteristic groups of these azo-compounds and ortho- quinouehydrazones are combined together in the same manner ; whereas from their modes of formation it would be expected that 0 0 $*OH -C *NzN*Ph the groups would be represented by the formulae *q=0 respectively. Between the various constitu- .CIN-NHPh and tionad formulae which have been proposed this reaction which Occurs a t a high temperature cannot of course decide. 111 carrying out the reaction 1 part of the azo-compound or hydr- is heated with 2-3 parts of carbon bisulphide in a sealed tube for eight! hours. The temperature necessary is 190-210" except in the case of benzenedisazoresorcinol when the reaction ta.kes place a t 150-155" but proceeds less smoothly than with the other corn- pounds.The products of the reaction of benzeneazoparacresol and caiabonORUANCC c]H~~lIS'l'€tY. 249 0 umidocresol C6H,3&fe<N>C*NHPh. The former crystallises from dilute alcohol in colourless stellar aggregates of needles melting at 2 L6-217". The second compound crystallises from the same solvent in long colourless needles which melt at 205-206". Its picrate melts at 216-817" and its acefyl-compound at 86-87'. The first product of the reaction of benzeneazopsendocumenol and carbon bisulphide thiocarbamidocumenol C6HMe3<N>C*SH crystal- lises in colourless needles melting at 252-253".By the action of iodine on its sodium salt it is converted into the bisulphide S [ C<g> C6HMe3] which separates from chloroform solution i n colourless prismatic crystals melting at 150-1 51". The second 0 compound formed carbaniZarnidocurnenoZ C6HMe3 < N> C-NHPh crystallises in broad colourless needles melting at 145". Its picrate melts at 197-198'. The products of the reaction of benzenedisazoresorcinol and carbon bisulphide are more difficult to purify than those previously men- tioned. The first thiocarbodiawiidoresorcinol C,H,[ <:>C*SH ]? forms an amorphous yellowish-white powder which commences to blacken at 250" and melts with decomposition at 270". Carbanildi- amidoresorcinol C6H2[ <N>C*NHPh] 2 is likewise an amorphous powder which blackens at 240° and melts with complete decomposi- tion at 270".I t unites with 2 mols. of picric acid forming a picrate which melts above 240". The two compounds obtained by the reaction of naphthaquinone- hydrazone and carbon bisulphide are isomeric with those obtained from benzeneazo-@naphthol in which the nitrogen and oxygen- atoms are in the a- and p-posit'ions respectively. In the compounds to be described these positions are reversed. Thiocarbamido-a- naphthol C,,,H,<O>C*SH crystallises in long colourless needles which melt with decomposition at 259-260" and are readily soluble in warm alcohol acetic acid and benzene. Jt is converted by potas- sium ferricyanide into the bisulphide. The second compound c a d - anilamido-ol-na~hthol Clo&<O yC*NH-Ph crystalhes from chloro- form in colourless needles melting at 232-233" and is easily soluble in benzene alcohol and acetic acid.Its picrate forms microscopic prisms and melts at 213-214". Phenanthraquinonehydrazone and carbon bisu1phide.-Thiocarb- uniidophenanthrol C14H8<E>c*sH is formed in very small quantity and is an amorphous colourless powder. Carbanilaniidophenanthrol 0 0 N N 0 CI,H8<N>C*NHPh 0 crystalliseR from glacial acetic acid in pale- yellow needles united to stellate aggregates which melt at VOL. LVIIl. S250 ABSTRACTS OF CHEMICAL PAYERS. 192-195". It is readily so1ut:le in alcohol and benzene less so in acetic acid and is resolved by alcoholic potash into aniline ammonia carbonic anhydride and hydrophenanthraquinone. Its picrate forms microscopic prisms melting a t 235-236" and its acetyl-deriva- tive crystallises in small colourless plates and melts at 163-164".The hydrazones of orthodiketones (formerly regarded as mixed azo-compounds) do not act in this manner with carbon bisulphidc. Parahydroxyazo-compounds are attacked but resinous products are formed. Azobenzene on the other hand is converted a t 280-300" into the compound C6H,<s >C*SH described by Hofmann (Abstr. 1887 823). H. G. C. By 0. BURCHARD (Anualen 254 115-128 ; compare Abstr. 1889 138) .-a-Ethylenephenylhydrazine (m. p. 90.5") dissolves in concentrated sulphuric acid and on adding a trace of nitric acid an intense purple-red coloration is prodiiced. When i t is treated with sodium nitrite in dilute hydrochloric acid solution nitrosoethylenediphenyldiamine (m.p. 160') is precipitated. The sulphafe C2H,(NPh*NH,)?,HzS0 crystallises from dilute alcohol in colourless needles and is only sparingly soluble in alcohol. The nitrate C,H,(NPh*NH2)2,2HN03 crystallises from alcohol in colourless needles or plates is readily soluble in water and melts at 172-173" with decomposition. The oxalate. C,H,(NPh.NII,),,C2HPOj crystallises in needles melting a t 183" with decomposition. The tiiLccetyZ-derivative C2H4(NPh*NHAc)2 crystallises from alcohol in slender colourless needles melts at 222" and is readily soluble in glacial acetic acid but only sparingly in cold alcohol and insoluble in ether. N Ethylenephenylhydrazine. Eth y lenepheny 1 hy drazin edisuccin ic acid C2H4 ( N P h*C 0.C2Hi C 0 OH) prepared by heating the hydrazine (1 mol.) with succinic anhydride (2 mols.) in alcoholic solution separates from dilute alcohol in colourless crystals melts at 203" and is almost insoluble in alcohol but readily soluble in water. The sodizm salt is cr-ystalline ; the lead salt separates from hot water in which it is only very sparingly soluble in the form of a crystalline powder. Succin y lethy Zenep hen y lhy drazine CJ& < PhaN H. > C,H4 is obtained when the hydraeine is heated at about 180" with succinic anhydride. It is a colourless powder readily soluble in alcohol and chloroform but insoluble in ether; i t has no well-defined melting point as it begins to sinter together af 100-llO" and only becomes completely liquid a t about 126". When boiled with alcoholic potash it is couverted into a compound probably ethylenephenylhydrazineauccinic acid which has acid properties ; this substance is a colourless powdei- melts a t 137-140" with previous softening and is readily soluble in alcohol but only very sparingly in ether a n d chloroform.by NP h*N Ha C 0 NPh-NH.70 Oxaly lethy Zen epheny 1 hydrazine C2H4<Nph.N H o prepared0 ROAN10 CHEMISTRY. 8.51 heating the oxalate a t about 183" is a cglourless amorphous powder soluble in alcohol. Ethylenet ,.iphenylthiosemicarbaziae N H Ph-C S-NH-N Ph*C2HA*NPh*NH2 separates as an oil when an alcoholic solution of the hydrnxine is warmed with phenylthiocarbimiile ; i t crystallises from alcohol in slender needles melts at 164*5" and is moderately easily soluble i n alcohol.Ethylenetetra~he?~yldithiose?,ticarba~~de C2H,( NPh-NHC S*NH Ph) is a crystalline powder melts a t 194*3" and is sparingly soluble in alcohol. pre- pared by boiling the hydrazine with acetone in alcoholic solution crystallises from alcohol in colourless plates melts a t 71-72" and has basic properties. The acetophenone condensation-product C?H,(NPh.N:CMePh) crystallises from alcohol in golden needles nielts a t 117-118" and is only sparingly soluble in alcohol. Attempts to prepare condensation-products with dialdehydes and diketones were unsuccessful. F. S. K. ,4 cetonet h y 1 enephen y I h y drazine CMe, N. N P ha C,H4*NP h*NH2 Oximes. By H. GOLDSCHMIDT ( B e y . 22 3101-3114). - f arb- nniZidobenzaZdoztnze C H P1i:N.OCO.N HPh is obtained when benm l(1- oxime (1 mol.) is warmed with phenylcnrbimide (1 mol.) in benzene solution.It crystallises from benzene alcohol and ether in colourlrss needles melts a t 135-136" and is decomposed when heated above its melting point yieldiiig diphenylcarbnmide benzonitrile water and carbonic anhydride ; other carbanilidoximes give analogous de- composition-products under the same conditions. When warmed with alcoholic potash it is decomposed into benzaldoxime and ethyl phenylcarbamate and when boiled with alkalis it jields benzaldoxime and aniline. Carba?.~ilidonnisaZdo,cinze OMe*C,H4-CH:N*O*CO*NHPh crystallises from benzene in long needles melting a t 82". Dicarbanilidosal ic y la ld oxi me NHPh*CO.ON:CH.CsB,.O*CO.SHPh crystallises from benzene in small scales melting a t 1 1 5 O .CarbaniZidofurfuraIdozinze C,~,O.CH:~*O.CO*NHPh crystallises from benzene in needles melting a t 138". Carbanilidoacetoxime CMe2:N*O*CO*NHPh crystallises from benzene in needles and melts a t 108'. Carbanilidoacetoy hmo?teoxime ClMePh:N*O*CO.NHPh crystallises in small colourless needles and melts a t 1 2 6 O . Cnrbanilidobenzophenor7eoaime CPh2:N*O*CO*NKPh crystallises from benzene in colourless microscopic needles melting at 176". CarbaniZidocarcoxi?i.le CloH,,:N*O-CO*NHPh crystallises from ben- zene in prisms and melts at 130". The corresponding derivative of isocnrvoxime crystallises from benzene in needles melting at 150". Carbanrlidocawyhoroxinze C,,H,,:N.O.CO*NHPh crystallises from benzene in needles and melts at 94" ; it is decomposed when heated s 22.52 AnSTllACTS OF CHKERIICAL PAPERS.at 120-1 30" yielding diphenylcarbamide campholenenitrile carbonic anhydride and water. Propionaldoxime and raleraldoxime combine with phenylcarh- imide with development of heat yielding oily compounds ; mesitylene- oxime also gives a n oily product. Carbanilicloqzcinoneoxinze C,H,O:N*O.CO.NNPh crystallises in short yellow prisms begins to decompose a t about IlO" and decomposes completely at lGO" but without melting. I t is decomposed by boiling alcohol yielding quinoneoxime and when treated with alkalis i t is decomposed into quinoneoxime aniline and carhonic anhydride ; other carbanilidoximes of this class show a similar behaviour with a1 kal is. Cadmnilidot hymoquinoneoxime C ,,H,,O N.0.C 0.N HP h crystal lises in long yellow needles niclting a t 131-132".Cart anilido-a-napht haqu inoneoxime C lo H N*O*C O*NH Ph crystal - lises in yellow prisms begins to decompose at about 160" and melts at 170". Carbanil&do-P-nayhthaquiPzone-p-oxime prepared from p-nitroso-a- naplithol crystnllises from benzene (with benzene) in greenish-yellow microscopic prisms and decomposes a t 119-120". Cccl.Lan.ilido-p-na~~t}ia~ui~~~ne-a-ox~n~e prepared from a-nitroso-p- naphthol crystallises in small yellow needles and melts a t 126-128". When /3-naphthaquinonedioxime (1 mol.) is warmed with pberiyl- carbimide (2 mols.) i n henzene solution diphenylcarbamide is preci- pitated and the solution contains /3-naphthaqninonedioxime anhydride (m. p. 78"). Toludiquinoyltebroxime is also converted into the an- hydride under the same conditions the pbenylcarbimide being con- certed into diphenylcarbamide.Carbanilidoisonitrosobut y 1 metli y I ketoiw COMe-C Pr:N*OC O*NH Ph ci*ystallises from benzene in colourless plates and melts a t 92-93". Carbai~ilidomethylproyy Zglyoxi,ne NO H:CMeCPr:N-O*CO*NHPh is obtained when the preceding compound is treated with hydroxyl- amine hydrochloride in alcoholic solution ; it crystallises from benzene in colourless plates melting at 129-13.". Dicarbanilid(vmethy1prop ylglyos*i?ne NHPh.CO*O*N:CMe*CPr:N*O*CO.NHPh prepared by treating methylpropylgl~oxime wit 11 phenylcarbimide in Ibenzene solution ciystallises in nacreous plates melts a t 1 6 6 1 70" with deconiposition and is only sparingly soluble in warm benzene.Carbanilido- Aenzi,Zmonoz ime COP h*C P h N O C 0.N H P h prepared from a-benzilmonoxime crystal lises from benzene in small prisms itielts at 144" and is decomposed when warmed with alkalis yielding aniline and a-benziloxime ; it turns yellow on exposure to light. Ca~bnnilido-~-benzilmonoxime prepared from ybenzilmonoxirne crystallises from benzene with 8 mol. of benzene in colourless needles loses its benzene at lOU" aud melts a t 143" i t turns yellow on exposure to light and is decomposed by alkalis yielding aniline and the yoxime. Dicnrbanil ic~o-a-benzildioxime N HPh.CO*O.N:CPh*CPh:N*O*CO.NHPh,ORGANIC UHEJIJSTRT. 258 crgstallises in colonrless microscopic plates melts a t 180' and is only sparingly soluble in the ordinary solvents ; it is decomposed by alkalis.1)icarbaniEido-P-benzildioxime crystallises from benzene in small prisms melts at 187" and is decomposed by alkalis Dicclrbanilido-r-benzildioxime crystsllises from benzene in colourless needles containing benzene and melts at about 175" ; when warmcd with alkalis i t is decomposed into aniline and berizildioxime an- hydride (m. p. 94'). The fact that all the benziloximes react with phenylcarbimide with equal readiness yielding compounds of equal stability is evidence in favour of Auwers' and Meyer's views namely that the benziloximes are st ereochemically isomeric. CarbariilidoisobenzaZdoxiwze CI4Hl2N2O2 is obtained when isobenzald - oxime (1 mol.) is treated with phenylcarbimide ( 1 mol.) in ethereal solution the precipitate quickly separated by filtration and recryst;llA lised from cold ether.It separates from benzene in colonrless needles and from ether in quadratic plates melting a t 94' wit,h decomposition. It is much more readily decomposed by alkalis than its isomeride (see above) yielding diphenylcarbamide aniline and isobenzaldoxime ; this behaviour is not i n accordance with Beckmann's formula for iso- benzaldoxime neither is the fact that carbanilidoisobenzaldoxinie readily undergoes intra-molecular change. When a few bubbles of hydrogen chloride are passed into a cold saburated benzene solo- tion of carbanilidoisohenzaldoxime it is wholly converted into the isomeride (m. p. 135-136O) some of which separates from the solution in crystals; the same change is brought about but more slowly by a trace of phenylcarbimide.F. 8. K. Amidoximes and Azoximes.. By F. TIEMANN (Ber. 22 3124-313U).-General remarks on the papers of Wurm (this voJ. p. 258) Zimmer (next abstract) Stieglitz (next' page) and Hoch ( t h i s vol p. 260). Action of Aldehydes on Benxenylamidoxime. By H. ZIMMER (Bey. 22 3140-3147).-Tiemann bas shown (this vol. p. 44) that acetaldehjde farms a condensatimi-product with benacnylamidoxirne. The author has extended this reaction to other aldehydes. B e n z e n y l h ~ d r a z o ~ i e ~ ~ i i ylethylidene CPh<r:>C€€ CH2Ph is formed when phenylacetaldehyde acts on benzenylamidoxime. It forms small white needles sparingly soluble in boiling water easily so in ether chloroform and benzene and melts at 136". Aqueoii~ hydrochloric acid resoives the compound into its components but dry hydrogen chloride forms with it a crystalline hydrochloride.Whcn oxidised with the calculated quantity of potassium permanganate the hy drazo xime yields benzen y 1 azoximepheny 1 eth eny 7 This is crystalline insoluble in water soluble in alcohol and ch1o1.o-254 ABSTRACTS OF CHEMICAL PAPERS. form sparingly so in ether and melts a t 118". alkalis have anv action on it. Neither acids nor u Benzeiay 1 hydraxoxillze~i.o~2/1if,Zene C P he::> CH E t obtained by the action of propaldehyde on benzenylamidoxime forms colour- less crystals spariugly soluble in water easily so in organic solvents and melts a t 64". When heated with alkalis or acids it is resolved into its components. The hydrochloride is crystalline. Eenzenyl- trzoximepropenyl CPh<",O>CEt - i R a colourless oil boiling a t 230-235".Acids and alkalis are without action on it. Benzenylhydrazoaiiiieisobutylidene CPh<~~>CH*CHMe forms silky needles soluble in boiling water in organic solvents and in cold concentrated hjdrochloric acid. When heated with acids or alkalis i t is resolved into its component,s. The hydrochloride is crysta,lline. ~enzenyEazoximei~.cbbule~~?/l is an oil soluble in alcohol ether and chloroform boils a t 253-255" and is indifferent towards acids arid a 1 k a1 is. BenzenylhydrazoximeisoanyZidenc CPh<:;(:>CH*CH2*CHMe2 is sparingly soluble in boiling water easily so in organic solvents crjstallises in colourless needles and melts at 83". It is decomposed by hot acids or alkalis and forms a crystalline hydrochloride.Ben- zr,n~Zaxoximeisoamen!/l is an almost colourless oil of slightly aromatic odour and is solnble in organic solvents. It boils a t 257" and is indifferent to acids and alkalis. No analogous hjdrazo-compound could be obtained from benz- aldelijde dibenzenylazoxime melting a t 107" being a t once formed. Benzeny lhy d ruzoxiwesa Zicideiz e C P h e N > C H - C6H4*OH c r j s tal- It is sparingly soluble Benzeny1azmi:im esaliceny Z CPb<=$& CsH,* OH is isomeric with Stdker's salicenylazoximebenzenyl OH*CsHc*C<N>CPli N-0 (this ~ o l . 1). 143) and resembles it in all its properties. It is therefore 1)robable that these two compounds are identical a molecular re- arrangement taking place during one or other mode of furmatiorr.The hydrochlorides of all these hydrazoximes are decomposed by water and are only formed t y the ackion of dry hydrogen chloride. L 1'. T. It is solnble in a1colio1 insoluble in water. N*O lises in colourless needles and melts a t 155". in water easily so in organic solvents and in cold alkalis. Be haviour of Ami doximes towards Diazo b ens ene- deriva- tives By J. STIEGLITZ ( H r r . 22 3148-3160).-When benzenyl- amidoxime acts on diazobenzene chloride or sodium diazobenzene- sulphonate diazoamidobeneene and a componnd C,,H,,N,O are formed. The li~tter compound seems to be formed from 2 mols. of the amid- oxiine tlie diazo-compouud playing the part of deterniining agentORGANIC CHEMISTRY. 2 55 only probably acting as it sometimes does as a mixture of aniline aild nitrous acid.The author has obtained the same compound C,lH,,N,O by the action of nitrous acid and of some mild oxidising agents though the yields were small. This compound benzenyl- hydrazoximeamidobenzylidenc CPh<Z:>CPh*NH crystalliscs in rhombic plates and melts at 124-125" being resolved into benzo- nitrile and benzenylamidnximc. It is insoluble in WR ter spsringly soluble in ether moderately so in alcohol benzene and chloraform. It has no acid properties and is only verj slightly basic its unstable hydrochloride only being formed when dry hydrogen chloride is passed into a chloroform solution of the base. This salt is soluble in water but after a time the aqueous solution gradually deposits the free base. I t crystallises i n colourless microscopic needles which melt a t 144-145" and a t a few degrees higher temperature decompose into ammoniLim chloride dibenzenylazoxime and small quantities of benzonitrile.The same decomposition takes place very rapidly wh(.n the alcoholic solution is boiled. The platinochloride forms a pale- yellow precipitate melting a t 125.5" and charring a t 130-14U". The picrate forms a golden-yellow precipitate melts a t 148-14Y0 and explodes at? a few degrees higher. The free base is not attacked by cold dilute acids or alkalis b u t when boiled with alkali is at once resolved into benznnitrile and benzenylamidoxime. When hcated with strong aqueous hydroc3hloric acid a t loo" benzenylamidoxime henzoic acid dibenzenylazoxime and ammonia are formed. Boiling glacial acetic acid or alcoholic solution of hydrogen chloride yields dibenzenylamidoxime.The absence of a free oximido-group is shown by ferric chloride giving no coloration. This base is stable towards nitrous acid. Heated with carbon bisulphide at loo" i t yields the compound C,HcN2S2 (Schubart this vol. p. 49) .probably after previous partial decomposition into benzenylamtdoxime and benzo- nitrile. Taking all these facts into consideration the author considers. the above to be its most probable formula. Orthohomo benzenylhydrazoximenmido-orthohomobenzyliden e was obtained by the action of sodium diazobenzenesulphonate on orthohomobenzenylamidoxitne. I t forms colourless microscopic crystals easily soluble in chloroform alcohol and benzene less so in ether and insoluble in water and aqneous acids and alkalis.It meIts at 109 -1 lo" and although stable at ordinary temperatures gradually decomposes in hot summer weather into orthotolunitrile and ortho- I~omobenzenylamidoxime. The same decomposition is readily effected Ijy hydrochloric acid a t 100". The author had not enough of this hydra zoxime to prepare ortkohomobenzoyl-o.1.thohomobenzel,y7umid~xi~,e C,H,Me*C (NH2):N*0.CO-C6H,Me directly from it b u t obtained the latter compound by the action of orthoioluic chloi4de on orthohomo- benzenylarnidoxime. I t crystallises in long silky needles resembling 2sbestos is easily soluble in alcohol chloroform ether and benzene and in acids is almost insoluble in water and alkalis and melts ah256 ABSTRACTS OF CHEMICAL PAPERS. 117-118'.At 180" water is given o% and di-orthohomobenzenylaz- ozinae C6H4Me*c<,>C*C6H4Me is formed. This forms very t h i n silky needles exceedingly soluble in alcohol ether benzene aud chloroform and melts a t 58-59'. It sublimes unchanged and volntilises in steam or alcohol vapour. N*O Metan.itrobei~zenylhydrazoxin~~amido-metanitrobenzylidene was obtained by the action of sodium diazobenzensulphonate on metani trobenzenglamidoxime ; it is a pale-yellow substance almost insoluble in the usual solvents. It is most soluble (1 2000) in alcohol. It melts at 150-151'. When boiled with alkalis it is decomposed into the nitrile and amidoxime but a trace of metanitro- benzen y lazoximem et an; t r o ben zen y Z NOz* C6H4* c<,>c *c 6H4*N0 2 is also formed. The latter is however best obtained by the action of strong cold snlphuric acid on the hydrazoxime.A mixture of meta- nitrobenzenylamidoxime and metanitrobenzonitrile gave no trace of the azoxime with sulphuric acid. The azoxime may also be obtained from the hydrazoxime by boiling the latter with glacial acetic acid. It forms microscopic micaceous needles sparingly soluble in cold organic solvents melts a t l68" and sublimes unchanged. The author obtained the same compound by acting on metanitrobenzenylamid- oxime with metanitrohenzoic chloride. Attempts to get analogous compounds by the action of dia,zobenwne chloride on compounds of the general formula NHR*CPh:N*OH have as yet proved fruitless. In the course of his work the author finds that in the action of hydroxylamine on thiamides and thianjlides the presence of excess of alkali is an advantage.Thiobenzort hotoluide C SPh*NH*C6H4Me is formed by fusing benzorthotoluide with phosphoric pentnsulphide. It crystallises from benzene in pale-yellow prisms and melts at 85-96'. When heated with an alcoholic solution of hydroxylamine hydrochloride it yields benzmylorthotoEuidozime NOH:CPh-NH*C6H4Me. When excess of alkali is present the reaction is veiay much accelerated. This com- pound crystallises in hexagonal prisms is easily soluble in acids alkalis and organic Bolvents and melts a t 147". Constitution of' Benzhydroxamic Acid. By G. MINUNNI ( B e r . 22 3070-3071).-l'he compound N,HPh:CPh*OH is formed when benzhydroxamic acid is heated at 130-140" with phenylhjdrazine ; i t crystallises from dilute alcohol in colourless needles and melts at 165-166".The formation of this compound shows that benzhydr- oxamic acid has the constitution OH-CPLNOH. F. S. K. N* 0 L. T. T. Oils of Wintergreen and Birch. By H. TRIMBLE and H. J. M. SCHROETER (Phnrm. J. Trans. 20 166-168).-The authors find that the oils of wintergreen and birch are physically and chemicallyORGANIC CHEMISTRY. 257 identical each consisting of methyl salicylate and small qunntities of benzoic acid and ethyl alcohol together with from 0.3 to 0.447 per cent. of a hydrocarbon of the formula C15H24 A sample of artificial oil of wintergreen had the physical but not the chemical properties of these oils and was not pure methyl salicylate. Methysticin. By C. POMERANZ (Monntsh.10 783-793 ; com- pare Abstr. 1888 1207 and l889,278).-This compound exists in the root of Mrtcropiper mefhysticum from which it may be best prepared by exhaustion with boiling 80 per cent. alcohol ; t,hc solution is con- centrated and allowed to remain in a cool place for some days when a crystalline deposit separates and this on recrystallisation from boiling alcohol furnishes pure methyst.icin in the form of inodorous tasteless prismatic needles melting a t 137". It has the formula C15H1405 is insoluble in cold water only slightly soluble in hot water light petroleum and ether but is readily dissolved by boiling alcohol and cannot be distilled unchanged. On treatment with potash o r soda the compound is dissolved with formation of the potassium or sodium salt respectively of an acid which the author has named methysticinic acid.The free acid C1iH1206 crystallises in yellow prismatic needles resembling piperic acid is sparingly soluble in ordinary solvents dissolves readily in solutions of the alkalis melts at 180" with evolution of carbonic anhydride and is coloured red by a solution of ferric chloride. On oxidation with a solution of potas- sium permanganate i?i is converted into a compound identical with Fittig and Remsen's piperonylic acid CH2:0,:C6H3*COOH [O COOH = 1 2 41 which melts at 227" and gives a charac- teristic calcium salt. Methysticol is obtained on boiling methysticinic acid with alkalis or dilute acids. It melts at 94" is insoluble in alkalis but is readily dis- solved by alcohol o r ether crystallises in flat prisms forms a cum- pound with phenylhydraxine which melts at 143" and has the formula C ,,H1203.In consideration of its behaviour with potash methysticin must be regarded as the methyl salt of methysticinic acid CH2:02:C,H3*C7H70:3 [O C7H,0a = 1 2 41 the group C7H703 if methysticiiiic acid is regarded as a 13-ketonic acid being represented by the chain -CH:CH*CH:CH*CO*CH,*COOH. The author has not succeeded in detecting the least trace of benzoic acid in the oxidation-product of methysticin (compare Kiilting and Kopp &Ion. Sci. 1874 921). G. T. M. R. R. Tannins. By C. ETTI (Monatsh. 10 805-806; compare this vol. p. 164).-Since the tannin ClfiHl4OS obtained from the aqueous extract of the wood of the Slavonian oak is a dimethoxy-derivative of a ketonic acid formed by the condensation of 2 mols.of pallic acid each of which has two hydroxyl-groups placed symmetrically t) the carboxyl-group ; and since the formation of the ketonic acid must be accompanied by the spliting off of a molecule of water from one of the carboxyl-groups the ketonic acid must hare the constitutional '3.K5 1' 2 3 4 6 formula C6H2 (OH) 3*C 0.C6H (OH),.C OOH.258 ABSTRACTS OF CIIEJIICAL PLlPERS It has j e t to be determined which of the bydroxyl-groups represent the two methoxyl-groups in the tannin. G. T. M. Ethyl Diphenacylacetoacetate. By C. PAAL and A. HOEKMAYN ( B a r . 22 3225-3232).- Paal has previously shown (Abstr. 1884 5118) that ethyl phenacylacetoacetnte (ethyl acetophenoneacetoacetate) is converted by dilute aqueous potash into phenacylacetone.In i his reaction a small quantity of a semi-solid insoluble substance is always obtained consisting of a crystalline mass saturated with oil. The latter may be removed by extraction with cold alcohol and tlie residue recrystallised from the hot liquid. Two kinds of crystals are thus obtained and can be scparated mechanically. The corn- 1)ound present in smaller quantity Cl6Ul3BrO does not combine with I rhenylhydrazine or hydroxylamine. and is very stable towards re- tlricing agents b u t the amount obtained was too small for further examilia tion. The second compound may be obtained pure by recrysrallisation from alcohol and forms large transparent monosymmetric tables which have the composition C22H2205r and consist of ethyl ciiplwmcyl- acetoacetate CAc( CH2*COPh),.COOEt the ethyl salt of a tri- ketonic acid.It forms large monosymmetric crystals a b c = 1.6766 1 1.1152; /3 = 86' 18'. It melts at 82-83" is insoluble in water sparingly soluble in alcohol but readily in chloroform acetic acid and benzene. With plienyliiydrazine it yields a dihgdrnzoue CJ4HJ4N4O3 wliich forms jellow crystalline flocks melting a t 88-92' :mcl readily undergoing decomposition. With hydroxylamine i t forms according to the conditions of the experiment a mono- di- or tri- oxime ; all three are amorplious soluble in alkalis and most organic solvetits but insoluble in water. The mono- and di-oxime melt a t 61-63" and the trioxime at 66-68'. The ethyl salt is very stable towards aqueous potash but is readily converted by alcoholic potash into the potassium salt of diplienacyl- acetic acid which i 3 identical with the acid previously obtained by I'aal and Kues (Abstr 1987 261) and +ids with phenylhydrazine t IIC same derivative l-S-diphenyl-5-phenacyl-6-pyrida~onephenyl- 113 drazone N<bpl,.CH,> CH*CH,*CPh:N,HPh.When heated with alcoholic ammonia diphenylacetic acid is con- i-ei-ted into 2 (;-diphen~lpyridine-4-carboxylic acid. By the action of alcoholic ammonia on ehhgl diphenacylaceto- acetate two compounds melting at 192" and 136" respect~velj are obtained both of which yield one and the same acid on hydrolysis and appear to be the nmideand ethereal salt of this acid. YPh-CO H. G. C. Benzenylazoximemethenylcarboxylic Acid and some of its Derivatives. By A. Wui:?lr (Uer.22 3 130-3139).-E/hy7 hemen?yl- ( L I I I idozl?n eoxcl Zat e NH,.C P ti :N.O*CO.CO*O I! t is obtained as a pre- cipitate or oil when a well-cooled chloroform solution of benzenyl- atliidcxime (2 niols.) is added to a similar solution of ethyl chlor-ORGANIC CR EXIST RT . 259 oxalate (1 mol.). When this substance is separated frcJm the benzen.1- arnidoxime hydi~ocliloride simultaneously formed by boiling with water and subsequently precipitated from alcoholic solution i t f o r m s small glistening white needles which decompose suddenly a t 118". It is insoluble in water chloroform and benzene sparingly soluble in ether and very soluble in alcohol. When digested for some days with water at 100" or saponified with weak alkali i t yields benzenyl- anzidoximeorulic arid NHr.CPh:N*O*CO*C'OOH7 which crystallises iri scales soluble in boiling water and melts at 159".When the chloroform filtrate from the oxalate is allowed to evaporate spontaneously ethyl benzen y l a z o x i n a e m e t h ~ i z ~ l c ~ ~ b o ~ ~ j l a t e CPh<Tg>C*COO E t is ob- tained. It may also be prepared by heating together benzenylamid- oxime and ethyl cbloroxalate and is the substance formed by the sudden decomposition alieeady meritioned of t h e oximeoxnlate ; finally i t may be prepared by heating t h e silver salt with ethyl iodide. It crjstnl- lises i i i needles or plates is moderately soluble in ether and alcohol readily in chlorofoi~m and very sparingly in cold water. It melts a t -51" and distils unchanged at 260". When hydrolysed it yields the j r e e acid which crystallises in needles is soluble in ether and alcohol sparingly so in cold water and melts at 98'.It is very slightly volatile in steam and chars when heated above its melting point. The potassium and calcium scrlts are white and crystalline the silvey and lead salts wliite powders the copper salt a green powder and the nzethyl salt (obtained by heating methjl iodide and the silver salt together at 100') farms pale silky-white needles which are insoluble in water but easily soluble in the usual organic solvents; it melts at 38" and boils at 216". The benzyl saZt obtained by digesting the silver salt with benzyl chloride at 200" forms long needles soluble in alcohol arid ether insoluble in water; i t melts at 105" turns brown at 21C" and distils with considerable decomposition at 300".The atrtide C9H5NZO2*NKZ is formed when the ethyl salt is digested a t 100" with a saturated alcoholic solution of ammonia or by the action of am- monium carbonate on the chloride. It crybtnllises i n needles insoluble in water and alkali soluble in organic solvents and melts at l i 3 " The chloride is prepared by acting on the dry pure acid with excess of phosphoric oxjchloride. It is a clear limpid liquid with an intensely irritating odour and boils at 153-15.5". It is miscible with cllloro- form and benzene is moderately soluble in ether and alcohol and is heavier than water i n contact with which the chloride is gradually decomposed. Dibenzenyldiazoxinzeoxalene CPh<rg>C-C GN->CPh 0.Y is ob- tained by t h e action at 40" of t h e above chloride on the sodium salt of benzenylamidoxime suspended in chloroform. It crystallises i n very pale glistening scales which are soluble in alcohol and ether sparingly so in chloroform insoluble in ether and melt at 142". It dissolves in boiling water without change and is tolerably stable towards acids and alkalis.This substance is isomeric with Zinkeisen's oxalenediazoximedibenzenyl (this vol p. la;<) and analogou; to the succinic derivative obtained by Schulz (Abstr. 1885,12L9). It is prob-260 ABSTRACTS OF CHE.\IICA\L PhPERS. able that duriiig its formation a transitory intermediate product CPh <~~>C*CO*O*NnleCPh is formed. L. T. T. Action of Ethyl Chloracetate on Benzenylamidoxime. By H.KOCH (Ber. 22,3161 -3163).-When ethyl chloracetate (1 mol.) is gradually added to an alcoholic mixture of benzenylamidoxime (1 mol.) and sodium ethoxide (2 mols.) and the whole boiled for three hours sodium benzenylamidoximeglycollate is obtained. This forms white crystals very soluble in water moderately so in alcohol. Acids liberate from this salt benzenylamidoximeglycollic acid NH,.C P h N- 0 43 K,*C 0 0 H. It crystallises in white needles melts a t 123-224" and is easily soluble in alcohol arid et,her sparingly in water. It has both acid and basic properties dissolving readily in acids and in bases but its aqueous solution has a strongly acid reaction. When a solution of the acid in hydrochloric acid is boiled for some time the ajzh?qdride CPh<NH N'o*CHz .bo ' is formed.This internal anhydride is hoieyer Lest obtained by heating the acid for some hours at 130-140". It is easily soluble in alcohol ether glacial acetic acid and boiling water ; crystallises in colourless needles and melts at. 148". I t has no longer basic properties but is still a strong acid and yields wel!- developed salts. It is very stable not being affected by bromine- water or sodium nitrite. Permanganates and analogous oxidising agents readily attack it benzonitrile being formed. It appears to be analogous _ _ - in composition and character to bezizenylimidoximecarhonyl CPh<EE>CO. L. T. T. Oxidation of Paratolyl Benzyl Ketone. By E. RUCHER (Chem. Cenh. 1889 ii 445 ; from Arch. sci. phys. nat. GenBce 22 75-76).- The usual oxidising agents split up the paratolyl benzyl ketone mole- cule ; if however certain of its bromine-derivatives are heated with water at 180" better resnlts are obtained.By treating the ketone with bromine in carbon bisulphide the author has obtained the five bromine subs ti tout ion-deri vati ves parato7yl b rom obenz y 1 ketone CHPhBr*COCsH,Me melting a t 79" ; paratolyl dibronaobewyl ketone CPhBr,*CO*CsH,Me melting a t 128.5" ; troinoparatolyl dibrornobenzyl ketowe CPhBr,*CO*C,iH,*CH,Br melting at 127" ; dibromoparatolyl di- brorntrbenzpl ketone CPhBr,.CO*C6Hd.CHBr melting a t 120" ; and tri- browtoparalolyl dibromobenzyl ketone CPhBi.,.CO.C,H,*CBr melting a t 124". By heating the dibromo-derivative with water in a sealed tube the diketone COPh-CO*C6H,Me. is obtained and from trhe pentabromo-derivative the diketonic acid COPh*CO*CsH4*COOH may be prepared by the same treatment.J. W. L. Azo-colours from Naphtharesorcinol. By S. v. ROSTANECKK (Ber. 22 3163-3168).-Believing that Zincke and Thelen's hydr-ORGANIC CHEMISTRY. 262 oxynaphthaqninonehydrazine (Abstr. 1884 1359) was really n naphthiwesorcinol-derivative analogous t o the nitroso-derivatives lately described by himself the aut,hor has re-examined it. He 6nds that when heated witjh acetic anhydieide and dry sodium acetate for H few minutes or even if digested with excess of acetic anhydride for snme hours a diacet!yZ-deriuati*ue N2Ph*CI,,H5( OAc) is fornied This cryst.allises from alcohol in needles melting a t 122- 123". The forma- tion of only a monacetyl-derivative was one of the chief reasons for Zincke and Thelen's formula and taking this and its general be- haviour into consideration the author believes this compound to be really phen ylazonaph tliaresorcinol C ,,H,( OH),*N,Ph.When this compound is dissolved in a litt.le alkali the requisite qunntity of sodium nitrite added and the mixture poured into dilute hydrochloric acid nitroso;pl~e~iylazona~htharesorcinol NZP h.C,,Hd (,ON*OH)*OH is formed. This crystallises in glistening brownish-red scales easily soluble in glacial acetic acid but very sparingly in alcohol and boil- ing water and alkalis. It diwolves in coiicentrated sulphuric acid to a dark-green solution; i t decomposes at 175". It dyes mordanted stuffs but much less intensely than nitrosophenylazoresorcinol.When reduced with tin and hydrochloric acid it yields amidonapht halic acid and aniline. This proves that the isonitroso-group has taken the remaining @-position in the nucleus. When pheiiylazoriaphtharesorcinol is dissolved in excess of alkali and diazo benzene chloride added dip?) eny Idisazonaphtharesorcinol C,,H4(KzPh)z(OH)2 is formed. This crystallises in long red needles and is insoluble in alkalis but soluble in chloroform and alcohol ; i t melts with decomposition a t 225". When reduced with tin and hydrochloric acid it yields amidonaphthalic acid arid aniline like the above ni troso-compound and has thus the composition [(N,Ph), (OH) = 1 3 2 41. It is very similar in appearance and character t o the analogous resorcinol-derivative. L. T. T. Oil of Camphor.By J. TRIMBLE and H. J. M. SCHROETER (Pharnt. J . Trans. 20,145-148).-A sample of the crude oil oE camphor a s obtained from Japan was found to have a reddish-brown colour sp. gr. 0.9632 at 16" ; i t boiled at 180". The odour resembled that of camphor and sassafras. By fractional distillation &c. the following definite constituents were isolated from the sample :-2ti2 ABSTRACTS OF CHhMlCAL PAP'k:RS. Formula. Boiling point. CloH16.. ...... 150" Cl,H,tj.. ...... 159 C,,H,,O.. .... l i 6 C:0H160.. .... 204 C,nHl,O ..... 213 C,nHl,,O ..... 232 CloH,,02 ..... %47 CioH16.. ...... 168 CloH16.. ...... 1 i l CIOI-3[16.. ...... 180 Per ceiit,. 0.40 12.00 13-00 3-00 15.00 4.00 10.00 30.00 i.00 2.00 The highest-boiling fraction (250-280"; 1.60 per cent.) WL~S a bluish-green oil ; the quantity was iiisuificient to ascertain if i t was a definite substmce.These compounds were fragraii t oils usually colourless and having high dextro-rotatory powers. The authors also experimented on seven other samples of oil of camphor which differed considerably from the former in physical properties and also in the proportionate amounts of the several fractions some of these being indeed entirely wanting in certain samples (compare Yoshida Trans. 1885 779). R. R. Strophanthus Hispidus. By T. R. FRASER (Pharm. J. Trans. [3) 20 328-835).-l'his paper is a very detailed account of phar- macological processes and of the reactions of the various extracts obtained from seeds and other parts of Strophanthns. The main results of the author's investigations have already appeared (Abstr.1888 €06). Strophanthin melts a t 172*5" dissolves in 55 parts of absolute alcohol 300 parts of acetone and 1000 parts of amyl alcohol and is only very slightly hjdrolysed by ptyalin. Strophanthidin is phj sio- logically extremely active. R. R.. Senegin from Polygala senega L. By A. FUNARO (J. P h ~ m . [ 5 ] 20 450-453 ; from Gazzetta 19 Sl).-Skn&gin extracted by Gelhen in 1804 was found by Queveniie to yield a white powder which he named polygalic acid. Bolley i n 1855 concluded that these two substances were identical and also the same as sapoiain obtained by Bussy from the root of Saponaria. The author finds five samples of s6n6gia to give a mean of C = 54.13 ; H = 7.45 ; but these amounts differ notably from Bolley and Quevenne's figures and also from the results published by Rochleder and by Christophson for saponin.On boiling skndgin with dilute acids glucose is formed and a gelatinous substance separates containiiig C = 62.26 H = 8.21. These figures are very wide of those obtained for sapoghnin prepared in a crystal- line form by Rochleder. The formation of se'ne'!ye'nin C40H3014 and glucose from shn6gin is represented as follows C6,H,01034 + 4H,O = The author evidently considers that saponin and sdnhgin are dif- ferent compounds although closely related. C,OH~,OI~ -k 4C6H1206. J. T.ORGANIC CHEMISTRY. 263 Pyrroline-derivatives. By C. PAAL mid N. P. BKAIKOFF (Ber. 22 3086 -3096). - Et liy I ort hotdy Zdip henylp yrro linecarbox y late [C6H,Me COOEt Ph = 1 3 2 51 prepared by boiling ethyl phenacylbenzoylacetate with orthotoluidine in glacial acetic acid solution crystiillises from alcohol in long colourless needles melts at 134 -13.5" and is readily soluble in alcohol ether glacial acetic acid and benzene.The corresponding acid C2iH19N02 obtained by hydrolysing the ethyl salt with alcoholic potash crystallises from hot alcohol in colourless scales melts a t 226-227" sublimes undecomposed and is only moderately easily soluble in ether alcohol and benzene. ()rthotoZyldi~hen?l7y~~rr~line G3HI9N is obtained by distilling the mid over lime; it crystallises from alcohol in flat colourless needles melts at 114-115" boils above 300" without decomposition and is readily soluble in most organic s o l ~ e n t s . E t h y l pnratol~ldiphenylpyr~oli~~ecn,-box~lat~ ci*ystallises from glacial acetic acid in slender coiourless needles melts at 145" and is readily soluble in hot alcohol benzene and ether but only sparingly in light petroleum.The acid crjstallises from hot glacial acetic acid in small colourless plates melts a t 205-206" sublimes without decoiii- position and is readily soluble in boiling nitrobenzene but only spar- ingly in ether alcohol and benzene and insoluble in light petroleum. Paratolyldiphenylpyrroline can be prepared as described in the case of the corresponding ortho-compound ; i t crystallises from glacial acetic acid in colourless needles boils without decomposition and is identical with t h e substance obtained by Bttumaiin (Abstr. 1887 736) by distilling para tolylpyri*olinedibenzoic acid over bargta.Ethyl ?netuxy I~lclipl~en2/Zp~rrolin~ carboxy late [ C,H,Me COOEt Ph =1 3 2 51 prepared by boiling ethyl yhenacylbenzoylacetate wit11 metaxylidine in glacial acetic acid solution is a thick oily compound. The ncid C25H21N02 cry. tallises from glacial acetic acid in c o l o u i ~ l e ~ ~ needles mcl ts at 253-254" sublinies umdecomposed and is moderately easily soluble in hot alcohol and benzene. 1C~etazllZyZcliphen?/lpyrroline C2,H,,N crystallises i n short colourless needles melts at 147-149" distils without decomposition and is soluble in most organic solvents. E t h y l ~-naphth!~ldiphenylpyrrol~necarbox~~late C,,H,,NO crystal Iises in colourless necdles or plates melts a t 181- 18d" and is readily solu- ble in hot alcohol and glacial acetic acid but only moderately easily in benzene.The acid C2;H19N02 crystallises from glacial acetic acid in colourless plates melts at 271%- 272" sublimes undecomposcd and is sparingly soluble in boiling alcohol and benzene and insoluble in light petroleum. The potassium salt is sparingly soluble in boiling water and insoluble in concentrated potash. a-Na~hth?lIdiphen2/lpyrroline C26H 19N crystal lises from hot alcoli 01 in small yellowish needles melts at 148-149" distils without de- composition and dissolves freely in most organic solvents when warmed therewith. Ethyl /3-nap ht h! ldiphen ylpyrrolinecarbox?lIate cryst a1 lises from hot alcohol and glacial acetic acid in small colourIess needles melting ;it264 ABSTRACTS OF CLtEJIICAL PAPERS.181-182". The acid is obtained by boiling the ethereal salt for a. long time with a large excess of alcoholic potash ; it crystallises from Iiot. glacial acetic acid in coloiirless plates melts above 350" sublimes undeaomposed and is only sparingly soluble in all ordinary solvents. ~-Na~hthyIdiphenylpyrl.oline forms fla.t colourless needles or long plates melts a t 207-d08" and is soluble in hot alcohol glacial acetic acid mid benzene. Ethyl orthohydroxyp?ien~ldipheny~~yr~oliii~ca~boxy2ute OH*C,H,*C,N HPh2.C OOE t prepared by boiling ethyl phenacylbenzoylacetate with orthamidophenol in alcoholic solution separates from alcohol or acetic acid in colour- less indented crystals melts a t 158-159* and is soluble in alkalis and all organic solvents. The acid C27H17N03 crystallises from glacial acetic acid in colourless ill-defined needles melts at 24&245" sublimes without decomposition and is readily soluble in ether alcohol and glacial acetic acid but only sparingly in benzene chloro- form and light petroleum.Ort holr ytll.,,ryphenyldiphenzll/7yrroline C,,H,,NO cry stall ises from glacial acetic acid i n yellowish needles melts a t 175-176" and is readily soluble in ether alcohol benzene and alkalis. E t hy 1 pcwapken y lenedi-d ip h en y 1pgrrolin.ecarbox y late crgstnllises from alcohol in yellowish scales melts a t 249-250" and is soluble in glacial acetic acid and benzene. Thi! acid C40H29N201 Eeparates from hot alcohol in small crystals rnelt,s above 300° sub- limes undecomposed and is moderately easily soluble in alcohol and glacial acet>ic acid but only sparingly in benzene and light petroleum.F. S. I(. Action of Hydroxylamine on Pyrrolines. By G. CIAMICIAY and C. U. ZANETTI (Ber. 22,3176-3179 ; compare Abstr. 1889,1208). -Acetonjlacetoxime NOH:CMe*CH,.CH,.CMe:NOH (m. p. 236.5" cow.) identical with the compound prepared by P a d (Abstr. 1885 505) is formed when 2 5-dimethylpyrroline is boiled for about six hours with hydroxylamine hydrochloride and sodium carbonate in alcoholic solution. This reaction tends to prove that the compound (m. p. l i 3 " ) obtained by treating pyrroline with hydroxylamine (Zoc. czt.) IS i n reality the oxime of succinaldehyde. When acetonylacetoxime is reduced with sodium and alcohol it is converted into a base the hydrochloride of which is a colourless crystalline compound and has the composition CsH16N2,2HC1. This base has the same composition as the dianiidohexane ohtained by Tafel (Abstr. 1889 976) by reducing the dihydrazone of acetonyl- acetone.With hydroxylamine metadimethylpyrroline yields a compound which is soluble in water and has powerful reducing properties ; this new substance is converted into a base CsHd when i t is reduced with sodium and alcohol. F. S. K.ORGAXIC CHEMISTRY. 2G5 Derivatives of LHydroxyquinoline. By E. LIPPMANN and F. FLEISSXER (Monatsh. 10 794-797). -Amidohydroxyquinoline has been isolated by Fischer and Renouf (Abstr. 1884 1370) but may be more conveniently prepared from the corresponding nitroso-curn- pound which is obtained as hydrochloride by adding sodium nitrite (25 grams) t o hydroxyquinoline (50 grams) in an aqueous solution containing hydrochloric acid (100 grams).The hydrochloride of the nitroso-compound forms an orange-coloured crystalline mass which is only slightly soluble in water but more soluble in dilute hydrochloric acid; it is decomposed on boiling its aqueous solution but may be obtained in yellow- or brownish-coloured scales or needles by very careful recrystallisation. With sodium acetate it gives a gelatinous precipitate which becomes crystalline on standing. Nitrosohydroxy- qninoline NO*C,NH,*OK [= 4 13 crystallises from alcohol in pale-yellow or greenish needles only slightly soluble in benzene ether and chloroform and decomposes on heating to 230". The plutinochloride ( C,H,N,O?) H2PtC16 crystallises in brown glistening scales and is decomposed on boiling with water.In order to deter- mine the relation O F t h e nitroso-group to the hydroxyl-group the authors converted it by means of nascent hydrogen into amidohydroxy- quirioline which on oxidation with potassium dichromate and sul- phuric acid and reduction with sulphurous anhydride furnished quinol. If the reduction is brought about by means of tin added a little at a time to a solution of the nitroso-compound in hydroc!iloric acid a violent reaction ensues and a crystalline double salt is obtained. On freeing this froin t i n by hydrogen sulphide and adding t o the solution sodium acetate a dichlornmidohydroxtlquinoline C,NH3C12 (NH?)*OH separates out as a white crjstalline mass whilst amidohpdroxy- quinoline remains in solution.The dichloro-derivative crystallises from alcohol benzene or chloroforin in slender white silky needles which decompose at 160" and furnishes a hydrochloride crystallising from dilute hydrochloric acid in yellow needles and readily decom- posed by boiling water. If stannous chloride is substituted for the metal amidohydroxyquinoline is the sole reductiou-product and from this a dihydroxyquinoline sulphate decomposing at 2&" and identical with the compound described by Fisher and Renouf (Zoc. cit.) may be obtained. It must therefore be concluded that the nitroso- compound contains the nitroso-group in the para-position relatively to the hydrox yl -group. By A. C LA US (J. pr. Chem. [ 21 40,444-447) .-Bromoquinolinesuiphonic acids may be obtained (1) By synthesis from bromamidobenzenesulplionic acid ; (2) by brominating qninolinesulphonic acids ; (3) by suiphonating broino- quinolines ; (4) by substitutiiig bromine for a hydroxyl- amido- &c.group in a hydroxy- amino- &c. quinolinesulphonic acid. Of thest four possible methods the third gives the best results. The orienta- tion of the acid is settled by treatment with tin and hydrochloric acid (Lellmann Ahstr. 1888 296) which produces a hjdroquinuline- sulphonic acid. The hydroquinolinesulphonic acitls are being investi- gated in the author's laboratory. G. T. M. B romoquinolinesulphonic Acids. VOL. LVIII. t266 ABSTRACTS OF CHEMICAL PAPERS. Hydroquinoline-4-sulphonic acid crystallises in large rhombic tahles or monoclinic leaflets which begin to melt at 318" (uncorr.) with decomposition.Hydroquinoline-1-sulphonic acid crystallises in pointed needles and decomposes at 243" (uncorr.). Hy droquinol ine-3-sulp honic acid forms characteristic glassy s h ork monoclinic prisms the measurements of which are given. It decom- poses a t 277" (uncorr.). A. G. B. Sulphonic Acids of 4'-Bromoquinoline. By A. CLAUS and W. SCHMEISSER (J. pr. Chern. [2] 40 447-454) .-4' 4-Bromoquinoline- sulphonic acid is obtained by heating 4'-bromoquinoline with sulphuric acid for some time at 250"-300"; it crystallises from alcohol in beautiful silky needles and from water both in long slender needles (with 1 i mols. H20) and in large anhydrous prisms which become needles whcn recrystnllised from hot water.It is insoluble in ether decomposes above 300" without melting and is stable in alkaline solutions. When treated with tin and hydrochloric acid it is con- verted into hydroq~iiioline-4-sulphonic acid. The potassium salt (with 1 mol. H20) the sodium salt the calcium salt (with 7 mols. H,O) the barium salt (with 3 mols. H,O) the copper salt (with 7 mols. H20) and the silver salt are described. The ethyl salt forms transparent needles melting at 125" (uncorr,). The chloride C,NH,Br-S02C1 crystallises from chloroform in needles and from ether in thick prisms which melt a t 82" (uncorr.). The amide forms small slender needles melting at 255" (uncorr.). 4' 2-Bromo~uinolinesui$?~or,ic acid is formed together with the above 4-sulphonic acid when 4'-bromoquinoline (1 part) is heated with sulphuric acid ( 5 parts) containing 30-40 per cent.of sul- phuric anhydride for about an hour on the water-bath. If the heating is longer or the temperature higher the 2-sulphonic acid is converted into the 4-sulphoriic acid. The two acids are sepa- rated by crystallising from water and treating with 96 per cent. alcohol when the 4-sulphonic acid dissolves. 4' 2-Bromoquinoline- sulphonic acid crystallises in colourless rhombic tables which are sparingly soluble in cold water and insoluble in other solrents; it can be heated to 300" without melting or decomposing. It is not acted on bv hot alkalis. Tin and hydrochloric acid convert it into a hydroquinolinesulphonic acid which melts a t 2,55" and has not yet been described ; it is probably hydroquinoline-2-sulpkonic acid.The sodiura salt the potassium salt (with 1 mol. H20) the barium salt (with 1 mol. H,O) the calcium salt (with 4 mols. HsO) the copper srrlt (with 1 mol. H20) and the silver salt are described. The ethyl sult forms short needle-shaped crystals melting at 100" (uncorr.). The chloride C9NH5Br*S02CI crystallises from chloroform in colour- less needles and from alcohol in beautiful lustrous leaflets ; it melts at 130" (uncorr.). The amide crystallises from hot water in small white slender needles melting a t 213" (uncorr.) and soluble in alcohol. When these two acids me brominated they yield different tri- bromoyninolines. The 2-sulphcnic acid yields a tribromoyuinoline0 RGANIC CHEMISTRY. 267 which crystallises in colourless lcstrous pi-isms melting at 171" (unvorr.) ; while the 4-sulphonic acid yields a tori bromoquilnoline which crystallises in slender colourless needles melting at 300" (uncorr.).A G. B. Sulphonic Acids of 4-Bromoquinoline. By A. CLAUS and 0. WURTZ (J. pr. Chem. [217 40 454460).-Wiien 4-brornoquinoline (1 part) is heated in a flask with sulphuric acid containing 50 per cent. of sulphuric anhydride ( 5 parts) a t 130-140" for 6-8 hoiirs the 1- and 3-sulphonic acids of 4-bromoquinoliue are obtained the former in considerable quantity the latter in small quantity. Th:y are separated by crystallising from water when the 1-sulphonic acid crystallises first. At higher temperatures disulphonic acids are produced a t the same time. 4 1-Bromoqzcinolineswl~honic acid crystallises (with 2 mols.H,O) in colourless lustrous needles or prisms which dissolve in hot water but not i n cold water o r in alcohol. The anhydrous acid is uncbanged below 300". When reduced by tin aiid hydrochloric acid it yields hydroquinoline-1-sulphonic acid. The sodium salt (with 2 mols. H,O). the potassixm salt (with 2 mols. H,O) the calcium salt (sbith 4 mols. H,O) the bam'um salt (with 3 mols. HLO) the copper snlt (with 5 mols. H,O) the silver salt and the lead suit are described. The ethyl salt melts at 110" (uncorr.). The chloride C,NH,Br*SO,Cl crystallises from ether in small colourless prisms and from alcohol in tables; it melts a t 125" (uncorr.). The amide forms small needles melting at 2 0 5 O (uncorr.) arid soluble except in water. 4 3-Bromoquinolinesulpho?iic acid crystallises in small lustrous colourless anhydrous needles soluble in alcohol and in water.The sodizm salt (with 1 mol. H20) the calciunz salt (with 7 mols. H20) and the barium salt (witn 2 mols. H,O) are described. The ethyl salt melts at 130° (uncorr.) ; the chloride melts a t 95" (uncorr.) ; the amide forms small dark-yellow crystals melting at 195" (uncorr.). When the acid is reduced with tin and hydrochloric acid. it yields hydroquinoline-5sulphonic acid (?) melting a t 171" ; and when brorri- nated it yields a tribromoquinoline melting at 248" (uncorr.). 3 LBromoquinolinesulphonic Acid and 4 3-Nitrobromo- quinoline. By A. CLAUS arid G. ZUSCHLAG ( J . pr. Chem. [ a ] 40 460-464).-La Coste (Abstr. 1883 96) obtained several sulphonic acids by sulphonating parabromoquinoline.The authors using fuming sulphuric acid (30 per cent. sulphuric anhydride) a t 1.20-125" only obtained one sulphonic acid. 3 1-Bromoquir~olinesulphonic acid crgstallisees in beautiful Iud,rous white needles and prisms which are anhydrous do not melt a t 3.5U0 and are moderately soluble in hot water. The potassium salt (with 1 mol. H,O) and the silver salt are described; the ethyl salt forms long colourless silky needles melting a t 139". When brominated i t yields a tribrornoquinoline which cryst allisefi in colourless needles and melts at 185" (uncorr.). Reduction with tin and hydrochloric acid converts it into hydroquinoline-1-sulphonic acid. La Coste's nitrobrornoquinolitie (Abstr. 1683 91) is 4 3-nitro- A.G. B. t 22ii8 ABSTRACTS OF CHEMICAL PAPERS. Zlromoquinoline; i t melts a t 130" (uncorr.) not 133" ; its hydrochloyide platiuochlmide and methiodide were obtained. 4 3-amidobromoqninoline (Zoo. cit.) melts a t 160" (uncorr.) not 164". Hydroxyquinolinesulphonic Acids. By E. L I m i A s N and F. F L E ISSN ER (Monatsh. 10 798-804) .-When 1-hydroxyquinoline (1 part) is heated with sulphuric acid (3 parts) in a sealed tube for three hours a t IhO" the product is a light-brown syrup which scarcelv smells of sulphurous anhydride and cou tains a sulphonic acid OH*C,NH,.SO,H + l$H,O which crystallises in pale-yellow needles melts with decomposition a t 275" is only slightly soluble in alcohol and is insoluble in ether. The aqueous solution is strongly acid gives a green coloration with fewic chloride and an almoht insoluble crystalline precipitate with lead acetate.The potassium salt is anhydrous and crystallises from water in light rose-coloured glistening scales. Its aqueous solution gives a green granular prcci- pitate with a solution of cuprie sulphate and a crystalline precipitate with mercuric chloride; the silver sa!t is a crystalline powder; the barium salt is an almofit insolu'ble powder. Besides the above-described cornpound l-hydl.oxyquitioZinecEisul~?~- nuic ucid OH*C9PU' H,(SO,H) is simultaneously formed in small yiiantities. It may be more readily obtained by heating a mixture of hydroxjquinoline (25 grams) snlphuric acid (7.5 grams) and phos- phoric anhydride (30 grams) a t 200" f o r five hours. It is a very hygroscopic substance and decompoces a t 200".The hydrogen potassium salt is a crystalline precipitate; the basic salt OK.CeNH,( S03K)2 IL compound sparingly soluble in water ; the basic copper salt Cu[O*CgNH4(S03),Cu] + 10H,O a light-green powder. G. T. M. Paradiasine-derivatives. By 9. W. ABENIXJB (J. pr. Chem. [2] 40,425-444 ; compare Abstr. 1889 134). Brornacetnnilide NHPh-OO*CH,Br is obtained by mixing benzene solutions of aniline (2 niols.) and bromaeetic bromide (1 mol.) eva- porating the benzene a t the ordinary temperature and washing the residue with water which leaves bromacetanilide undissolved. It crystallises in slender whiten eedles which melt at 130-131" and are soluble in alcohol ether and benzene but not in water. Chloracety lphe q L g Z y cine CH,CI*CO*NPh.C H,* C 0 OH is formed when phenjlglyciue suspended in ether is shaken with an ethereal solution of chloracetic chloride (eq.mols.) ; the ether is distilled off and the residue treated with water when .the ehloracetylphenylgly- cine separates as an oil which soon crystallises. It fornis four-sided tables o r prisms melting a t 132-133O soluble in alcohol aud benzene. A. G. B. Dip Leny ldiket odih ydropnra dimkne N P h < CH,,CO>NPh ' O°CH2 is iden- tical with Meyer's p'henylglycine anhydride (this Journal 1878 294) ; it may also be obtained by the action of alcoholic potash OII bromacetauilide and by heating chloracetylphenylglycine (1 mol.) with aniline (2 mols.) a.t 143-150' ; this last reaction settles its con- stitution. It melts a t 263".ORGANIC CHEJl ISTRT.2(;9 Phenylglycinylphenylglycine has been described before (Abstr. 1888 854; compare Hausdorfer Abstr. 1889 1014) ; it melts a t l2n-130". Bronzacetoparatoluidide C6H,Me*NH*C0.CH2Br [Me NH = 1 41 obtained in the same way as bromacetanilide crystallises from hot alcohol in long colourless needles which melt a t 164". Dipayato ly ldiketod ihydropnradiazine is obtained from broniacet,oparatoluidide or from paratolylglycocine in t,he same way RS diphenyldiketodihydroparadiazine is obtained from the corresponding phenyl compounds. I t crystallises from alcohol in beautiful long white needles which melt a t 232-253" and are soluble in glacial acetic acid but only sparingly soliiblc in other sol ve 11 t s. RthylgZycol~lparatoluidide C6H,hle*N HCO-C H,*OEt [Me NH = 1 41 is obtained as a bye-product in preparing the above parudiazine from bromacetoparatoluidide and alcoholic potash and may be sepa- rated from the mother liquor of the paradiazine by ether which dis- solves it.It crystallises in beautiful transparent prisms which melt a t 32" and are soluble except in water. Purahromaceto-z?lZidide C6H3Me2*NH*CO*CH,Br [Me2 NH=l 4 31 prepared by mixing benzene solut,ions of paraxylidinc (2 mols.) and bromacetic bromide (1 mol.) crystallises in slender white needles which melt at 14.5". Dipamxy 1 y 1 dike tud i?y drop aradiaxine C6H3NeZ'N<CH2.C4 Co*cHz>N-C6H,Me2 [Me2 N = 1 4 21 is obtained by the action of alcoholic potash on parabromticeto-xylidide it crystallises from hot alcohol in beautiful flat needles melting at 203" and soluble in benzene and acetic acid but not in water and ether.Ethylgl~col~~lya~axylidide C,B,Me,*NH.CO*CH,.OEt [Me NH = 1 4 23 is extracted by ether from the mother-liquor of the last- mentioned paradiazine ; it crystallises i n prisms melting a t 50" and soluble in the usual solvents. Di- a-nap ht hy Id iketodih y droparadiazin e obtained from chloracetonaphthalide and alcoholic potash crystallises from glacial acetic acid in flat needles melting at 27&275" and sparingly soluble in alcohol benzene and ether. Methyl mdanitrocunzate N02~C,H3Pr*C00Me [ P r Me0 NO2 = 4 1 31 is obtained by dissolving nitrocnmic acid in methyl alcohol and saturating i t with hydrogen chloride ; i t forms large crystals like nitre which melt at 64" and are soluble in most aolvents.Methyl metamidoc~~rnnte is obtained by reducing the nitrocumate with tin and hydrochloric acid ; it crystallises in colourless transpa-270 ABSTRACTS OF CHEMICAL 'PAPERS. rent prisms or tables melting a t S1-52" and easily soluble except in light petroleum. Meth y Z metnchloracet amidocumat e CH,Cl*C O*NH-CsH,Pr*C 0 OMe [Pr COOMe NH = 4 1 31 is prepared by mixing benzene solu- tions of the metamidocumate (2 mols.) and chloracetic chloride (1 niol.) evaporating the benzene at the ordinary temperature and washing the residue with water which leaves the chloraceto-deriva- tive undissolved. It crystallises from hot dilute alcohol in long slender colourless needles melting a t 101-102" and easily soIuble In most solvents except water and light petroleum.If bromacetic bromide be substituted for chloracetic chloride in the above prescrip- tion methyl metctbromacetamidocumnte is obtained ; it melts a t 106-107". Uipl.opyld~phen2/ldiketodihyd?.g,aradiazinedicarboxilic acid CINzH4(C6H,Pr*COOH) [COOH Pr N = 1 4 31 is prepared by heating alcoholic potash (1 gram) with methyl meta- chloracetamidocumatc (4 grams) in alcohol for half an hour then adding another gram of potash and heating for another half hour ; the alcohol is now evaporated the residue treated with water and an excess of hydrochloric acid added ; this throws down a resinous sub- stance which is washed and heated with alcohol. Part dissolves (see below) leaving the dicarboxylic acid as an insoluble powder which decomposes before melting and dissolves in alkalis being reprecipitated by acids. The ethyl salt obtained by the action of dry hydrogeii chloride on an alcoholic solution of the acid crystallises in flat lustrous oblique-ended needles melting a t 192-193" and soluble ill alcohol.2CZetethyZglycodyZanzidocumic acid OEt-CH2*CO*NH-C6H3Pr*COOH [COOH Pr NH = I 4 31 is tEat portion of the above-mentioned resin which dissolves in alcohol ; the alcohol is evaporated the residue dissolved in potash reprecipitated by hydrochloyic acid and crysta 1- lised from weak alcohol. It forms four-sided tables melting a t 140° and soluble except in water and petroleum. Y h eny lort hot oly 1 dike t odih y dro paradiaxin e NPh<Co*CRz>N*CsH,Me CHz*CO ,[Me N = 1 21 is obtained by heating chloracetorthotoljlglycine (1 mol.) with aniline (2 mols.) in a sulphuric acid bath a t 160"; the product is heated with water and hydrochloric acid filtered and the undissolved portion crystallised from alcohol.It forms slender white needles melting a t 165-166" soluble in hot alcohol and benzene but insoluble i n ether. It forms no platinochloride. Orthotoly lparatoly ldiketodihydroparndiu,z~ne C H ~ ~ * N < C ~ . ~ ~ > N ' C ~ H M ~ CO*CH [Me N = 1 2 and 1 41 is obtained by substituting paratoluidine for aniline in the prepara- tion of the last compound. It crystallises in long white felted needles melting a t I79-l8O0 soluble in alcohol and benzene but not in ether. A. G. B.ORGANIC CHEMISTRY. 271 Ditriazole-derivatives. By J.A. BLADLN (Ber. 22 3 1 1 6 . I 3117 ; compare Abstr. 1889 138). N- GEt prepared by boil- SEt-N N*NPh'c'ceNPh*N Di-pheny leth y ltriazo le ing cyanophenylhydraeine with excess of propionic anhydride crystal- lises from alcohol in prisms melts at 186-5-187" and is readily soluble in alcohol but insoluble in water. The hydrochloride C20HLON6,2HCl crystallises in microscopic prisms and is decomposed by- water. The platinochloride crystallises in orange-yellow unstabie prisms. Di-diphenyltriazoZe C29'E3C20N6 prepared by treatinq cyanophenyl- hydrazine with benzoic chloride crystallises from alcohol in colour- less needles witdh 2 mols. H20 loses its water at loo" melts at 2.57-258" and is only sparingly soluble-in alcohol very sparingly in ether and insoluble in water; it is a very feeble base. Di-paratoZy lmat h y I triaxole Cz0HZON6 is obtained when cyanoparatol y I - hydrazine is boiled for a few minutes with excess of acetic anhydride.It crystallises from alcohol in long prismatic needles melts a t 259-260". and is moderately easily soluble in alcohol but only sparingly in benzene and insoluble in water. The hydrochloride is readily soluble. Di-para,tolylet?Lyltriazole C22H21N6 prepared from propionic anhy- dride in like manuer separates in crystals from alcohol aqd benzene in which i t is readily soluble melts at 202-2203" and is ins;oluble in water. D i-pnmtol y lp JLeny 1 triazol e CMHZ1N6 prepared from benzoic chloride in like manner crystallises from alcohol in microscopic needles with 2 mols. H20 and from benzene in small plates with 1 mol.of benzene ; it melts at about 300" is insoluble in water and is only a very feeble base. F. S. K. Bases formed by the Action of Potassium Hydroxide on the Halogen-klkyl Salts of Papaverine. By A. CLAUS (J. pr. CJhem. r2] 40 465-4T9).-1n this paper the author replies to t h e recent kticisrns of Goldschmiedt (t'his vol. p. 179) on the work which he (the author) and others have already published on this subject (see Abstr. 1885 996 ; 1889 414). A. G. B. Belladonine. By E. D~~RKOPF (Ber. 22 3183-3184).-The brown syrup from which atropine has been obtained (commercially) is a mixture of helladonine atropine hyoscyamine hyoscine and their decomposition-products tropine pseudot,ropine and tropic acid. When the syrup is boiled with chloroform and ether in acid solution the hydrocarbons &c.are removed and the atropine in the purified base can by some suitable means be converted into tropine and tropic acid ; the belladonine is not changed by this treatment but the hyoscine (18-20 per cent.) passes into solution and can be easily iso- lated by means of the aurochloride. This salt C17H23N03,A~C19 crystall&es in prisms melts at 200" and is sparingly soluble in water; F. S. K.2 i 2 ABSTRACTS OF CHEMICAL PAPERS. Fumarine. By R. REICHWALD (Zeit. am-zl. Chem. 28 622-623). -Fumarine is soluble in 11.2 parts of chloroform and in i8.68 parts of benzene but is only very sparingly soluble in water alcohol ether and petroleum. When treated with Frohde's reagent it first. turns violet then dark-green ; with vanadyl sulphate i t gives an emerald- green colour which after some hours becomes yellowish-green ; with sulphuric acid and sugar it gives a dirty-violet coloration ; with selenosulphuric acid a pure violet.It is not coloured by chlorine- water but becomes violet-brown with bromine-water and sulphuric acid. A crjstal of potassium nitrate thrown into its solution in sulphuric acid coloors the liquid as it dissolves first preen then violet and lastly yellow. Potassium dichromate added to a fumarine salt throws down funiarine chromate ; on adding concentrated sulphuric acid intense green and violet streaks are produced passing after a few minutes into green. M. J. S. Preparation and Properties of Albumin free from Ash. By E. HABNACK (Ber. 22 3046-3052 ; compare Abstr.1882 747).- Albumin free from ash can be obtained a s follows:-The copper- compound of albumin prepared as previously described (Zoc. cit.) is purified by dissolving i t in very dilute soda yeprecipitating with acetic acid and washing well with water the process being repeated several times; the precipitate is then dissolved in a considerable quantity of soda the solution kept for 24 hours the albumin precipi- tated by neutidiuing with hydrochloric acid washed with water and dried at 100". It is thus obtained in the form of a gelatinous transparent brittle. yellowish-red mass which is almost free from ash 1 gram leaving a residue of about 1 milligram on ignition. I t is free from phosphorus and phosphates and iron could not be detected. When the moist subetance is treated with pure cold water it gradually swells np and dissolves ; the solvent action being hastened considerably by boiling. The dry substance shows a like behaviour but i t dissolves much more slowly. The residue obtained on eraporating the aqueous solution to dryness seems to have the same properties as the original substance.Albumin free from ash is precipitated from its aqueous solution by acids the precipitate being insoluble in excess ; also by neutral salts for example sodium chloride but the precipitate dissolves again if the solution is diluted very considerably. The precipitated albumin has the same properties as the original substance but if the precipitate is boiled with the solution it is gradually converted into a modification insoluble in water Albumin free from ash is precipitated from its aqueous solution by salts of the heavy metals phosphomolybdic acid potassium ferro- cyanide &c.; b u t it is not precipitated by alcohol ether phenol or tannic acid. F. S. I(. Heat Coagulation of certain Proteids. By J. B. HAYCRAFT and C. W. DUGGAN (Brit. Med. J. 1890 i 167-169).-1t is found that there are various circumstances that affect the temperature a tORGANIC CHEN ISTRT. 2’73 which any prote’id enters into the condition of a heat-coagulum. If a solut,ion of a coagulable protei’d is heated quickly the proteid will be foiind to coagulate a t a higher temperature than if the heat is applied more slowly. The coagulation point is considerably raised by diluting the solution and a very dilute solution may not coagulate even on boiling.The presence of certain neutral salts lowers of others raises the coagulation temperature. The presence of acids lowers of alkalis r R ises the coagulation temperature. These facts were ascertained to be true for egg albumin serum albumin vitellei’n and sernm globulin. Halliburton ( J . Physiol. 5) and Corin and Berarci (Abstr. 1889,1075) attempked to separate proteids by means of fractional heat coagulation. Without doubting the possibility of fractionating some prote’ids the result of the present experiments seems to cast a doubt on the method adopted unless other differences be denionst,rated to exist between the various proteids thus separated. It is thus possible that serum albumin or egg albumin may be single prote‘ids and the fact that various precipitates at different temperatures are obtainable can be explained in one of two ways either that the heat when applied foi.a long time (in Corin and Berard’s experiments for upwards of an hour) alters the character of the proteid i n solution so that its tem- perature of coagulation is heightened or that the result is simply the effect of dilution ; a solution of serum albumin is raised to 73” ; a precipitate occurs and is filtered off; that left in solution is now more diluted hence its coagulation temperature is higher. Precipitation of Albuminoids from Urine. By - BOYMOND (J. P h a ~ m . [5] 20 481-482).-1n attempting to form a filter of talc (previously washed in hydrochloric acid and water) €or the filtration of turbid urine the whole of the globulin contained in the urine was found to be removed by the so-called neutral substance composing the filter; whether any serei’n (? serum-albumin) was removed has not yet been determined.Experiments were instituted with other neutral substances and i t was found tbat bismuth subnitrate completely removed both globulin and “ serein.’’ This research is still being Fro- secuted. J. T. By A. JAQUET (Zeit. physiol. Chem. 14 289-296). -A sample of dog’s h~~moglobin prepared according to Zinoffsky’s method (Abstr. 1886 ZCS) gave the folloiving percentage composi- tion which may be compared with the results obtained previously with dog’s Emmoglobin (Ahstr. 1888 731) and with Zinoffsky’s analysis of horse’s haemoglobin in the following table :- W.D. H. Haemoglobin. Heemoglobin of dog. r-A-- 7 Previous analysis. Present analysis. Of horse (Zinoffsky). C . . .... 53-91 54.57 51.15 H.... .. 6.62 7.22 6.76 N.. .... 15-98 16.38 17-94 S.. .... 0.542 0-568 0.39 Fe .... 0.333 0.336 0.335 o...... 22-62 2( 1-93 23.432174 ABSTRACTS OF CHEMICAL PAPERS. The formula for dog’s haemoglobin deduced from this second analysis is C,5sH,?,3N,,,SJFe0,18. An analysis of hen’s hEmoglobin wits also made; the percentage composit,ion was C 52.47 ; H 7-19 ; N 16.45 ; S 0.8586 ; Fe 0.3353 ; 0 22.5 ; P 0.1973. The relation of S E’e = 9 2 ; the relation of Fe P = 1 1. The only other preparation of birds’ blood that has been analysed is that of goose’s blood by Hoppe-Seyler. He also found phosphorus present (0.7- per cent.) and this has generally been regarded as due to admixture with nucle‘in ; the relation of phosphorus to iron in the present research seems to indicate that the phosphorus may be actually in the hEmoglobin-molecule.W. D. H.ORGANIC CHEN ISTRT. 2230 r g anic C hem i s t ry.Constitution of Petroleum. By J. A. LE BEL (BUZZ. SOC. Ghim.[3] 2,305-307).-The author considered that normal paraffins mightalone be present in petroleum the occurrence of the secondary paraffinsbeing due to isomeric change occurring dnring its manipulation. Hefound however after isolation of the amylenes from natural petr-oleum and subsequent treatment with concentrated hydrochloric acidin the cold that dimet.hylethy1 chloride boiling a t 86" was obtained,which proves the occurrence of other than normal paraffins inpetroleum and according to him negatives the fermentation theoryof petroleum formation since no fermentation is known whichproduces both classes of compounds a t a time.Diallyl Tetrabromides.By G. WAGNER (Ber. 22 3056-3057).-The author has previously stated that diallyl is probably a mixtureof two isomerides (compare Abstr. 18813 226) a view which ifcorrect would explain the existence of the two tetrabromides,C,H,,Br,. Ciamician and Anderlini (this vol. p. ZO) in assnmingthat these two bromides are geometrically isomeric have probablyoverlooked the author's previous paper.T. 0. N.F. S. K.Action of Hydrocyanic Acid on Calomel. By FouQuEr(J. Yharm. [ 5 ] 20 397-400).-The statement that corrosivesublimate is produced by the action of hydrocyanic acid on calomelis incorrect.Mercury is set free with the formation of mercuriccyanide and hydrochloric acid in equivalent quantities. The reactionis almost always incomplete; bnt it may be started again byneutralising the free hydrochloric acid.Ammoniomercuric Cyanides. By R. VARET (Compt. revd. 109,903-904).-Alcoholic ammonia is saturated with mercuric cyanide,a current of ammonia gas being passed through the liquid whilesolution is taking place. The solution is heated a t 50" to 60° againsaturated with dry ammonia and allowed to cool. After some time,it deposits trmispareiit prismatic needltbs of the compoundHgCy2,2NH3 which become opaque and rapidly lose ammonia whenexposed to the air.At loo" it loses the whole of the ammonia in afew hours,If concentrated aqueous ammonia is saturated with mercuriccyanide mixed with more ammonia and cooled it yields long white,prismatic needles of the compound HgCy2,2NH3,+H20 ; this readilyloses water and ammonia on exposure to air although it is morestable than the preceding compound. A t IGO" it decomposes com-plet,ely and mercuric cyanide is left.The compound HgCy2,NH3 is obtained in small hard transparentcrystals by heating aqueous ammonia with a large excess of mercuriccyanide in a closed vessel a t 40". It dissolves in ammonia alterswhen exposed to air and loses all its ammonia a t 100". The actionJ. T224 ABSTRACTS OF CHEMKCAL PAPERS.of dry ammonia on finely-powdered mercuric cyxnide yields ayellowish-white product of the composition 10HgCp2,NH,.If ordinary ammonia is saturated with mercuric cyanide mixed withone-tenth its volume of ammonia solution and cooled to 0" i t yieldssmall white crystals of the compound HgCy2,NH,,$H20 very solublein aqueous or alcoholic ammoilia very unstihle when exposed to air.At looo it loses the whoIe of its water and ammonia.C.H. B.Interaction of Haloi'd Salts of Mercury and Zinc. By R.VARET (C~mpt. rend. 109 809-812).-A concentrated solution ofzinc bromide is added drop by drop to a boiling saturated solution ofmercuric cyanide with vigorous agitation. The greater part of theprecipitate redissolves but the liquid remains turbid. It is filteredand allowed to cool when it deposits white crystals of the compoundHg?ZnBrzCy4 + 8Hz0 which alters little if a t all on exposure t oair is somewhat soluble in water and becomes anhydrons a t 100" orin zt vacuum.When the hydrated compound is heated it loses water,blackens and decomposes in to mercury cyanogen mercuric bromide,and zinc carbonate. Nitric acid converts it into zinc nitrate mercuriccyanide and mercuric bromide hydrocyanic acid being evolved. Dryammonia expels the combined water and forms a compound,HgpZnBrzCy4 + 2NH3 which loses ammonia when exposed to air andis decomposed by water.That this compound has the constitution ZnCyz,HgC'y2,HgBr +8H20 and is not a compound of mercuric cyanide with zinc bromide,is proved by the following facts. Potassium iodide added to theaqueous solution produces at first a precipitate of zinc cyanide fol-lowed by a precipitate of mercuric iodide ; and Berthelot has shownthat potassium iodide combines with merciiric cyanide with liberationof heat but has no action on zinc cyanide.Cupric sulphate liberatescyanogen and produces a peach- blossom coloured precipitate ofmercuric cupric bromo-cyanide.The addition of zinc cyanide to a boiling concentrated solution ofmercuric bromide yields the same compound and i t is evident thatits formation limits the action between mercuric bromide andcyanide and zinc cyanide and bromide whatever may be the arrange-ment of the atoms in the initial system. C. H. B.Mannose. By E. FISCHER and J. HIRSCHBERGER (Ber. 22,3218-3224).-The mannose employed in these experiments wasobtained from vegetable ivory nuts by a niodification of Reiss' method(Abstr.1889 687) instead of by the oxidation of mannitol. Com-parative experiments made with mannose from thc latter sourceshowed the complete identity of the two sugars. The method ofpreparation was as follows Sifted ivory-nut shavings (1 part) weredigested with 6 per cent. hydrochloric acid (2 parts) on the water-bath for six honrs filtered hot the residue pressed and again ex-tracted with water. The brown solution after treatment with animalcharcoal was neutralised with caustic soda solution and an excess ofphenylhydrazine acetate added. The resulting hydrazone was pnriORGANIC CHEMISTRY. 225fied and converted into mannose by the method previously described(Abstr.1839 481).Mu,nnonic Acid.-For the preparation of this acid a solution ofmannose (1 part) in water (5 parts) is mixed with bromine (2 parts)at the ordinary temperature frequently shaken and allowed toremain 24 hours after the bromine has dissolved. The latter is theneliminated in the usual manner and the resulting solution of man-nonic acid converted into the phenylhydrazide C12H18N20fi by Fischerand Passmore's method (this vol. p. 152) ; this forms small colour-less brilliant prisms which melt at 214-216" with decomposition,are soluble in hot water but sparingly in cold wa'ter or alcohol. Itmay also be obtained directly from ivory nuts in the following manner:The ivory-nut shavings are heated with 6 per cent.hydrochloric acid,and the solution treated with animal charcoal as previously described.The quantity of mannose in solution is determined by precipitating aknown quantity with phenylhydrazine and for every part of sugarfound 2 parts of bromine added to the solution. The whole isfrequently shaken until all the bromine has dissolved and thenallowed to remain. After evaporating off the free bromine the solu-tion is nearly neutralised with lead carbonate filtered precipitatedwith lead acetate solntion and again filtered. The filtrate may bethen converted into the hydrazide as before. The latter after re-crystallisation is decomposed by boiling baryta-water the liberatedphenylhydrazine extracted with ether. and the boiling liquid exactlyprecipitated with sulphuric acid.Tho filtrate on evaporation leavesa syrup which solidifiev to a slightly brown crystalline mass. Thisis extracted twice with a little alcohol and the residual white com-pound recrystallised from this solvent. The crystals obtained formstellate groups of colourless needles and hare the compositionC6H1006 and are therefore tlhe Zactone of mannonic acid ; this melts at149-153" is readily soluble in water but less so in alcohol. Itsaqueous solution is dextrorotatory [a]= = 53.81 and has a neutralreaction but quickly dissolves carbonates on boiling forming salts ofmannonic acid. The ccxlciiim salt (C6H1107)2Ca + 2H& formsmicroscopic prisms. The strontium salt with 3 mols. H20 crystallisesfrom alcohol in small prisms.The barium salt has not yet beenobtained crystalline.Mannonic acid is oxidised by nitric acid to a bibasic acid whichdiffers from saccharic and metasaccharic acids and seemingly alsofrom isosaccharic acid. This compound is undergoing further exami-nation.The authors have previously stated that mannose undergoes fer-mentation with yeast and they have been able to confirm t h i s by arepetition of the experiment with larger quantities. A 5 per cent.solution when mixcd with fresh yeast at the ordinary temperature,evolves carbonic anhydride in 10-15 minutes and in 24 hours thereaction is complete. Prom the filtered solution ethyl alcohol can beseparated by fractional distillation the yield seemingly being thesame as that from dextrose.The liquid obtained by boiling ivorynuts with 6 per cent. hydrochloric acid also ferments after neutra-lisation with lime although more slowly. As fkom 900-1001) ton226 ABSTRACTS OF OHEMICAL PAPERS.of such shavings are obtained yearly and these yield 33 per cent. oftheir weight of sugar it would seem that a commercial process forthe preparation of alcohol from this source might be successfullyfounded.Marinose is acted on by acetic chloride in exactly the same manneras dextrose. The acetochloromunnose obtained likewise forms a syrup,which is sparingly soluble in water but is decomposed by long-con-tinued boiling with the latter into mannose and acetic and hydro-chloric acids. H. G. C.Sugar from the Quebracho. By C. TANRET (Compt.rend. 109,908-910).-The bark of the quebracho (Aspidosperwm qwbracho)yields a sugar quebrachite of the composition C7HI4O6 which crystal-lises from alcohol in anhydrous rhomboidal prisms with a very sweettaste. It is very soluble in water and somewhat soluble in boilingalcohol but insoluble in ether. It melts a t 186-187" boils in avacuum and condenses in beautiful needles ; rotatory power [a!= =-80" ; sp. gr. a t 0' = 1.54. Quebrachite ferments only in contactwit.h beer-yeast and has no action on Fehling's solution but reducesammoniacal silver nitrate. It is not affected by boiling dilute solu-tions of acids or alkalis and gives no precipitate with basic leadacetate but is precipitated by ammonincal lend acetate provided thesolution is not very dilute.Monohydrated sulphuric acid dissolvesi t readily especially at loo" with slight discoloration forming que-brachisulphuric m i d a lavogyrate acid which yields soluble non-crjs-tallisable barium and calcium salts. When heated with acetic anhy-dride and zinc chloride it yields a crystalline derivative which meltsat 89'. With nitric and sulphuric acids it yields an unstable nitrin,and when heated with nitric acid it gives rhodizonic acid.When heated with hydriodic acid quebrachite yields methyl iodideand an inosite which crystallises from alcohol in very brilliant,slender efflorescent prismamtic needles soluble in 2.3 parts of waterat 12" very slight.ly soluble in I.oiling alcohol and insoluble in ether.It melts at 238" is somewhat less volatile than quehranhihe and hasa la?vorotntory power of [ajD = -55".With nitric acid it gives thein osit e react ion. C. H. B.Formation of Rafflnose. By F. HERLRS (Chem. Centr. 1889 ii,421-422 ; from Bohm. Zeit. Zucker-It'd. 13 455).-The author hassubjected cane-sugar to the action of calcium hydroxide a t varioustemperatures but without being able to detect any formation ofraffinose a result in agreement with t h a t obtained by Cech (Chem.Centr. 1889 i 682). He draws the conclusion that the formation ofrafinose takes place in the beet,root. He also confirms the correct-ness of Herzfeld's statement (ibid. $04)) that it is forrited by freezingthe beetroot. The author 6nds that the preservation of the beetrootfor too long a time favours the formation of raffinose.J. W. L.Melitriose and Melibiose. By C. SCHEIBLER and H. MITTELMEIER(Ber. 22 3118-3 124 ; compare Abstr. 1589 953).-Melitose,prepared from cotton-seed meal exactly as dkscribed by BertheloORGANIC CHEJIISTRI'. 227(Compt. rend. 103 533)' iR not changed by boiling baryta-water doesnot reduce Fehling's solution and crystallises unchanged from alco-hol. Berthelot's statement (Zoc. cit.) that melitose is decomposed byalcohol into raffinose and eucalyn is therefore incorrect and melitoseis identical with raffinose.When melitriose is treated with a dilute solution of invertin a t theordinary temperature for two hours it is decomposed into melibioseand levulose; but when it is kept for 36 hours at 40" with a con-centrated solution of invertin it is decomposed into dextrose galac-tose and levulose ; Berthelot's eucalyn is therefore identical withmelibiose.When melibiose is reduced with sodium-amalgam a t the ordinarytemperature the solution being kept as neutral as possible i t is con-verted into a substance ( m e l i b i o t i t e ) which does not reduce Fehling'ssolution but if a little of the solution is boiled for a short time withn few drops of sulphuric acid it acquires powerful reducing proper-ties galactose bc;.ng one of the decomposition-products of meli bio-tite.F. S. K.Molecular Weights of Maltose and of several Inulin-likeSubstances. By A. G. EKSTHAND and R. MAUZELIUS (Chena. CerLtr.,1889 ii 444 ; from Vetensk. Aknd. Forhandl. 1889 157).-The mole-cular formulte given below were determined by Raoult's method :-Anhydrous maltose C,zH22011.Triticin C:36H6& from the root ofDracmua riibra melts at 140" and has the specific rotation [a]D- -36.61.specific rotation [.In = - 41.07. Graminin C18H800.10 from Trisetuliialpestre melts a t 220" and has the specific rotation [.ID = -44.47.Irisin CssH1600so from Iris pseudo-acorus melts at 160" and has theRpecific rotation [.ID = -51.20. Phlein from Phleuin pratense,melts at 215" arid has the specific rotation [ a ] D = -47.94; themolecular weight could not be determined.Triticin from T r i l i c u m repens melts a t 160" and has theJ. W. L.Animal Cellulose. By R. ScHijrrzF (Chem. Centr. 1889 ii 588 ;from Mitt. pharm. Inst. Erhngen 2 Heft 280-281).-The authorhas examined the mantle of I'hallusia rnammillaris it being purifiedby boiling first with water shen repeatedly with 20 per cent.potas-sium hydroxide solution and 10 per cent. hydrochloric acid andfinally by digestion with hydrofluoric acid and hydrochloric acid.The white cellulose substance contained 43.47 per cent. of carbonand 6-85 per cent. of hydrogen.Solution of cupric oxide in ammonia dissolves the substance andsolution of iodine in zinc chloride or sulphuric acid Btairis it variouslyfrom red to violet. Nitric and sulphuric acids form an explosivenitrate with it which is somewhat soluble in ether.When heated with 10 per cent. sulphuric acid in a closed flask at loo" a substance is formed which reduces Fehling's solution andwhich ferments with yeasf with formation of carbonic anhydride.The ether extract of the mantle contained small quantities ofcholesterin fat and free fatty acids ole'ic valeric and probably alsopalmitic and stearic acids228 BBSTRACTS OF CHEMICAL PAPERS.The mineral matter included in the cuticle freed from fat consistedof Silica 2.76 alumina 9.52 ferric oxide 15.81 phosphoric acid (com-bined with iron and aluminium) 12.72 calcium phosphate 3-91,calcium carbonate 49.22 and magnesium carbonate 6.03 per cent.J. W.L.Lignin. By G. LANGE fZeit. physiol. Chem. 14 217-226).-Theinvestigation of the l i p i n of beech and ash wood previously recorded(Ahstr. 1889,1235) has in the present research been extended to thatof pine wood (Pinus d i e s L.).The lignin was prepared from this bythe same methods as those previously employed ; it was found to con-sist of 32 to 55 per cent. of cellulose two brown substances calledlignic acid ; and as a result of fusing with alkali formic acetic andtraces of higher fathy acids oxalic acid catechol prot,ocatechuic acid,ammoi,ia and traces of higher bases were obtained. No succinicacid was obtained as Erd.niann stated (Annulen 138 1). The per-centage compositions of the lignic acids obtained from the threevarieties of wood were as follows :-Lignic acid soluble in alcohol.C 61.475; H 5.48Insoluble in alcohol.Beech .... . . C 59.04; H 5.37Ash .. .. .. . . 61.61 5.47 58.83 5.15Pine.. .. .. . . 61.28 4.95 60.51 5.22Experiments designed to ascertain the constitution of these sub-stances were unsuccessful. W.D. H.Gum Tragacanth. By J. OGLE (Pharm. J. Trans. [3] 20 3).-A sample of Syrian tragacanth yielded moisture 18.92 soluble gum35.94 ash 2.73 and insoluble gum 42.39 per cent. The precipitateproduced in the aqueous solution by the addition of alcohol was foundnot to be identical with arabin and no evidence of the presence ofstarch could be obtained. R. R.Absence of Rotatory Power in Amine Salts. By J. A.LE BEL (BuZl. SOC. Chirn. [ 3 ] 2 305).-The order in which thesubstitution of radicles is effected in the NH3 molecule does not in-fluence the nature of the resultin? amine from which it follows thateither the molecule alters its confipurstion according to the substitu-tion or that intramolecular migration of the substituted radiclesoccurs ; if then in the former case the radicles :we definitely located 8compound of the formula CI*NHR'R2RJ should exhibit rotatorypower since R' R2 and R3 cannot be in the same plane.With a viewto determine t h i s experimentally the author prepared methylet.hy1-propylamine hydrochloride which he found to be devoid of rotatorypower and consequently the first hypothesis is untenable.T. G. N.Propargylamine and Derivatives of Allylamine. By C. PAALand C. HERMANN (Bey. 22 3076-3085).-I)ibromopropybaminehydrobromide C3H,Br2*NH2,HBr is obtained when an ice-cold aqueoussolution of allylamine is slightly acidified with concentrated hydro-bromic acid and then treated with bromine (1 mol.) ; the yield iORGANIC CHEMISTRY.229quantitative. It separates from hot water in well-defined transparentcrystals melts a t 164" and is only sparingly soluble in hot a,lcohol m dcold water but readily in hot water; i t is not decomposed by mode-rately concentrated sulphuric acid even when boiled therewith forhalf an hour. The salt ( C3H,Br2*NH.!),,2HBr,PtC14 crystallises inorange-red p1at.es and decomposes at 200° but without melting. Thesalt C3H,Br,*NH2,HBr,AiiC13 crystallises in dark-red needles me1 tsat 124" and is moderately casily soluble in water.Brornallylamine hydrobromide melts at 175" and not a t 223-22&,as previously stated (cornpaye Paal Abstr. 1889 117).In prepa.ring bromallylaniine salts by the method previously de-scribed it is better to neutralise the aqueous distillate containingthe base with a dilute mineral acid instead of collectiug the dis-tillate in excess of acid; in this way the formation of additive-compounds is avoided.Tribromopropylarnine hydrobromide CsH4Br3*NH?,HBr prepared bytreating bromallylamine hydrobromide with bromine in well-cooled,aqueous solution crystnllises from water in large colourless platescontaining water of crystallisation ; the crystals effloresce on exposureto the air and melt a t 210" with partial decomposition. It crjstal-lises from alcoholic ether in slender needles and is moderately easilysoluble in hot alcohol.A base C3H,BrzN or (C3H,Br2N) is formed when tribromopropyl-amine hydrobromide is treat,ed with alcoholic.potash ; on distillingwith steam neutralising the distillate with hydrobromic avid andconcentrating t.he solution the hydrobromide C3H5Br,N,HBr is ob-tained in colourless crystals. This salt melts at 214" does notcombine with bromine and is readily soluble in water but only spar-ingly in alcohol. The salt ( C3H,Br2N),,2HBr,PtCI crystalliscs ingolden scales and decomposes a t 2Y0° but without melting. Thesalt C3H,Br2N,HBr,AuCl3 forms smaJl yeilow well-defined crystals.The free base is a yellowish unstable oil ; it does not give the carbyl-amine react,ion and it yields an oily nitrosamine which is insoluble inwater and dilute mineral acids.Proparg y Eami?ie C H 3*N H 2 is formed when a dibrom opropyl aminesalt is heated for 14 hours a t 100" in a sealed tube with an alcoholicsolution of sodium ethoxide (4 mols.).The contents of the tube aret,ransferred to a flask and hcated on the water-bath until most of thealcohol has distilled t'he distillate being collected in an alcoholicsolution of oxalic acid. The acid oxalate C3H3*NH2,C2H204 separatesduring the process in slender colourless needles which are perfectlypure i f the above conditions are observed. It is only very sparinglysoluble in boiling alcohol b u t readily in water from which i t sepratesin large plates melting a t 143" ; its dilute aqueous solution gives apurple-red coloration with auric chloride. The yield of the oxalateis about 51 per cent. of the theoretical; the residue in the flaskcontains not inconsiderable quantities of a non-volatile base.Allattempt,s to isolate propargylamine were unsuccessful ; it seems to bemuch more readily soluble in water and concentrated alkalis thanammonia or met'hylamine. Propargylatnine silver is precipitated whena solution of silver nitrate in excess of ammonia is added to an ammo230 ABSTRACTS OF CEEMICAL PAPERS.niacal solution of the oxalate ; it is a colourless compouiid darkensgradually on exposure to the air and explodes when heated. Thepicrate C,H,*NH2,C6H,N307 prepared by precipitating an alcoholicsolution of the base with picric acid ~ryat~allises in large reddishplates melts at 189" and is insoluble in ether. The 7~ydrochloride,C3Hl.NH2,HC1 prepared by passing hydrogen chloride into an alco-holic solution of the base crystallises in colourless plates is readilysoluble i r i water and alcohol and decomposes on exposure to light.The hydrobromide C,H,*NH,.HBr crystallises in thin colourlessplates begins to soften at 130" melts a t l'il" and decomposes onexposure to light.Met h?ylpropargylamine k y d ~ i o d i d e C3H3*NHMe,HI is obtained whenan alcoholic solution of propargylamine is treated with methjl iodide ;it crystallises in long colourless very hygroscopic needles melts a t83" and decomposes on exposure to light. The free base is a yellowish,volatile oil of ammoniacal odour. The ozalafe C4H,N,C2H,04 crys-tallises from dilute alcohol in colourless needles melting a t 141".Eth ylpropargy lnmine hydriodide crystallises in long needles ; propyl-prol)argylnmine hydrobromide crystallises in plates melting a t 180".Isoomylp~opargylamie is formed whm isoamyldibromoprnpylRminehydrobromide is treated with sodium ethoxide as described above ;the contents of the tube are treated with a little water to dissolve thesodium bromide the solution saturated with potassium carbonate,the supernatant alcohol separated dried over potash and distilled thedistillate being collected in an alcoholic solution of oxalic acid.Theoxalate C,H,*NH.C5H,,,C2H20 is thus obtained in small colourlessneedles melting at 204"; it crystallises from water with 1 mol. H,O.The free base is liquid. The hydrobromide C8H15N,HBr crybtallisesin uacreous plates melting a t 186". F. S. K.Action of Heat on Chloral-ammonia.By A. B ~ ~ H A L andCHOAY (Compt. rend. 109 817-820).-Personne showed that whenchloral-ammonia is heated at 100" it yields chloroform and formamide,but the decomposit,ion is not complete. If chloral-ammonia is heatedin a retort at 100" until chloroform ceases to distil orer a blackviscous mass with a slightly alliaceous odour is left ; this containsammonium chloride formamide and some other compounds.If this residue is boiled with strong alcohol the latter on coolingdeposits crystals of the chloralim ide described by Pinner andFnchs the yield being about 5 per cent. of the original chloral-a mmonia. Chloral im ide forms I on g colourless tasteless needlesslightly soluble i n water more soluble in alcohol very soluble inether.It is decomposed by a cold aqueous solution of platinicchloride with formation of chloral and ammonium platinochloride. Itis riot affected by water in sealed tubes a t 150° but a t 170" decom-poses completely into chloroform and formamide which undergopartial decomposition and yield some ammonium chloride carbonicanhydride and hydrochloric and formic acids. Chloralimide in dosesof 0.25 to 0.50 gram has remarkable antipyretic and analgesic pro-per tie s.If the residue in the retort either before or after extraction w i t ORUANIC OHEMISTRY. 231alcohol is boiled with a large quantity of water the liquid depositscrystals on cooling and if these are purified by treatment withanim.11 charcoal and recrystallisntion frotn alcohol the compoundC,CI,H,N,O is obtained in long colourless tasteless inodorousprisms very slightly soluble even in boiling water more soluhle inalcohol especially if heated and very soluble in ether.It melts at21 6-217" and almost immedistely decomposes with evolution ofgas. It is partially decomposed by platinic chloride and whenheated with excess of acetic anhydride i t yields an acetgl-derivativeof the composition C,CI,H4AcN2O2 which crystallises in long needlesvery soluble in acetic acid almost insoluble in water and only slightlysoluble in alcohol or benzene. Tbis derivative is not affected by aneutral or acid alcoholic solution of platinic chloride; it is stableeven a t a high temperature but does not melt without decomposing.The first compound C4C1?H5N2O2 is prohably didehydrotrichloro-dihydroxypiperazine formed by the condensation of 2 mols.ofchloral-ammonia with elimination of 3 mols. of hydrogen chloride,but this view requires further investigation. C. H. 13.The Indian Grass Oils. By F. D. DODGE ( A m e r . Chem. J. 11,4.56-469).-These are a t least five in number namely oils of citron-ella lemon-grass Indian or Turkish geranium ginger-grass andvetivert or cus-cus. They are derived from various tropical grassesof the genus Andropogon but there is some confusion as to theparticular species from which the individual oils are obtained.The commercial varieties are often adulterated withkerosene ; the pure oil is a clear greenish-yellow liquid with a sharpburning taste and a strong aromatic odour. Its sp.gr. a t 16" is 0.8770,at 26.5" 0.8750. It distils betneen 200" and 240" leaving 10 per cent.of a thickoily residue having a pungent odour. It gives most of thereactions of aldehydes combining with hydrogen sulphites and withphenylhydrazine although not with ammonia; i t also reacts withacetic and benzoic chlorides and gives a mirror with an ammoniacalsilver solution. Two litres of the oil were distilled in a current ofsteam and collected in fractions of 1100 C.C. and 4UO c.c. the residueof 500 C.C. not being readily volatile. The first fraction (1100 c.c.)was treated with a solution of sodium hydrogen sulphite the mixturebeing kept cool with ice and water. The liquid solidified to a whitemagma and the sodium hydrogen sulphite compound was thenpressed between flannel and washed wit,h ether; the filtrake yielded3.50 C.C.of residual oil. The sodium hydrogen sulphite compoundwas mixed with dry sodium carbonate and distilled in a current ofsteam; about 700 C.C. of aldehyde was thus obtained. This wasshown by analyses and a vapour-density determinat,ion to have theformula CloH180 and is thus isomeric with borneol and geraniol.l'he author names it citronellic aldehyde and considers i t t o be13- met h y 1 - 6 -is o b u t y 1 a.11 y 1 ace t a1 d e h y de C H P,S C H C H Me C H C H 0,since this formula is most in accordance with its reactions. It uniteswith 2 atoms of bromine and when reduced with sodium amalgamand acetic acid i t yields citronellyl alcohol C,,H,,O boiling a.t225-230" ; this decolorises bromine solution and has a pleasautCitronella Oil232 ABSTRACTS OF CHEMICAL PAPERS.odour of roses.It forms compounds with phenylhydrazine withaniline and paratoluidine and with acetic acid but these productshave not yet been isolated. It is dextrorotatory and when oxidised,appears to yield fatty acids ; with potassium permanganate it yieldsa mixture of acids smelling strongly of ordinary valeric acid. Whentreated with phosphoric anhydride some large colourless plates(melting a t 140") were deposited and two oils formed one boiling a t175" which was shown by analysis to be an irniiure terpene and oneboiliiig above 300° which had a pleasant odour resembling the high-boiling fractions of citronella oil.The 350 C.C.filtered from the sodium hydrogen sulphite compoundsyielded (1.) 75 c.c of a light oil boiling a t 177" and having a pleasant,citrene-like odour ; this was analysed and its vapour-density deter-mined the results indicating that it was an impure terpene; (2.)120 C.C. of a thicker oil of rose-like odour boiling a t 222-224" andof sp. gr. = 0.8741 at 2G*5" which appeared to be citronellyl alcohol ;(3.) 100 C.C. boiling above 240" dark brown viscid and having apeculiar odour.The residual 500 C.C. of the original oil not readily volatile in steamwas treated with sodium hydrogen sulphite and yielded about 10 C.C.of citronellic aldehyde and a residual 475 c.c. which when distilledbehaved like the residue from the other sulphite precipitate but yieldsa much larger amount of high-boiling products which oxidise readi]~,and are difficult to treat. Citronella oil therefore contains citronellicaldehyde and alcohol together with a terpene and oils boiling above240".Derivatives of Tetrachlorodiacetyl and of Tetrachloracetone.By S.LEVY F. C. WITTE and A. CURCHOD ( A w d e n 254,83-114;compare Abstr. 1889,1160 and 1136).-The compound C,,H,,Cl,N,O,prepared by boiling tetrachlorodiacetyl (Abstr. 1889 390) wit,hexcess of phenylhgdrazine in alcoholic solution combiries with phenyl-hydrazine when warmed therewith with evolution of ammonia; i t isdecomposed by alcoholic potash with liberation of aniline and whentreated with fumingnitric acid i n sulphiiric acid solution i t is convertedinto a yellow compound which is precipitated on adding water.separates incrystals when tetrach!orodiacetyl (1 mol.) is treated with orthophenyl-enediamine (1 mol.) in hot aqueous solution. It crystallises fromalcohol in small colourless nacreous plates and from benzene inlarge well-defined triclinic plates u b c = 0.8198 1 0.9698 ;a = 92" 4' p = 121" 56' y = 85" 22' ; it melts at 177" and distils at ahigh temperature with partial decomposition.It is readily soluble inhot chloroform alcohol and benzene but only sparingly in the coldsolvents and in ether and is insoluble in water ; it dissolves in concen-trated sulphuric acid with a yellow colorationThe compound C2H,(NH.CHCl.CO.CO.CHCI,) can be obtainedby gradually adding an aqueous solution of tetrach1orodiacet)plto an ice-cold aqueous solution of ethylenediamirle but it is bestprepared by dissolving the t w o substances in 95 per cent.alcohol,The study of these oils is to be continued. C. F. B.N:F-CHCI,C6H4<N :C*CHCI,' Tetrach lorodimet? y lquinoxalh2eOROXNlC CHEMISTRY. 233and warming until the colour of the solution changes to red. Itcrystallises f'roni dilute alcohol in colourless slender needles melts a t222-223" with decomposition and is readily soluble in alcoliol ether,chloroform and benzene but only sparingly in light petroleum andalmost insoluble in water.Trichlorcmidod;acstyl CHCl:.CO.CO*C HCl*NH prepared by gradu-ally adding ammonia (3-4 c.c.) to a dilute alcoholic soiution of tetra-chlorodiacetyl(2 grams) and heating the mixr;urc to boiling crystallisesfrom benzene in colourless needles melts a t 127" and is readily solublein alcohol and ether but only moderately in water or benzeneand very sparingly in light petroleum.It has feeble basic properties,and is decomposed by soda with evolution of ammonia. When treatetiwith hydrochloric acid it is converted into two substances one ofwhich crystalliscs in large prisms melting a t l57" the other in small,colourless needles of lower melting point.TetraclLEo~oiliacet?/~cet~ ldicyadit$r. in,C H C=l,*C (OH) (CN ) *C (OH) (CN ) CRC 12.is formed when tetrachlorodiacetyl is heated with excess of concen-trated hydrocyariic acid at 30-40' for 4 to 5 hours. The product is cx-tracted with ether and repeatedly treated with light petroleum tofree it from the monocyanhydrin.It separates from a mixture ofether and l i g h t petroleum in spherical aggregates sinters together a tabout 110" and melts at about 135-137" with decomposition. It isreadily soluble in water ether and alcohol but only sparingly i l lcarbon bisulphide chloroform arid benzene and insoluble in lightpetroleum. It is decomposed when warmed with water a t a tem-perature below 100". The dlacetyl-derivative C,,H,Cl,N,O preparetlby heating the cyanhydrin with acetic chloi-ide crystallises fronidilute alcohol in colourless needles melts at 1 6 3 O decomposes ata higher temperature and is readily soluble iu ether alcohol andchloroform but only spdringly in bemene and boiling water autlinsoluble in light petroleuin.crystallises from benzene in which it is readily soluble in co1uurle.-splates melts at 110-111" and decomposes a t about 153".r i 1 he mo?iocyanhydri?i CHCl,*C(OH)(CN).CO*CHCl (see above),CO-7 (OH)*CHC12Tetrach lorodiinethy Etartarimide NH<CO.C (OH) .(-H(J2' is Oh-tained together with a small quantity of a ;ellowish acid when thedicyanhydrin (2 grams) is heated a t 110" for two hour with 35 percent. hydrochloric acid (15 c.c.).It separates from n mixture ofbenzene and ether in dendritic crusts melts a t 239-240" and isreadily soluble in alcohol ether and hot water but almost insolul,lein chloroform benzene and light petroleum. l'he ti.iacetyZ-dei.ivati\ e,C,,H,,Cl,N O crptalliseu from dilute alcohol in small colourlessprisms or needles melts at 176-177" with decomposition aiid isreadily soluble in alcohol and ether but only sparingly in hot aridinsoluble in cold water.l't:tradhlorudinzetIiyItartara )wide,C H C 12. C (0 H) ( C 0 N H,).C( 0 H) ( C 0 N H 2 ) * J H C12,VOL LTIII. 232 ABSTRACTS OF CHEMICAL PAPERS.is formed when concentrated sulphuric acid is gradually added to aconcentrated glacial acetic acid solution of t h e dicyanbydrin and themixture warmed gently until the crystals which separate from thesolution have redissolved. It crystallises from boiling chloroform inslender colourless needles melts at 183' and is readily soluble inwater alcohol and ether but only very sparingly in boiling chlom-form and insoluble in light petroleuiri.It is converted into the imideby 35 per cent. hyd-rochloric acid a t 110" or when warmed withsulphuric acid i n glacial acetic acid solution.Tetrachlorhydroxyisobutyramide (m. p. 156") i s best prepared fromtetrachloracetonecpnhydriu (Abstr. 1889 1136) by dissolving thelatter i n glacial acetic acid adding concentrated sulphuric acid andheating t o boiling for a few minutes. I t crystallises from etlier infour-sided pyramids is readily soluble in alcohol and moderatel!.easily in benzene b u t only sparingly in chloroform and insoluble inlight petroleurn.The compound C4H,C13N02 probably the amide of trichloropropyl-enecxidecai boxylic acid is obtained when the preceding compound istreated with sodium carbonate in the cold.It crystallises in needles,mclts at l Z " and is readily solnble in ether alcohol chloroform andben7ene moderately easily i n carbon bisulpbide and sparingly inlight petroleuin.TehachlorhydToq isobu tlyric acid 0 Ha C ( CH Cl,) !.C 0 0 H preparedby heating the amide a t 110-120" with hydrochloric acid of sp. gr.1.16 crystallises from light petroleum in needles melts at 69-71",and is readily soluble in water ether alcohol chlo~oform and benzene,but only sparingly in carbon bisulphide and light petroleum. Thepotassium salt C4H3C140.,K crystallises from water in transparentprisms and is very readily soluble in water but only sparingly inalcohol ; i t is decomposed by hot water.ByV. ACCER and A. B ~ ~ H A L ( B u l l .Sor. Chiin. [3] 2 144-145).-To pre-pare acetic chloride sulphur (1 mol.) or sulphur dichloride (1 mol.)is placed in a fiask with glacial acetic acid (2 mols.) and chlorine ispassed into the mixture cooled by ice and salt until no fulthvrabsorption occurs ; after distillation of the resulting product a t 60",and agitation of t h e distillate with mercury or powdered copper toremove a sulphur compound subsequent fractionation jieltis apure product; 600 grams of acetic acid gave 500 grams of aceticchloride.Chlorscetic acid is obtained under conditions similar to those above,except that the mixture of sulphur and acetic acid is to be boiled:chloracetic acid is obtained in a very pure condition only traces ofacetic chloride and of acetic. anhydride being produced ; 800 grams ofacetic acid yielded after 12 hours' chlorination 1000 grams of themonochlorinated derivative. T.G. N.F. S. K.Preparation of Acetic Chloride and Chloracetic Acid.Action of Triethylamine on Ethyl a-Bromobutyrate andEthyl a.Bromopropionate. By M. E. DuvrrmEn (Bull. SOC. Chirn.[YJ 2 139-142; compare Abstr. 1888 !249).-'I'he action of triOROASIC CHEhl ISTRT. 233ethylamine (3 mols.) on ethyl a-bromobntyrate (1 mol.) at 100"yielded a considerable amount of a-hydroxybutyric acid and this wasaccompanied by a sm2ll quantity of butyric and crotonic acids,whilst traces of tetrethylammonium hydroxide were produced.The substitution of ethyl a-bromopropionate for ethyl a-bromo-butyrate determines the production of much lactic acid and of smallquantities of tetrethylammonium hydroxide and of betaine (1 percent.) in which latter respect the bromo-derivative differs from thecorresponding chloro-compound from which under similar conditions,Bruhl could not obtain betiine (this Journal 1576 i 699).T. G.N.Preparation of Alkyl Salts of p-Ketonic Acids. B y J.HAMONET (Bull. SOC. Claim. [3] 2 334-337; compare Abstr. 1888,235).-The product of the action on a normal acid chloride (1 mol.)of sublimed ferric chloride (2 mols.) is poured into cold absolutealcohol and when the reaction is completed the upper layer of liquid,which contains the salt of the (%ketonic acid is dried and frac-tionated.Propionic chloride yields by this process ethyl a-propiopropionate,a colourless liquid of sp.gr. 0.9987 a t 0" boiling at 196-197".Butyric chloride and heptoic chloride when similarly treated yieldrespectively ethyl a-butyrobutyrate boiling a t 217 -219' and e t h y la-hpptohepfoate boiling a t 290-292".As ethyl ,phntyrobutyrate when treated by Ceresole's method,yields but yrobutyric acid whose barium salt decomposes on warminginto a carbonate and butyrone i t is to be regarded as a P-ketonate.Jsobutyric acid yielded by the author's method valerone and ethylcaZrrocaZPrate boiling at 238-2134" and of sp. gr. 0.9492 at 0".From a mixture of propionic and butyric chlorides the author ob-tained by this method ethyl propyl ketone boiling a t 1-22' and ethyla-p?*opiobzityrcrte boiliilg at 207-209" and of sp. gr.0.9884 a t 0".The theory of the reactions is discussed. T. G. N.Ethylenelactic Acid from Flesh Extract. By E. KLINENRO( R e r . 22 3182-3183).-The author corrects the statement of Sieg-fried ( B e y . . 22 2711) that he (Klimenko) was unable to isolate anamorphous zinc salt from lactic acid obtained from flesh extract.F. S. I<.Alkyl Hydrogen Oxalates Dichloroglycollates and Chlor-oxalates Tetralkyl Oxalates. By R. ANSCHGTZ (ArtmzZen 254,1-42 ; compare Abstr. 1886 785 and 101 l).-The alkyl hydrogenoxa.lates gradually undergo spontaneous decoiuposi tion into the neutisals ilt and oxalic acid ; they decompose potassium acetate i n alcoholicsolution forming alkyl potassium oxalates.MethyZ phenyloxamate NHPh*CO.CC;OPJe prepared by heatingmethyl oxalate with aniline crystallises from alcohol in whic-h i t isreadily soluble in large yellowish plates and from light petroleumin small colourless needles melting at 114'.'l'he corrcispoildingp~opyl salt NHPh-COCOOPr crystnllises from alcohol i n c,,louI less r 236 ABSTRACTS OF CHEMICAL PAPERS.needles melts a t 92" and is readily soluble in alcohol but onlysparingly in light petroleum. The isopropyl salt crystallises fromlight petroleum in long white silky needles and melts a t 52". Thei s o t u f y l salt forms mall colourless plates melts at 65". and is readilysoluble i n alcohol. The an2y1 salt crystallises from light petroleumin needles and m e h - a t 60".Bimethyl dichloroglycollate OMe-CCl,*COOMe prepared by heat iiigmethyl oxalate with phoaphoric chloride f o r 1 2 to 18 hours a t130 -135" and fractionating the crude product under reduced pres-sure is a colouraess liquid boiling at 179-181" (at 72" about12 mni.).Dli.cobutyZ dicldoroglycollate C,H7g0.CC1z-COOC,H7 is a colourlessliquid boiling a t 128" {about 14 mm.).The alkyl cliloroxalates can be obtained by distilling the dislkyl(1 i chlorogl y collat es under the ordinary pressure.Methyl chloroxdlate COCkCOMe is best prepared by heating di-methyl dichloroglycollate at 200-215" for 40 hours ; i t is a colourlessliquid boiling at 118-120".The corresponding ethyl salt COCl-COEt boils a t 135-136" (at30" about 10 mm.) the normal propyl salt a t 153-154" (at 50",about 12 mm.) the i s o h d y l salt a t 163-165" (at S2" about 10 mm.),and the amyl salt a t 183-185" (at 68" about 10 mm.).Tetralkyl-derivatives of oxalie acid can be obtained by treating thedialkyl dichloroglycollates with .sodium compounds of alcohols inalcoholic ethereal solution.Tetramethyl oxaZate C(OMe)&OOMe is acoloudess liquid boiling at75-76" (ahout 12 mm.).The corresponding ethyZ salt C(OEt),.COOEt,boils at 98" (about 12 mm.) the normal propyl salt at 256-257" (at12!)-1W0 about 12 nim.) the isobutylsalt a t 146" (about 10 mm.),and the amyl salt at 190" (about 10 mm.).Dimethyl diethyl oxalate OMe*C( OEt),*COOMe is formed whend imetliyl dichloroglycollate is treated with sodium ethoxide inethereal solution ; i t boils at 90-92" (about 13 mm.). If the reactionis carried out in alcoholic ethereal solution a liquid boiling a t945-965" (about 12 mm.) probably methjl triethyl oxalate isobtained.When dimdhyl dicblorog€ycollate is heahed with oxalic acid atabout 50" carbonic oxide carbonic anhydride and hydrogen chlorideare evolved and tlie residue consists of methyl oxalate; other di-alkyl dichloroglycollstes could probably be converted into the corre-sponding alkyl oxalate in like manner.When teti ameth.yl oxalate is treated with phosphoric chloride itis converted into methy 1 oxalate with evolution of methyl chloride ;tetrethyl oxalate yields ethjl oxalate u d e r the same conditions.F. S.K.Constitution of Succinic Chloride. By W. 0. EMERY (Bey. 22,3184- ilY6). - Met hgl snccinate prepared by treating succinicchloride with sodium methoxide in ethereal solution is identical withthe compound obtained by heating silver succinate with methyl iodideat 100° ; i t melts tit 19" and boik at 8u" (10-11 mm.).F.S. KORGA4hrIC CHEYISTRY. 2.3 7Substituted Succinic Acids. By C. A. BISCHOFF (Be).. 22,31 79-3180) .-The author has hydrolysed a number of ehhereal s Lit'sof alkyl- and beczyl-isobu tenylti*icarboxylic acids ; two isomeric acidswere obtained in every case. A large number of ethereal salts ofother unsaturated tricarboxylic acids will be examined in this direc-tion. F. S. K.Synthesis of Aconitic Acid from AcetylenedicarboxylicAcid. By J. M. LOVBN (Bey. 22 3053-3056).-When dibromo-succinic acid is boiled for a long time with a slight excess ofalcoholic yotssh it is converted into oxalic and nconitic acids.Acetylenedicarboxyiic acid under the same conditions gives thesame products so that the bromosuccinic acid is first converted intoacetylenedicarboxylic acid ; the yield of aconitic acid is 30 per cent,.o r more of the acetylenedicarboxylic acid employed.I?. 8. K.Oxidation of Ketones by Potassium Permanganate inAlkaline Solution. By G. GLUCICSMANN (nlonatsh. 10 7 70-782) .-Potassium perrnanganate has no action on pinncoline in cold or warmneutral solution; but when the ketone (PO parts) suspended inwater is gradiinlly treated with a mixture of potassium perniangannte(63 parts) and sodium hydroxide (20 parts) dissolved in water( 2 litres) oxidation takes place the products being the until nowunknown trhnethyZpyruuic acid CGH,,,O and a little trimethyl-acetic! acid.The new acid crystallises in colourless irregular-pointedprisms having a peculiar acid odour is sparingly soluble in cold,hut readily soluble in hot water and in ether is fairly soluble inbenzene cilrbor1 bisulphide chloroform and carbon tetrachloride isvolatile in a current of steam melts a t 90-91" and has the constitu-tion CMe.3. COCOOH.With phenylhydrazine trirnet,hylpyruvic acid forms a compoundC,2H,6NL02 which crystdlises from dilute alcohol in long pale-yellow needles and melts a t 157-158" with evolution of carbonicanhydride and formation of aniline. On heating with a 33 percent. solution of hydrochloric acid trimethylpyruvic actd is notYegenerated but an aldehyde probably that of trimetliylaceticacid is the product.The calcium salt of trimethylpyruvic acid,(C6H903)rCa + 3H,O is very soluble in water; the sodium salt isanhydrous and crystallises in long colourless rhombic plates ; thesilver salt which is also anhydrous in gleaming scales.Trimethylpyruvic acid is converted into trimethylacetic acidwhen oxidised with silver oxide or with potassium dichromate ant1sulphuric acid. On reduction with eight times its weight of 4 percent. sodium amnlgam it is converted into trimethyleth~lidenelactil:~ c d CMe.3*CH(OH).COOH in nearly theoretical quantity. This acidforms colourless probably monosymmetric crystals (u b c =1.45 1 1.10 qprox.) melts a t 87-88° is readily soluble in waterand in ether and gives copper silver and zinc salts which are notvery characteristic.Thc oxidation of pinacoline to trimethylpyruvic acid is not i238 ABSTRACTS OF CHEMICAL PAPERS.accordance with Popow's rule for the oxidation of ketones and bheauthor to explain the reaction supposes that in the operatmion anintermediat,e condensation-product CMe3.CO*C tl :CMe*CMe is formedwith elimination of 1 niol.of water and that this condensation-pro-duct on oxidation with 3 atoms of oxygen is converted into tri-methylpyruvic acid aad pinacoline the latter again undergoingthc condensation and oxidation processes. The author has alsosucceeded in obtaining pyruvic acid by the oxidation of acetone withperniangnnste i n alkaline solution and suggests tha,t the formation oftrimethylp~ruvic acid from pinacoline may perhaps be a typicalreaction.G. T. 31.Isomeride of Tricarballylic Acid. By E. GUINOCHET (Compt.q-end. 109 906-908).-The action of sodium amalgam on the tri-bromotricarballylic acid formed by the action of bromine on aconit,icacid yields an isomeride of tricarballylic acid. It crystallises in con-fused almost opaque macled prisms and melts at 181" ; carballylicacid melts at 15$" and crystallises in large perfectly transparentprisms. It is only slightly soluble in water whilst carballylic acid isvery soluble. Its barium salt is cr.ystallisable anhydrous and some-what soluble in water; the calcium salt crystallises with 12 mols.H?O in long hard trmsparent efflorescent prisms.C. H. B.Fucusol. By K. BIELER and B. TOLLENS (Bey. 22 3062-3063).Constitution of the Aromatic Nucleus. By S. A. SWORN(€'Ail. Mag. [ 5 ] 28 4 0 2 4 1 5 and 443-451).-Arguments arebrought forward in favour of Thomsen's octahedral formula forbenzene (Abstr. 1887 362) these being chiefly based on the evidenceof direct linkage between symmetrically disposed carbon-atoms(para-linkage). In some cases arguments derived from the studyof pyridine-derivatives are applied by analogy to the derivatives ofbenzene the author considering that this is justified by the result ofrecent researches. It is first shown that the central nucleus of ant)hra-cene is truly aromatic and that in t h i s nucleus the carbon-atoms aredirectly linked to one another. The abnormally low molecularvolume and absorption of ultra-violet rays by anthracene the oxida-tion of anthracene to a substance of the yuinone type and the oxidationof acridine t'o a quinoline-derivative are all advanced in favour of theabove views.The diketonic nature of quiiione and its behaviouron reduction are best explained on the assumption of a para-linkage,the author being of opinion that when a para-linkage is broken tbenmdeus opens out into a hexagonal ring and the remaining para-linkages are se-c-ered with the formation of olefinic bonds this viewbeing supported by Baeyer's work on the additive compounds of tere-phthalic acid. The fwmulae of Meyer and Ladenburg representbenzene a s containing para-linkages but the optically active coninewould have no asymmetric carbon-atom in the symbol derived fromthese formule a requirement which is however satisfied by that of'l'homsen.In the same \my symbols for naphthalene and fluorent:-A claim for priority. (Compare Illaquenne this vol. p. 33.ORGANlC CHENISTRT. 239cannot be satisfactorily derived from the formulae of Meyer andLadenburg but can be readily deduced from the Tbomsen formula.An objection to the Thomsen formula which the author himselfraises is tlhat were the configuration of the benzene-molecule as awhole oct,ahedral we should expect the crystals of benzene t o belongto the regular system whereas they are rhombic. It is considered,therefore that the above formula requires still further deveiopmentbefore it caii be brought into accordance with all the facts.H.C.Paracyanobeneyl Chloride and its Derivatives. By W.MELLINGHOFF (Ber. 22 3207-321f).-Paracyunobenzl/l chloride,CN*C6H,*CHzC1 is obtained in a similar manner to orthocyanobenzylchloride (Gabriel and Otto Abstr. 1887 lo%) b,y passing chlorineinto paracyanotolnene nearly at its boiling point until the weight hasincreased 30 per cent. allowing to cool and recrystnllising thesolid portion from alcohol. It forms colourless well-developed,rhomblc prisms a b c = 0.7495 1 0.4314 melts a t 79*5" boilsat 263" (uncorr.) and is sparingly soluble in hot water more easilyin alcohol ether chloroform and benzene.Paracyitnobenxyl cyanide CN*C6EL4.CH2*CN is formed when theabove compound is treated with potassium cyanide. It crystallisesfrom alcohol in needles melts a t loo" boils above 360" and is slightlysoluble i n hot water more readily in alcohol ether and chloroform.It is the dinitrile of homoterephthalic acid into which it may be con-verted in the manner shown below.There are seven possible inter-mediate products all of which have been prepared.Paracyanophetzylacetamide CN*C6H4.CHz-COXHP is prepared bywarming the dry powdered dinitrile with 38 per cent. hydrochloricacid (15 parts) until effervescence commences. It separates fromdilute alcohol in crystals which melt at 196.5 (uncorr.) and issoluble in hot water and alcohol. In addition to this compound para-cyanophenylacetic acid and a substance of unknown consfitution,CnH,,N are also formed.w- ChZoroparatoZuamicle CONH2*CGH4*CHzCI is obtained by allowingpaxacyanobenzyl chloride to remain with concen trahed sulphuric acidin the cold for 12 hours.It is a white crystalline precipitate,melts at 173" (uncorr.) and is soluble in the common solvents.w-Cyarzopal.atoluat,Licle CO NH2.C6H4.CH2*CN is formed by heatingthe foi egoing compound with potassium cyanide. It crystallises fromalcohol in small colourless plates melts a t 182" (uncorr.) and isreadily distinguished from the isomeric paracyanophenylacet,amideby its appearance.Paracy anophen y lacetic acid CN* C,j€€:1*CH2* C 0 0 H is prepared byheating paracyariobenzyl cyanide with fuming hydrocliloric acid untilthe temperature has reached 105" and then almost neutralising withammonia.It forms prismatic crystals melting a t 152' (uncorr.) andforms an emerald-green copper salt.w-Chloroparatoluic acid COOH*C6H4*CH2C1 is formed when w-chloro-paratoluamide is heated with 25 times its weight of officinal hydro-chloric acid for la hours. It crystallises from alcohol in microscopi210 ABSTRACTS OF CHEBI[CAL PAPERS.needles melts a t 199" (uncorr.) and yields a light-brown precipitatewith solutions of copper salts.w-Cyanoparafolziic acid COOE€*CsH4.CH,*CN is formed from thecompound just described by acting on its potassium salt withpotassium cyanide. I t melts a t 201" (uncorr.) and is readily so-luble in hot water alcohol and ether less so in cold water.Homoterephthalamide C:ONH2*C~H,*CH,.CONH2.-To prepare thissubstance paracyanobenzyl cyanide is dissolved in 8 parts of coldconcentrated sulphnric acid and allowed t o remain for 12 hours;water is then added and the acid neutrdised with ammonia. Theamide forms a white precipitiite or nodules of crystals and meltsa t 235" (uncorr.).It is very sparingly soluble in indifferent sol-\Tents but dissolves readily in concentrated hydroch:oric acid.Womoterephthalamic acid COOH*C,H,.CH,*CONB is obtained fromw-cyanoparatoluic acid by the action of cold Concentrated sulphuricacid and may be purified by crystallisation from alcohol in which i tis sparingly soluble. It melts at 261" (uncorr.) and forms a light-blue copper salt.Homoterepht ha Zisoamic acid c ON H2*C6H,C H2*COOH is formedin like manner to the foregoing from paracyanophenylacetic acid.It melts at 229" (uncorr.) and is distinguished from its isomerideby greater solubilit'y in alcohol and by forming a malachite-greencopper salt.HomoterephthaZ;c acid COOH*C6H**CH,*COOH is best obtainedfrom the diarnide by heating it for 3-4 hours with 20 parts of 25per cent.hSdrochloric acid and crystallising the product from dilutealcohol Jt dissolves in 7 parts of alcohol a t 30" and in 100 partsof water a t 50" but is almost insoluble in ether and benzene. Itmelts a t 285-288" (uncorr.) and gives with copper salts a verdigris-like precipitate.The corn pounds described as homoterephthalic acid by Paternb(Gazzetta 7 361) and as insolinic acid by Hofmann (AnnaZen 97,177) probably consist of impure terephthalic acid.H. G. C.Chloraniso'ils. By L. HUGOUWENQ (BUZZ. Xoc. Chim. [3] 2 273-2@0).-Chlorine is passed into cold anisoi'l (432 grams) in the dark,until the weight increases t o 680 grams ; after washing and subsequentsteam distillation the portion which fractionates a t 230-237.5" isretained. This liquid resisted crystallisation and not until it hadbeen exposed to the cold of a winter's night were acicular crystalsobtained which after removal of the trichlorinnted derivative bypressure were recrystallised from alcohol. As thus obtained dichlor-anisoil melts a t 27-28" but the presence of traces cjf trichloranisoilreduces the melting point to 16". Prom the alcoholic mother liquor,large orthorhombic prisms of dichloranisoil separate having the axialratios a b c = 0.6556 1 0.5231.The substance boils a t 232-239"under a pressure of 743.45 mm. (corr.) ; i t is soluble in alcohol ether,benzene and chloroform but is insoluble in water. When heated a t145" in sealed tubes with hydriodic acid (sp. gr. la?) methyl iodideand dichlorophenol (1 2 4) were obtained.Dichloyonitroanisoi'l is obtained by the action of fuming nitric aciORGAXIC CHEJlISTRY. 241on dichloranisoil ; it crystallises from alcohol in pale yellcwish-greenneedles melting a t 43.5".Trzchloranisoi'l is formed by passing chlorine into cold aniso'iluntil the hydrogen chloride evolved and absorbed by cold waterequals the weight of aniso'il employed ; the product is washed dis-solved in boiling alcohol and recrgstallised when needles are ob tainedwhich melt a t 60-5" are soluble in benzene chloroform and carbonbisulphide and distil at 240 under a pressure of 738.2 mm.(corr.).When heated a t 180" in sealed tubes with concentrated hydrochloricacid or a t 14O-15OJ with hjdriodic acid trichlorophenol [l 2 4 61is produced.Trichloronitroanisoi'l [OMe C1 NO = 1 2 4 6 31 forminglong nacreous needles melting at 48-50" results from the actionof a mixture of sulphuric and fuming nitric acids on the precedingderivative. A trichlorodinitroanisofL [l 2 4 6 3 51 cr~ystallisingin prisms which melt a t 90-91" is farmed by the action of nitric andsrilphuric acids on trichloroaniso'il at 70-75".Tetrachloranisciil results from the action of chlorine a t 70" onanisojil containing 5 to 6 per cent.of iodine; some pentachloraniso'il isalso produced and may be separated by recrystallisation from hotalcohol. Tetrachloraniso'il cr3;stallises in slender needles which aresoluble in alcohol ether chloroform benzene and carbon bisulphide ;it is sublimable and boils with partial decomposition a t 278" under apressure of 745.85 mm. (corr.). When hydrolysed by hydrochloricacid a t 175" or by hydriodic acid a t 150" orthotetrachlorophenol,hitherto undescribed is produced ; this substance the author isstudying.Pentachlorani#oil crystallises in long hard crystals melts a t107-108" and is slightly soluble in cold alcohol easily in benzene,carbon bisulphide chloroform and boiling alcohol. Under a pressureoC 745.45 mtn.it boils a t 289' with partial decomposition. Whenheated with hydriodic acid a t 186" it yields pentachlorophenol.T. G. N.Derivatives of Symmetrical. Dinitroresorcinol. By P. KEHR-MANN ( J . pr. Chma. [ 21 40 49$-497).-Chlorodi~iitror~sorcillol[(OH) C1 (NO?) = 1 3 2 4 61 is obtained by suspendingfinely powdered dinitroresorcinol i n ether and passing chlorine,diluted with carbonic anhydride through the liquid. It formslong yellow vitreous prisms melting at 181-182" and soluble inmost solvents. The neutral potassium salt was obtained.The chlorodiamidoresorcinol stannoch loride is obtained by reducingthe nitro-compound with excess of stannous chloride b u t attemptsto isolate the hydrochloride or base result in the formation of ch7or-n?nidohydrox~jquinonrinzide [0 CI OH NH NH2 = 1 2 3 4 61,which is best obtained by treating the stannochloride with ferricchloride in aqueous solution ; it crystallises in violet needles and isconverted into chlorodihydroxTquinone (next abstract) by dilutepotash solution.A. G. B.Derivatives of Metadichloroquinone. By F. KEHRNANN andW. TIESLER (J. pr. Chem. [2 J 40 480-4!34).-Metadichloroquinon242 ABSTRACTS OH' OHEhlICAL PAPERS.is best prepared as follows :-Commei*cial trichlorophenol(200 grams)is dissolved in sufficient glacial acetic acid at 40-50" and is mixedwith a solution of chromic anhydride (120 grams) in sufficientwater to dissolve i t and twice that volume of glacial acetic acid.After the mixture has remained a t 30-40" for a quarter of anhour much water is added ; this precipitates the metadichloro-quinone in yellow needles ; it melts a t 121".Metadichloroquinol,CsH2C12(0H)2 crystallises in flat long leaflets melting a t 164". Thediacetyl-derioative forms slender needles melting at 98" and solublein the usual solvents.When alcoholic potash (10 per cent.) is dropped into an alcoholicsolution of metadichloroquinone the liquid becomes first green andthen brownish-red but as soon as hhe potash is in excess the coloui*begins to fade; red crystals of a potassium salt are then deposited,the yield being 5-6 per cent. of the quinone.Chlo~odiimidoquinoZ [(N.E3)z (OK) C1 = 1 4 2 5 61 is pre-pared by dropping strong ammonia into a saturated (at 50-60") solu-tion of metadichloroquinone not more animonia than one quarter ofthe volume of the quinone solution beiiig added in all.After half anhour crystals separate which are washed with alcohol and purifiedby crystallisation from glacial acetic acid ; they amount to 20-2.5 percent. of the quinone. Chlorodiimidoquinol forms lustrous bronze-coloured t h i n leafy crystals which sublime without melting butwith partial carbonisation at 258-260"; it is insoluble in coldwater and alcohol but dissolves partially in hot alcohol with aviolet colour ; i t dissolves in strong hydrochloric and sulphuricacid with a blue colour and is precipitated on dilution. When heatedwith dilute acids it loses nitrogen as ammonia and is converted into achlorodihydroxyyuinone (see below).When heated with potash solu-tion i t is converted into the red potassiuwz salt obtained above;when this is dissolved in water and a slight excess of strong hydro-chloric acid added large yellow-red leafy crystals of chloropara-rlihydroxyquinone C6HC1O2(OH) gradually separate ; this quinonemelts at 240". The ammonizbm salt forms an insoluble brownish-red crystalline precipitate when ammonium chloride is added tothe solution of the potassium salt; the salts of most heavy metalsgive insoluble brown precipitates under the same circumstaLces ;the strontium and silver salts are described.When chlorine diluted with carbonic anhydride is passed througlla dilute acid solution of chloroparadihydroxyquinone cbloranilicacid is obtained ; if bromine be used bromochloranilic acid is formed.Iodochlorodihydroxyquinone [02 (OH) I C1 = 1 4 2 5 3 61is obtained as a red crystalline powder when a strongly acidsolution of the chlorodihydroxyquinone is dropped into the calcu-lated mixture of potassium iodide and iodate ; it is insoluble in coldwater and is decomposed by hot water ; it decomposes a t 275" ; hotdilute hydrochloric acid converts it into chloranilic acid with separation of iodine.Nitroso- and nitro-chloranilic acids are obtained respectively whenchloroparadihy droxyquinone is treated with nitrous and nitric acidsrespectively.These acids are still under investigationOHQANIC CHEMISTRY. 213Chloi-oyaradiaminoquinol hydrochloride obtained by digesbing chloro-diimidoquinol with stannous chloride and hydrochloric acid crjstal-lises in large colourless rhomloic octahedra or prisms very solubleiu water.The free base has not been obtained.Tetracetylparadiamidochloroquinol [ (OAc) (NHAc)? C1 =1 4 2 5 61 is obtained by heating the above hydrochloride withacetic anhydride and sodium acetate for half an hour and addingwater ; it crystallises from hot glacial acetic acid in lustrous white,four-sided tables melting at 255" and sparingly soluble.Chloroparadiacetamidoquinone [O (NHAc)~ C1= 1 4 2 5 61is formed when the above tetracetyl-compound is dissolved in dilutealkali acidified and ferric chloride added in slight excess. Itcrystallises in brilliant golden needles melts a t 225--LZb" andis soluble in hot alcohol and glacial acetic acid.When suspendedin ether and treated with hydrochloric acid and stannous chloride,chloro~aradiacetn?nidop z~inol is formed ; this crystallises in colourlessprisms melting a t about 30O0 and soluble in hot water alcohol andether.A discussion of the constitution of some of the foregoing com-pounds concludes the paper. A. C;. B.Desmotropy in Phenols. By J. HERZTG and S. ZEISEL (Monatslz.,10 735 -769 ; compare Abstr. 1888 826 ; and 1889,247 and 966) .-On adding bromine to tetrethylphloroglucinol in molecular propor-tion half the halogen is converted into hydrogen bromide and amixture of two isomeric bromotetrethylphloroglucinols is formed. Inthis operation it is necessary to brominate a solution in absolute alco-hol the presence of water in the alcohol leading to the formation ofdibromotetrethylphloroglucinol. The two isomeric monobrornotetr-et hylphloroglucinl 1s are best separated by fractional crystallisationfrom petroleum (b.p. 60-90') in which the a-compound is leastsoluble and from which it crystallises in thick quadratic platesa b c = 1.0029 1 1.3749) melting at 85-83". The /+compoundis more soluble and crystallises in needles melting a t 115-118".If the a-compound is dissolved in cold potash soda or ammonia and,after remaining some time precipitated wltti hydrochloric acid i t ISconverted into the /%compound ; the pure P-compound is however notalways the most stable form for when a solution in acetic acid is pre-cipitated with water a mixture of the a- and /$compounds is obtained.If the acetic acid solution is boiled the coilversion of the /3- into thea-compound takes place completely and the same result is producedon boiling a solution of the @-compound in benzene or some othersolvent without chemical action on it.Sodium /3-bromotetrethyl-phloroglucinol C14H20Br03Na is obtained in long colourless crystals,readily soluble i n water on dissolving the F-compound in a suallexcess of pure caustic soda ; the potassium salt much resembles i t ;the silver salt is crystalline and soluble in water and in alcohol. Thea-compound furnishes the same salts.On heating with acetic anhgdride both a- and P-bromot'etrethyl-phloroglucinol gave the same monacetate CI4H,,BrO3Ac which c r j s-tallises in monoclinic prisms (a b c = 1.7 1 x) and melts a214 ABSTRACTS OE' CHEMICAL PAPERS.66-68'. When @-potassium bromotetrethylphlorogl ricinol is heatedwith an excess of ethyl iodide for three hours ethyliodotetrethyl-phloroglucinol crystallising from petroleum in asymmetric plates( a b c = 1 1.0961 0.8947) and melting at 51-53" is formed.Both a- and p-bromotetrethylphloroglucinol give the same tetrethyl-phloroglucinol (m.p. 210-212") on reduction with zinc aud the samedibrornide on bromination in dilute alcoholic solution. The dibromidemelts a t 80-82' crystallises from dilute alcohol in flat needles of con-siderable length contains no hydroxyl-group and gives on reductionwith zinc and acetic acid tetrethylphloroglucinol (m.p. 209-211°),and on heating with acetic anhydride the above described monacetate.The general beh aviour of the isomeric bromotetrethylp hloro-glucinols leads the authors to attribute the constitution[0 Et2 0 E t 0 H,Rr = 1 2 3 4 5 61,to the a-compound and [OH Et 0 Et 0 Br = 1 2 3 4 5 61to the P-ccmpound ; the dibromide produced from both being formedby isomeric change and represented by the constitution[ O E h 0 B1-8 0 Et2 = 1 2 3 :4 5 61.(3. T. &I.Constitution of Asarone By J. F. ETKMAN (Rer. 22 3172-31 76).-The vapour- density of asarone the crystalline constituent ofasarum oil determined under reduced pressure was found to be102.9; an optical examination of a mixture of asarone and Pafroleshowed that asarone contains a propenyl- and not an allgl-group.The constitution of asarone is therefore [(OMe)3 C,H = 1 2 5 41,where C3H5 = CECHMe.The liquid constituent of asarum oil is probably a methyl ether ofisoeugenol.F. S. K.New Sugar with an Aromatic Nucleus. By MAQUENNE(Corirpt. rend. 109 812-814).-A commercial sugar pinite derivedfrom the resin of the Pirius lambertiana of Nebraska resembles thepinite described by Berthelot which was derived from the sameFource but differs from it in melting point and rotatory power.Both are very soluble in water slightly soluble in alcohoi crystallisei n nodules and have a high rotatory power. Berthelot's pinite hasa rot,atory power of [a]j = + 58.6 ; the new sugar which the authordistinguishes as P-pinite has a rotatory power [a]n = 65O.51 and meltsat 186-187,' (corr.).It has the same melting point and rotatorypower as sennite and probably is identical with it.P-Pinite has a composition intermediate between C,H,,Os andCtiH,,07. When boiled for a short time with fuming hydriodic acid,it yields methyl iodide and a sugar C6H,,06 which crystallises insmall tetrahedra melts a t 245' (corr.) dissolves very readily inwater and is almost insoluble in alcohol and quite insoluble in ether.Cryometric estimation of its molecular weight gave the numbers176-178 so that i t is isomeric with glucose. When heated withllitric acid i t yields rbodizonic acid which can be converted intotetrahydroxyquinone by the action of hydrochloric acid. It followORGANIC CHEN IST R Y.245from these results that 6-pinite is the methyl salt of the sugarC6HI2O6 and the latter is a benzene-derivative isomeric with inosite ;it may be distingnished a s 6-inosite.Berthelot's pinite also yields methyl iodide and p-inosi te whentreated with hydriodic acid. C. H. B.Lactones derived from Glycines. By P. W. ARENIU~ (J. p i * .Clrem. [el 40 498-504 compare Abstr. 1888 825).-GZycoZyZ-pheTbyZgZycine OH.CH,.CO*KPh*CH,.COOH is prepared by heatingchloracetophenyl~lycocine with aqueous soda for half an hour addingexcess of hydrochloric acid and extracting with ether by distillingthe ether arid crjstallisinp the residue from a mixture of benzene andalcohol the new plycine is obtained in large transparent rhombictables melting a t 127-128° soluble in water and alcobol and sparinglyin ether and benzene.The caZcium salt (with 6 mols. H20) and thebarium salt (with 7 mols. H,O) are described.Anlaydroglycol~ZpJ~en~lgl~icir~e NPh<CH2:CO> 0 (compare Knori*'sphenylmorpholine Ahstr. 1889 l219) is obtained by heating gly-colylphenylglycine a t 160" ; it crystallises from hot alcohol in silkyneedles which melt a t 1G9" and dissolve with difficultv.GZycoZyZpheszyZgZ?lcin mnide OH*CH,~CO*NPh-CB2*CONH obtainedby passing dry ammonia throiiqh an alcoholic solution of the la3t-mentioned compound crjstallises in lustrous leaflets melts a t1.23-129" and dissolves easily in water and alcohol but only sparinglyin benzene.Gl~coly lorthotolyl glycine and anh yd roglycolylorthotolylgl yc'nehave been described before (Abstr.1888 825) ; the pottrssium scr Zt(with 1 mol. H,O) the silver salt and the barium salt (with 7 mols.HzO) of the former are here described.GZ?/coZyZo~thotoZylgZyc~nall ide OH*CH,.@O*N( CGH,Me)*CH2*CONH,,obtained from the latter i n like mantier to ~lycolylphen~lglgcinamicle,crystallises in rhombic tables and melts a t 152".!IO*CH,A. G. B.Metaphenylenediamine from Resorcinol. By A. SEYEWITZ(Conipt. rend. 109 814-817) -Resorcinol is heated i n sealed f u l mat 280-300" for three hours with four times its weight of anhydroiis(but not fused) calcium chloride previously saturated with dryammonia. The product is agitated with twenty times its weight ofcold water for ten minutes filtered the amine extracted with etherafter addition of a slight excess of potassium hydroxide and theethereal solution saturated with dry hydrogen chloride which pre-cipitates crystals of metaphenrlenediamine hydrochloride in quantityamounting to about 60 per cent.of the resorcinol taken. No un-altered resorcinol is left in t'he tube. The amine is not formedl d o w 200" and even a t 250" some resorcinol remains unaltered.Direct experiments show t'hat t8he maximum yield is obtained byheating for three hours at 300" ; longer heating rednces the quantityof diamine obtained. C. H. €32-46 ABSTRACTS OF CttEhl'ICAL PAPERS.Condensation-products of Carbodiimides and Orthodi-amines. By I. MOORE (Be].. 22 3186-3201; compare Abstr.,1889 98 3) .-Dimet hy ldip hen y Miamidome th y lsneort h op h pny lenediarnine,Cl9Hl6Na&Tez prepared by boiling the phenylene-base with methyl iodideand potash in alcoholic solution crystallises from alcohol in colourlessneedles or prisms and decomposes a t about 200° but without melting ;it is readily soluble in hot benzene and hot alcohol but only sparinglyin boiling water and almost insoluble in ether. The tetranitmso-compound C19H14N4(NO)4 separates in slender needles when thebase is treated with sodium nitrite in well-cooled glacial acetic acidsolution; it gradually decomposes at about 110" melts a t about137-138" and is readily soluble in ether glacial acetic acid hotbenzene and alcohol but insoluble in water.It dissolves freely inwarm dilute hydrochloric acid and dilute sulphuric acid and it givesLiebermann's nitroso-reaction.Diacet y 1 dipamtol y 1 diumidoineth y leneort hop hcn y lenediamine,prepared by warming the paratolyl-base (Zoc.cit.) witlh acetic an-hyd ride crvstallises from wai-m dilute alcohol in colourless needles,melts a t 142-143" and is readily soluble in alcohol benzene andether but almost insoluble in light petroleum. The dibenzoy7-derivative C21Hz,,0N4B~2 is obtained when the base is heated withbenzoic anhydride a t 130-140" for an hour ; it crystallises fromboiling alcohol in colourless needles or slender prisms melts a t184 -185" and is readily soluble in hot alcohol and hot benzene biitonly sparingly in ether and almost insoluble in light petroleum.Thetetrabenzoyl-derivat ive CzlHIBNIBzI prepared by heating the basewith benzoic anhydride at 240-250" for 2 i hours crystallises fromboiling alcohol in colourless slender needles melts a t 273-5274",and is readily soluble in boiling climene moderately easily in hotalcohol and benzene and almost insoluble in light petroleum. Thetetranitroso-derivative C,lH,8N1(NO)a crystallises in slender yellowneedles gradually decomposes a t about 120" and inelts at about130" ; it is readily soluble in alcohol ether and warm benzene butalmost insoluble in liqht petroleurn. I t gives Liebermann's nitroso-reaction.T ~ ~ t r a p h e n y Z d i a m i ~ ~ ~ ~ m ~ t ~ ~ ~ l e n e o r ~ h ~ p ~ ~ ~ y Z ~ n e c Z i a m i n e C,,H,,N isobtained when diphenyldiamidomet byleneorthophenylenedianiine isheit ted at 200" with carbodiphenylimide.It crystallises in colourless,well-defined rhombic prisms a b c = 0.6633 I 0.5685 melts at138-139" and is readily soluble in alcohol ether and benzene,but almost insoluble in light petroleum. When distilled it is de-composed into aniline and diphenyldiamidomethyleneorthophenylene-ciiarnine; it is also decomposed by 20 per cent. hydrochloric acida t 1.50" yielding diphenylcarbamitle and phenylenediamine. Thehydrochloride (C,,H28N6)2,SHCl crystallises in thiti colourless platesand is readily soluble in alcohol and hot water. The pZatino-chloride ( C32H28N6)4,3 H,PtC16 which crystallises in oranqe-red plates,is only sparingly soluble in hot alcohol and insoluble in waterand ether.The szrlphate CaH28N6,2H2S04 crystallises from alcohoORGANIC CHEMISTRY. 247in colourless prismatic needles and is readily soluble in hot alcoholand hot water but insoluble in ether. The tatramethyl-deriva-tive C32H24N6Me4 crystal1 ises from warm benzene in colourless,prismatic needles melts at 181-182" and is readily soluble in warmalcohol. ether and benzene and in mineral acids. The tetracetyl-derivative CSzETz4N,Ac crystallises from a mixture of benzene andlight petroleum in colourless well-defined prismq melts at 125-126",a n d is readily soluble in alcohol ether and benzene but onlysparingly in light petroleum. The tetrabelzzoyl-derivative C32H?4NSB~4,crystallisw from hot alcohol in small colourless needles o r prisms,melts a t 181-182" and is readily soluble in hot alcohol and benzene,but only sparingly in ether and almost insoluble in light petroleum.Tetraparatolylcxmidodimeth~ylen~ol-thophenylenediamine C36H761J6 canbe prepared by heating orthophenylenediamine (1 mol.) with carbo-diparatolylimide (1 mol.) a t 130-140" aud then adding a furtherquantity (1 mol.) of the imide and heating again for 3-4 hours a t%OOo.It crystallises from hot alcohol in colourless needles melts a t115-116" and is readily soluble in hot alcohol and benzene but onlyvery sparingly in ether and light petroleum. It dissolves in con-centrated sulphuric acid yielding a colourless solution and it is decom-posed by 30 per cent. hydrochloric acid a t 150" yielding ortho-phenylenediamiiie and diparatolylcarbamide.The hydrochloride,( C3,&,N6),,3HC1 crystallises from dilute hydrochloric acid in colour-less prismatic needles and is readily soluble in alcohol and hot water,bnt only verp sparingly i n ether. and iiisoluble in benzene. Theplnfinochloride ( C3,H,,N,)4,~H2PtC1 + 15H20 separates in orange-redplates when platinic chloride is added to a dilute hydrochloric acid so-lution of the base ; it loses its water at 100" and is insoluble in water,ether and benzene butl readily soluble in warm alcohol. The sulpliate,C3fiH36N6,(LH2S04 crvstnllises in colourless needles and is readilysoluble in hot alcohol and hot water but almost insoluble in benzeneand ether. The fetracetyl-derivative C36H32NSAc4 separates frombenzene in small granular crystals melt9 a t 114-11 5 O and is readilysoluble in alcohol hot benzene and hot light petroleum but verysparingly in cold ether. The tefi.abeizzoyZ-derivnt ive c3 H32N6Bz1,cryst~llises from alcohol in colourless needles melts at 145-146" andis rendily soluble in hot alcohol ether and benzene but almost in-soluble in light petroleum.Pentamidobenzene. By A.W. PALMER and C. L. JACKSON (Amer.Chein. J. 11 448-456; compare Abstr. 1888 825 and A. Barr,ibid. 822) .-Triamidodinitrobe?rzene C6H ( NH2),( SO,) was preparedby heating tribromodinitrobenzeiie melting a t 192" with alcoholic:ammonia at 100" under pressure. It mas obtained in two forms-inreddish-yellow needles and in black aniorphoas masses ; it doesnot melt even above 300" but is decomposed if heated inore intensely,and is iiisoluble in most ordinary solvents but dissolves slightly inalcohol and in chloroform from which solutions it crystallises in small,yellow plates.When reduced with tin and hydrochloric acid i tyields a trihydrochlovide o~pei?tnmidobenzene CsH(NH2),(NH,Cl) ; thiscrystallises in small colourless shombic plates turning brown after aF. s. I(218 ABSTRACTS OF CHEMICAL PAPERS.time and forming a tarry substance when heatad with hot water 01-oxidising agents. This substance is sparingly soluble in alcohol anddissolves easily in water from which it is precipit'ated by passingin hydrogen chloride ; it is insoluble in ether benzene and chloro-form. Evidencewas also obtained of the formation of a pentahydrochloride ofthis base.Tria~LiZidodin;trobpnxene C,H (NBP1i),(N02) was alsoprepared by heating aniline with tribromodinitrobenzene ; it melts at,179" and crystallises from alcohol in orange-red needles from etherin groups of short prisms ; from solution in benzene or chloroform i tis deposited in an amorphous form. It dissolves readily in benzene,chloroform and hot alcohol moderately in ether carbon hisulphide,acetic acid and acetone. It is not acted on by hydrochloric acid butdissolves in nitric and sulphuric acids forming yellow solutions.This research has been discontinued owing to the publication of a paperby Barr on the same subject.The free base cannot easily be prepared from it.C. F. B.Action of Carbon Bisulphide on certain Axo-compoundsand Hydrazones.By P. JACOBSON and V. SCHENCKE (Ber. 22,3232 -3245).-It has previously been shown by Jacobson (Abstr.,1888 487) that by the action of carbon bisulphide on benzeneazo-/j-naphthol two anhydro-compounds of a-amido-/?-naphthol are formed,namely thiocarbamidonaphthol C,,H,< .>C-SH and carbanilamido-naphthol Cl,H6<x>C*NHPh. The authors have examined theaction of carbon bisulph id e on benzeneazoparacresol benzeneazopsendo -cnmenol and benzenedifiazoresorcinol and find that in all these casestfhe reaction proceeds in a manner exactly analogous to that describedabove. They have also extended their experiments to the hydrazonesof P-naph thaquinone and phenanthraquinone and show that thesame reaction takes place in these cases also.The results obtainedform therefore a further confirmation of the supposition tliat theatoms in the characteristic groups of these azo-compounds and ortho-quinouehydrazones are combined together in the same manner ;whereas from their modes of formation it would be expected that,00$*OH-C *NzN*Phthe groups would be represented by the formulae*q=0 respectively. Between the various constitu-.CIN-NHPh andtionad formulae which have been proposed this reaction which Occursa t a high temperature cannot of course decide.111 carrying out the reaction 1 part of the azo-compound or hydr-is heated with 2-3 parts of carbon bisulphide in a sealed tubefor eight! hours. The temperature necessary is 190-210" except inthe case of benzenedisazoresorcinol when the reaction ta.kes place a t150-155" but proceeds less smoothly than with the other corn-pounds.The products of the reaction of benzeneazoparacresol and caiaboORUANCC c]H~~lIS'l'€tY.2490 umidocresol C6H,3&fe<N>C*NHPh. The former crystallises fromdilute alcohol in colourless stellar aggregates of needles melting at2 L6-217". The second compound crystallises from the same solventin long colourless needles which melt at 205-206". Its picratemelts at 216-817" and its acefyl-compound at 86-87'.The first product of the reaction of benzeneazopsendocumenol andcarbon bisulphide thiocarbamidocumenol C6HMe3<N>C*SH crystal-lises in colourless needles melting at 252-253".By the action ofiodine on its sodium salt it is converted into the bisulphide,S [ C<g> C6HMe3] which separates from chloroform solution i ncolourless prismatic crystals melting at 150-1 51". The second0 compound formed carbaniZarnidocurnenoZ C6HMe3 < N> C-NHPh,crystallises in broad colourless needles melting at 145". Its picratemelts at 197-198'.The products of the reaction of benzenedisazoresorcinol and carbonbisulphide are more difficult to purify than those previously men-tioned. The first thiocarbodiawiidoresorcinol C,H,[ <:>C*SH ]?,forms an amorphous yellowish-white powder which commences toblacken at 250" and melts with decomposition at 270". Carbanildi-amidoresorcinol C6H2[ <N>C*NHPh] 2 is likewise an amorphouspowder which blackens at 240° and melts with complete decomposi-tion at 270".I t unites with 2 mols. of picric acid forming a picratewhich melts above 240".The two compounds obtained by the reaction of naphthaquinone-hydrazone and carbon bisulphide are isomeric with those obtainedfrom benzeneazo-@naphthol in which the nitrogen and oxygen-atoms are in the a- and p-posit'ions respectively. In the compoundsto be described these positions are reversed. Thiocarbamido-a-naphthol C,,,H,<O>C*SH crystallises in long colourless needles,which melt with decomposition at 259-260" and are readily solublein warm alcohol acetic acid and benzene. Jt is converted by potas-sium ferricyanide into the bisulphide. The second compound c a d -anilamido-ol-na~hthol Clo&<O yC*NH-Ph crystalhes from chloro-form in colourless needles melting at 232-233" and is easily solublein benzene alcohol and acetic acid.Its picrate forms microscopicprisms and melts at 213-214".Phenanthraquinonehydrazone and carbon bisu1phide.-Thiocarb-uniidophenanthrol C14H8<E>c*sH is formed in very small quantity,and is an amorphous colourless powder. Carbanilaniidophenanthrol,00NN0CI,H8<N>C*NHPh 0 crystalliseR from glacial acetic acid in pale-yellow needles united to stellate aggregates which melt atVOL. LVIIl. 250 ABSTRACTS OF CHEMICAL PAYERS.192-195". It is readily so1ut:le in alcohol and benzene less so inacetic acid and is resolved by alcoholic potash into aniline ammonia,carbonic anhydride and hydrophenanthraquinone.Its picrateforms microscopic prisms melting a t 235-236" and its acetyl-deriva-tive crystallises in small colourless plates and melts at 163-164".The hydrazones of orthodiketones (formerly regarded as mixedazo-compounds) do not act in this manner with carbon bisulphidc.Parahydroxyazo-compounds are attacked but resinous products areformed. Azobenzene on the other hand is converted a t 280-300"into the compound C6H,<s >C*SH described by Hofmann (Abstr.,1887 823). H. G. C.By 0. BURCHARD (Anualen 254,115-128 ; compare Abstr. 1889 138) .-a-Ethylenephenylhydrazine(m. p. 90.5") dissolves in concentrated sulphuric acid and on addinga trace of nitric acid an intense purple-red coloration is prodiiced.When i t is treated with sodium nitrite in dilute hydrochloric acidsolution nitrosoethylenediphenyldiamine (m.p. 160') is precipitated.The sulphafe C2H,(NPh*NH,)?,HzS0 crystallises from dilutealcohol in colourless needles and is only sparingly soluble in alcohol.The nitrate C,H,(NPh*NH2)2,2HN03 crystallises from alcohol incolourless needles or plates is readily soluble in water and melts at172-173" with decomposition. The oxalate. C,H,(NPh.NII,),,C2HPOj,crystallises in needles melting a t 183" with decomposition. ThetiiLccetyZ-derivative C2H4(NPh*NHAc)2 crystallises from alcohol inslender colourless needles melts at 222" and is readily soluble inglacial acetic acid but only sparingly in cold alcohol and insoluble inether.NEthylenephenylhydrazine.Eth y lenepheny 1 hy drazin edisuccin ic acid,C2H4 ( N P h*C 0.C2Hi C 0 OH),,prepared by heating the hydrazine (1 mol.) with succinic anhydride(2 mols.) in alcoholic solution separates from dilute alcohol incolourless crystals melts at 203" and is almost insoluble in alcohol,but readily soluble in water. The sodizm salt is cr-ystalline ; the leadsalt separates from hot water in which it is only very sparinglysoluble in the form of a crystalline powder.Succin y lethy Zenep hen y lhy drazine CJ& < PhaN H. > C,H4 isobtained when the hydraeine is heated at about 180" with succinicanhydride. It is a colourless powder readily soluble in alcohol andchloroform but insoluble in ether; i t has no well-defined meltingpoint as it begins to sinter together af 100-llO" and only becomescompletely liquid a t about 126".When boiled with alcoholic potash it iscouverted into a compound probably ethylenephenylhydrazineauccinicacid which has acid properties ; this substance is a colourless powdei-,melts a t 137-140" with previous softening and is readily soluble inalcohol but only very sparingly in ether a n d chloroform.byNP h*N Ha C 0NPh-NH.70Oxaly lethy Zen epheny 1 hydrazine C2H4<Nph.N H o prepare0 ROAN10 CHEMISTRY. 8.51heating the oxalate a t about 183" is a cglourless amorphous powdersoluble in alcohol.Ethylenet ,.iphenylthiosemicarbaziae,N H Ph-C S-NH-N Ph*C2HA*NPh*NH2,separates as an oil when an alcoholic solution of the hydrnxine iswarmed with phenylthiocarbimiile ; i t crystallises from alcohol inslender needles melts at 164*5" and is moderately easily soluble i nalcohol.Ethylenetetra~he?~yldithiose?,ticarba~~de C2H,( NPh-NHC S*NH Ph),,is a crystalline powder melts a t 194*3" and is sparingly soluble inalcohol.pre-pared by boiling the hydrazine with acetone in alcoholic solution,crystallises from alcohol in colourless plates melts a t 71-72",and has basic properties.The acetophenone condensation-product,C?H,(NPh.N:CMePh) crystallises from alcohol in golden needles,nielts a t 117-118" and is only sparingly soluble in alcohol.Attempts to prepare condensation-products with dialdehydes anddiketones were unsuccessful. F. S. K.,4 cetonet h y 1 enephen y I h y drazine CMe, N. N P ha C,H4*NP h*NH2,Oximes.By H. GOLDSCHMIDT ( B e y . 22 3101-3114). - f arb-nniZidobenzaZdoztnze C H P1i:N.OCO.N HPh is obtained when benm l(1-oxime (1 mol.) is warmed with phenylcnrbimide (1 mol.) in benzenesolution. It crystallises from benzene alcohol and ether in colourlrssneedles melts a t 135-136" and is decomposed when heated aboveits melting point yieldiiig diphenylcarbnmide benzonitrile waterand carbonic anhydride ; other carbanilidoximes give analogous de-composition-products under the same conditions. When warmedwith alcoholic potash it is decomposed into benzaldoxime and ethylphenylcarbamate and when boiled with alkalis it jields benzaldoximeand aniline.Carba?.~ilidonnisaZdo,cinze OMe*C,H4-CH:N*O*CO*NHPh crystallisesfrom benzene in long needles melting a t 82".Dicarbanilidosal ic y la ld oxi me,NHPh*CO.ON:CH.CsB,.O*CO.SHPh,crystallises from benzene in small scales melting a t 1 1 5 O .CarbaniZidofurfuraIdozinze C,~,O.CH:~*O.CO*NHPh crystallisesfrom benzene in needles melting a t 138".Carbanilidoacetoxime CMe2:N*O*CO*NHPh crystallises from benzenein needles and melts a t 108'.Carbanilidoacetoy hmo?teoxime ClMePh:N*O*CO.NHPh crystallises insmall colourless needles and melts a t 1 2 6 O .Cnrbanilidobenzophenor7eoaime CPh2:N*O*CO*NKPh crystallisesfrom benzene in colourless microscopic needles melting at 176".CarbaniZidocarcoxi?i.le CloH,,:N*O-CO*NHPh crystallises from ben-zene in prisms and melts at 130".The corresponding derivative ofisocnrvoxime crystallises from benzene in needles melting at 150".Carbanrlidocawyhoroxinze C,,H,,:N.O.CO*NHPh crystallises frombenzene in needles and melts at 94" ; it is decomposed when heateds 2.52 AnSTllACTS OF CHKERIICAL PAPERS.at 120-1 30" yielding diphenylcarbamide campholenenitrile carbonicanhydride and water.Propionaldoxime and raleraldoxime combine with phenylcarh-imide with development of heat yielding oily compounds ; mesitylene-oxime also gives a n oily product.Carbanilicloqzcinoneoxinze C,H,O:N*O.CO.NNPh crystallises in short,yellow prisms begins to decompose a t about IlO" and decomposescompletely at lGO" but without melting.I t is decomposed by boilingalcohol yielding quinoneoxime and when treated with alkalis i t isdecomposed into quinoneoxime aniline and carhonic anhydride ;other carbanilidoximes of this class show a similar behaviour witha1 kal is.Cadmnilidot hymoquinoneoxime C ,,H,,O N.0.C 0.N HP h crystal lisesin long yellow needles niclting a t 131-132".Cart anilido-a-napht haqu inoneoxime C lo H N*O*C O*NH Ph crystal -lises in yellow prisms begins to decompose at about 160" and meltsat 170".Carbanil&do-P-nayhthaquiPzone-p-oxime prepared from p-nitroso-a-naplithol crystnllises from benzene (with benzene) in greenish-yellow,microscopic prisms and decomposes a t 119-120".Cccl.Lan.ilido-p-na~~t}ia~ui~~~ne-a-ox~n~e prepared from a-nitroso-p-naphthol crystallises in small yellow needles and melts a t 126-128".When /3-naphthaquinonedioxime (1 mol.) is warmed with pberiyl-carbimide (2 mols.) i n henzene solution diphenylcarbamide is preci-pitated and the solution contains /3-naphthaqninonedioxime anhydride(m. p.78"). Toludiquinoyltebroxime is also converted into the an-hydride under the same conditions the pbenylcarbimide being con-certed into diphenylcarbamide.Carbanilidoisonitrosobut y 1 metli y I ketoiw COMe-C Pr:N*OC O*NH Ph,ci*ystallises from benzene in colourless plates and melts a t 92-93".Carbai~ilidomethylproyy Zglyoxi,ne NO H:CMeCPr:N-O*CO*NHPh isobtained when the preceding compound is treated with hydroxyl-amine hydrochloride in alcoholic solution ; it crystallises from benzenein colourless plates melting at 129-13.".Dicarbanilid(vmethy1prop ylglyos*i?ne,NHPh.CO*O*N:CMe*CPr:N*O*CO.NHPh,prepared by treating methylpropylgl~oxime wit 11 phenylcarbimide inIbenzene solution ciystallises in nacreous plates melts a t 1 6 6 1 70"with deconiposition and is only sparingly soluble in warm benzene.Carbanilido- Aenzi,Zmonoz ime COP h*C P h N O C 0.N H P h preparedfrom a-benzilmonoxime crystal lises from benzene in small prisms,itielts at 144" and is decomposed when warmed with alkalis yieldinganiline and a-benziloxime ; it turns yellow on exposure to light.Ca~bnnilido-~-benzilmonoxime prepared from ybenzilmonoxirne,crystallises from benzene with 8 mol.of benzene in colourless needles,loses its benzene at lOU" aud melts a t 143" i t turns yellow onexposure to light and is decomposed by alkalis yielding aniline andthe yoxime.Dicnrbanil ic~o-a-benzildioxime,N HPh.CO*O.N:CPh*CPh:N*O*CO.NHPhORGANIC UHEJIJSTRT.258crgstallises in colonrless microscopic plates melts a t 180' and is onlysparingly soluble in the ordinary solvents ; it is decomposed byalkalis.1)icarbaniEido-P-benzildioxime crystallises from benzene in smallprisms melts at 187" and is decomposed by alkalis,Dicclrbanilido-r-benzildioxime crystsllises from benzene in colourlessneedles containing benzene and melts at about 175" ; when warmcdwith alkalis i t is decomposed into aniline and berizildioxime an-hydride (m. p. 94').The fact that all the benziloximes react with phenylcarbimidewith equal readiness yielding compounds of equal stability isevidence in favour of Auwers' and Meyer's views namely that thebenziloximes are st ereochemically isomeric.CarbariilidoisobenzaZdoxiwze CI4Hl2N2O2 is obtained when isobenzald -oxime (1 mol.) is treated with phenylcarbimide ( 1 mol.) in etherealsolution the precipitate quickly separated by filtration and recryst;llAlised from cold ether.It separates from benzene in colonrless needles,and from ether in quadratic plates melting a t 94' wit,h decomposition.It is much more readily decomposed by alkalis than its isomeride (seeabove) yielding diphenylcarbamide aniline and isobenzaldoxime ;this behaviour is not i n accordance with Beckmann's formula for iso-benzaldoxime neither is the fact that carbanilidoisobenzaldoxiniereadily undergoes intra-molecular change. When a few bubbles ofhydrogen chloride are passed into a cold saburated benzene solo-tion of carbanilidoisohenzaldoxime it is wholly converted into theisomeride (m.p. 135-136O) some of which separates from thesolution in crystals; the same change is brought about but moreslowly by a trace of phenylcarbimide. F. 8. K.Amidoximes and Azoximes.. By F. TIEMANN (Ber. 22,3124-313U).-General remarks on the papers of Wurm (this voJ.,p. 258) Zimmer (next abstract) Stieglitz (next' page) and Hoch( t h i s vol p. 260).Action of Aldehydes on Benxenylamidoxime. By H. ZIMMER(Bey. 22 3140-3147).-Tiemann bas shown (this vol. p. 44) thatacetaldehjde farms a condensatimi-product with benacnylamidoxirne.The author has extended this reaction to other aldehydes.B e n z e n y l h ~ d r a z o ~ i e ~ ~ i i ylethylidene CPh<r:>C€€ CH2Ph isformed when phenylacetaldehyde acts on benzenylamidoxime.Itforms small white needles sparingly soluble in boiling water easilyso in ether chloroform and benzene and melts at 136". Aqueoii~hydrochloric acid resoives the compound into its components but dryhydrogen chloride forms with it a crystalline hydrochloride. Whcnoxidised with the calculated quantity of potassium permanganate thehy drazo xime yields benzen y 1 azoximepheny 1 eth eny 7,This is crystalline insoluble in water soluble in alcohol and ch1o1.o254 ABSTRACTS OF CHEMICAL PAPERS.form sparingly so in ether and melts a t 118".alkalis have anv action on it.Neither acids noruBenzeiay 1 hydraxoxillze~i.o~2/1if,Zene C P he::> CH E t obtained bythe action of propaldehyde on benzenylamidoxime forms colour-less crystals spariugly soluble in water easily so in organic solvents,and melts a t 64".When heated with alkalis or acids it is resolvedinto its components. The hydrochloride is crystalline. Eenzenyl-trzoximepropenyl CPh<",O>CEt - i R a colourless oil boiling a t230-235". Acids andalkalis are without action on it.Benzenylhydrazoaiiiieisobutylidene CPh<~~>CH*CHMe formssilky needles soluble in boiling water in organic solvents and in coldconcentrated hjdrochloric acid. When heated with acids or alkalis,i t is resolved into its component,s. The hydrochloride is crysta,lline.~enzenyEazoximei~.cbbule~~?/l is an oil soluble in alcohol ether andchloroform boils a t 253-255" and is indifferent towards acids arida 1 k a1 is.BenzenylhydrazoximeisoanyZidenc CPh<:;(:>CH*CH2*CHMe2 issparingly soluble in boiling water easily so in organic solvents,crjstallises in colourless needles and melts at 83".It is decomposedby hot acids or alkalis and forms a crystalline hydrochloride. Ben-zr,n~Zaxoximeisoamen!/l is an almost colourless oil of slightly aromaticodour and is solnble in organic solvents. It boils a t 257" and isindifferent to acids and alkalis.No analogous hjdrazo-compound could be obtained from benz-aldelijde dibenzenylazoxime melting a t 107" being a t once formed.Benzeny lhy d ruzoxiwesa Zicideiz e C P h e N > C H - C6H4*OH c r j s tal-It is sparingly solubleBenzeny1azmi:im esaliceny Z CPb<=$& CsH,* OH is isomeric withStdker's salicenylazoximebenzenyl OH*CsHc*C<N>CPli N-0 (this ~ o l .,1). 143) and resembles it in all its properties. It is therefore,1)robable that these two compounds are identical a molecular re-arrangement taking place during one or other mode of furmatiorr.The hydrochlorides of all these hydrazoximes are decomposed bywater and are only formed t y the ackion of dry hydrogen chloride.L 1'. T.It is solnble in a1colio1 insoluble in water.N*Olises in colourless needles and melts a t 155".in water easily so in organic solvents and in cold alkalis.Be haviour of Ami doximes towards Diazo b ens ene- deriva-tives By J. STIEGLITZ ( H r r . 22 3148-3160).-When benzenyl-amidoxime acts on diazobenzene chloride or sodium diazobenzene-sulphonate diazoamidobeneene and a componnd C,,H,,N,O are formed.The li~tter compound seems to be formed from 2 mols.of the amid-oxiine tlie diazo-compouud playing the part of deterniining agenORGANIC CHEMISTRY. 2 55only probably acting as it sometimes does as a mixture of anilineaild nitrous acid. The author has obtained the same compoundC,lH,,N,O by the action of nitrous acid and of some mild oxidisingagents though the yields were small. This compound benzenyl-hydrazoximeamidobenzylidenc CPh<Z:>CPh*NH crystalliscs inrhombic plates and melts at 124-125" being resolved into benzo-nitrile and benzenylamidnximc. It is insoluble in WR ter spsringlysoluble in ether moderately so in alcohol benzene and chloraform.It has no acid properties and is only verj slightly basic its unstablehydrochloride only being formed when dry hydrogen chloride is passedinto a chloroform solution of the base.This salt is soluble in water,but after a time the aqueous solution gradually deposits the freebase. I t crystallises i n colourless microscopic needles which melta t 144-145" and a t a few degrees higher temperature decomposeinto ammoniLim chloride dibenzenylazoxime and small quantities ofbenzonitrile. The same decomposition takes place very rapidly wh(.nthe alcoholic solution is boiled. The platinochloride forms a pale-yellow precipitate melting a t 125.5" and charring a t 130-14U". Thepicrate forms a golden-yellow precipitate melts a t 148-14Y0 andexplodes at? a few degrees higher.The free base is not attacked bycold dilute acids or alkalis b u t when boiled with alkali is at onceresolved into benznnitrile and benzenylamidoxime. When hcatedwith strong aqueous hydroc3hloric acid a t loo" benzenylamidoxime,henzoic acid dibenzenylazoxime and ammonia are formed. Boilingglacial acetic acid or alcoholic solution of hydrogen chloride yieldsdibenzenylamidoxime. The absence of a free oximido-group is shownby ferric chloride giving no coloration. This base is stable towardsnitrous acid. Heated with carbon bisulphide at loo" i t yields thecompound C,HcN2S2 (Schubart this vol. p. 49) .probably afterprevious partial decomposition into benzenylamtdoxime and benzo-nitrile. Taking all these facts into consideration the author considers.the above to be its most probable formula.Orthohomo benzenylhydrazoximenmido-orthohomobenzyliden e,was obtained by the action of sodium diazobenzenesulphonate onorthohomobenzenylamidoxitne.I t forms colourless microscopiccrystals easily soluble in chloroform alcohol and benzene less so inether and insoluble in water and aqneous acids and alkalis. It meItsat 109 -1 lo" and although stable at ordinary temperatures graduallydecomposes in hot summer weather into orthotolunitrile and ortho-I~omobenzenylamidoxime. The same decomposition is readily effectedIjy hydrochloric acid a t 100". The author had not enough of thishydra zoxime to prepare ortkohomobenzoyl-o.1.thohomobenzel,y7umid~xi~,e,C,H,Me*C (NH2):N*0.CO-C6H,Me directly from it b u t obtained thelatter compound by the action of orthoioluic chloi4de on orthohomo-benzenylarnidoxime.I t crystallises in long silky needles resembling2sbestos is easily soluble in alcohol chloroform ether and benzene,and in acids is almost insoluble in water and alkalis and melts a256 ABSTRACTS OF CHEMICAL PAPERS.117-118'. At 180" water is given o% and di-orthohomobenzenylaz-ozinae C6H4Me*c<,>C*C6H4Me is formed. This forms very t h i n ,silky needles exceedingly soluble in alcohol ether benzene audchloroform and melts a t 58-59'. It sublimes unchanged andvolntilises in steam or alcohol vapour.N*OMetan.itrobei~zenylhydrazoxin~~amido-metanitrobenzylidene,was obtained by the action of sodium diazobenzensulphonate onmetani trobenzenglamidoxime ; it is a pale-yellow substance almostinsoluble in the usual solvents.It is most soluble (1 2000) inalcohol. It melts at 150-151'. When boiled with alkalis it isdecomposed into the nitrile and amidoxime but a trace of metanitro-benzen y lazoximem et an; t r o ben zen y Z NOz* C6H4* c<,>c *c 6H4*N0 2 isalso formed. The latter is however best obtained by the action ofstrong cold snlphuric acid on the hydrazoxime. A mixture of meta-nitrobenzenylamidoxime and metanitrobenzonitrile gave no trace ofthe azoxime with sulphuric acid. The azoxime may also be obtainedfrom the hydrazoxime by boiling the latter with glacial acetic acid.It forms microscopic micaceous needles sparingly soluble in coldorganic solvents melts a t l68" and sublimes unchanged.The authorobtained the same compound by acting on metanitrobenzenylamid-oxime with metanitrohenzoic chloride.Attempts to get analogous compounds by the action of dia,zobenwnechloride on compounds of the general formula NHR*CPh:N*OHhave as yet proved fruitless.In the course of his work the author finds that in the action ofhydroxylamine on thiamides and thianjlides the presence of excess ofalkali is an advantage.Thiobenzort hotoluide C SPh*NH*C6H4Me is formed by fusingbenzorthotoluide with phosphoric pentnsulphide. It crystallises frombenzene in pale-yellow prisms and melts at 85-96'. When heatedwith an alcoholic solution of hydroxylamine hydrochloride it yieldsbenzmylorthotoEuidozime NOH:CPh-NH*C6H4Me. When excess ofalkali is present the reaction is veiay much accelerated.This com-pound crystallises in hexagonal prisms is easily soluble in acids,alkalis and organic Bolvents and melts a t 147".Constitution of' Benzhydroxamic Acid. By G. MINUNNI ( B e r . ,22 3070-3071).-l'he compound N,HPh:CPh*OH is formed whenbenzhydroxamic acid is heated at 130-140" with phenylhjdrazine ; i tcrystallises from dilute alcohol in colourless needles and melts at165-166". The formation of this compound shows that benzhydr-oxamic acid has the constitution OH-CPLNOH. F. S. K.N* 0L. T. T.Oils of Wintergreen and Birch. By H. TRIMBLE and H. J.M. SCHROETER (Phnrm. J. Trans. 20 166-168).-The authors findthat the oils of wintergreen and birch are physically and chemicallORGANIC CHEMISTRY. 257identical each consisting of methyl salicylate and small qunntities ofbenzoic acid and ethyl alcohol together with from 0.3 to 0.447 percent. of a hydrocarbon of the formula C15H24 A sample of artificialoil of wintergreen had the physical but not the chemical propertiesof these oils and was not pure methyl salicylate.Methysticin.By C. POMERANZ (Monntsh. 10 783-793 ; com-pare Abstr. 1888 1207 and l889,278).-This compound exists in theroot of Mrtcropiper mefhysticum from which it may be best preparedby exhaustion with boiling 80 per cent. alcohol ; t,hc solution is con-centrated and allowed to remain in a cool place for some days whena crystalline deposit separates and this on recrystallisation fromboiling alcohol furnishes pure methyst.icin in the form of inodorous,tasteless prismatic needles melting a t 137". It has the formulaC15H1405 is insoluble in cold water only slightly soluble in hot water,light petroleum and ether but is readily dissolved by boiling alcohol,and cannot be distilled unchanged.On treatment with potash o rsoda the compound is dissolved with formation of the potassium orsodium salt respectively of an acid which the author has namedmethysticinic acid. The free acid C1iH1206 crystallises in yellow,prismatic needles resembling piperic acid is sparingly soluble inordinary solvents dissolves readily in solutions of the alkalis meltsat 180" with evolution of carbonic anhydride and is coloured red bya solution of ferric chloride. On oxidation with a solution of potas-sium permanganate i?i is converted into a compound identical withFittig and Remsen's piperonylic acid CH2:0,:C6H3*COOH[O COOH = 1 2 41 which melts at 227" and gives a charac-teristic calcium salt.Methysticol is obtained on boiling methysticinic acid with alkalis ordilute acids.It melts at 94" is insoluble in alkalis but is readily dis-solved by alcohol o r ether crystallises in flat prisms forms a cum-pound with phenylhydraxine which melts at 143" and has theformula C ,,H1203.In consideration of its behaviour with potash methysticin must beregarded as the methyl salt of methysticinic acid CH2:02:C,H3*C7H70:3[O C7H,0a = 1 2 41 the group C7H703 if methysticiiiic acidis regarded as a 13-ketonic acid being represented by the chain-CH:CH*CH:CH*CO*CH,*COOH. The author has not succeededin detecting the least trace of benzoic acid in the oxidation-productof methysticin (compare Kiilting and Kopp &Ion.Sci. 1874 921).G. T. M.R. R.Tannins. By C. ETTI (Monatsh. 10 805-806; compare thisvol. p. 164).-Since the tannin ClfiHl4OS obtained from the aqueousextract of the wood of the Slavonian oak is a dimethoxy-derivativeof a ketonic acid formed by the condensation of 2 mols. of pallicacid each of which has two hydroxyl-groups placed symmetrically t)the carboxyl-group ; and since the formation of the ketonic acid mustbe accompanied by the spliting off of a molecule of water from oneof the carboxyl-groups the ketonic acid must hare the constitutional'3.K5 1' 2 3 4 6formula C6H2 (OH) 3*C 0.C6H (OH),.C OOH258 ABSTRACTS OF CIIEJIICAL PLlPERS,It has j e t to be determined which of the bydroxyl-groups representthe two methoxyl-groups in the tannin.G. T. M.Ethyl Diphenacylacetoacetate. By C. PAAL and A. HOEKMAYN( B a r . 22 3225-3232).- Paal has previously shown (Abstr. 1884,5118) that ethyl phenacylacetoacetnte (ethyl acetophenoneacetoacetate)is converted by dilute aqueous potash into phenacylacetone. Ini his reaction a small quantity of a semi-solid insoluble substanceis always obtained consisting of a crystalline mass saturated withoil. The latter may be removed by extraction with cold alcohol andtlie residue recrystallised from the hot liquid. Two kinds of crystalsare thus obtained and can be scparated mechanically.The corn-1)ound present in smaller quantity Cl6Ul3BrO does not combine withI rhenylhydrazine or hydroxylamine. and is very stable towards re-tlricing agents b u t the amount obtained was too small for furtherexamilia tion.The second compound may be obtained pure by recrysrallisationfrom alcohol and forms large transparent monosymmetric tableswhich have the composition C22H2205r and consist of ethyl ciiplwmcyl-acetoacetate CAc( CH2*COPh),.COOEt the ethyl salt of a tri-ketonic acid. It forms large monosymmetric crystals a b c =1.6766 1 1.1152; /3 = 86' 18'. It melts at 82-83" is insoluble inwater sparingly soluble in alcohol but readily in chloroform aceticacid and benzene. With plienyliiydrazine it yields a dihgdrnzoue,CJ4HJ4N4O3 wliich forms jellow crystalline flocks melting a t 88-92',:mcl readily undergoing decomposition. With hydroxylamine i t forms,according to the conditions of the experiment a mono- di- or tri-oxime ; all three are amorplious soluble in alkalis and most organicsolvetits but insoluble in water.The mono- and di-oxime melt a t61-63" and the trioxime at 66-68'.The ethyl salt is very stable towards aqueous potash but is readilyconverted by alcoholic potash into the potassium salt of diplienacyl-acetic acid which i 3 identical with the acid previously obtained byI'aal and Kues (Abstr 1987 261) and +ids with phenylhydrazine,t IIC same derivative l-S-diphenyl-5-phenacyl-6-pyrida~onephenyl-113 drazone N<bpl,.CH,> CH*CH,*CPh:N,HPh.When heated with alcoholic ammonia diphenylacetic acid is con-i-ei-ted into 2 (;-diphen~lpyridine-4-carboxylic acid.By the action of alcoholic ammonia on ehhgl diphenacylaceto-acetate two compounds melting at 192" and 136" respect~velj areobtained both of which yield one and the same acid on hydrolysis,and appear to be the nmideand ethereal salt of this acid.YPh-COH.G. C.Benzenylazoximemethenylcarboxylic Acid and some of itsDerivatives. By A. Wui:?lr (Uer. 22 3 130-3139).-E/hy7 hemen?yl-( L I I I idozl?n eoxcl Zat e NH,.C P ti :N.O*CO.CO*O I! t is obtained as a pre-cipitate or oil when a well-cooled chloroform solution of benzenyl-atliidcxime (2 niols.) is added to a similar solution of ethyl chlorORGANIC CR EXIST RT .259oxalate (1 mol.). When this substance is separated frcJm the benzen.1-arnidoxime hydi~ocliloride simultaneously formed by boiling withwater and subsequently precipitated from alcoholic solution i t f o r m ssmall glistening white needles which decompose suddenly a t 118".It is insoluble in water chloroform and benzene sparingly solublein ether and very soluble in alcohol. When digested for some dayswith water at 100" or saponified with weak alkali i t yields benzenyl-anzidoximeorulic arid NHr.CPh:N*O*CO*C'OOH7 which crystallises iriscales soluble in boiling water and melts at 159". When the chloroformfiltrate from the oxalate is allowed to evaporate spontaneously ethylbenzen y l a z o x i n a e m e t h ~ i z ~ l c ~ ~ b o ~ ~ j l a t e CPh<Tg>C*COO E t is ob-tained.It may also be prepared by heating together benzenylamid-oxime and ethyl cbloroxalate and is the substance formed by the suddendecomposition alieeady meritioned of t h e oximeoxnlate ; finally i t maybe prepared by heating t h e silver salt with ethyl iodide. It crjstnl-lises i i i needles or plates is moderately soluble in ether and alcohol,readily in chlorofoi~m and very sparingly in cold water. It melts a t-51" and distils unchanged at 260". When hydrolysed it yields thej r e e acid which crystallises in needles is soluble in ether and alcohol,sparingly so in cold water and melts at 98'. It is very slightlyvolatile in steam and chars when heated above its melting point.The potassium and calcium scrlts are white and crystalline the silveyand lead salts wliite powders the copper salt a green powder and thenzethyl salt (obtained by heating methjl iodide and the silver salttogether at 100') farms pale silky-white needles which are insoluble inwater but easily soluble in the usual organic solvents; it melts at 38",and boils at 216".The benzyl saZt obtained by digesting the silver saltwith benzyl chloride at 200" forms long needles soluble in alcohol aridether insoluble in water; i t melts at 105" turns brown at 21C" anddistils with considerable decomposition at 300". The atrtide,C9H5NZO2*NKZ is formed when the ethyl salt is digested a t 100" witha saturated alcoholic solution of ammonia or by the action of am-monium carbonate on the chloride.It crybtnllises i n needles insolublein water and alkali soluble in organic solvents and melts at l i 3 " ,The chloride is prepared by acting on the dry pure acid with excess ofphosphoric oxjchloride. It is a clear limpid liquid with an intenselyirritating odour and boils at 153-15.5". It is miscible with cllloro-form and benzene is moderately soluble in ether and alcohol and isheavier than water i n contact with which the chloride is graduallydecomposed.Dibenzenyldiazoxinzeoxalene CPh<rg>C-C GN->CPh 0.Y is ob-tained by t h e action at 40" of t h e above chloride on the sodiumsalt of benzenylamidoxime suspended in chloroform. It crystallisesi n very pale glistening scales which are soluble in alcohol and ether,sparingly so in chloroform insoluble in ether and melt at 142".Itdissolves in boiling water without change and is tolerably stabletowards acids and alkalis. This substance is isomeric with Zinkeisen'soxalenediazoximedibenzenyl (this vol p. la;<) and analogou; to thesuccinic derivative obtained by Schulz (Abstr. 1885,12L9). It is prob260 ABSTRACTS OF CHE.\IICA\L PhPERS.able that duriiig its formation a transitory intermediate product,CPh <~~>C*CO*O*NnleCPh is formed. L. T. T.Action of Ethyl Chloracetate on Benzenylamidoxime. ByH. KOCH (Ber. 22,3161 -3163).-When ethyl chloracetate (1 mol.) isgradually added to an alcoholic mixture of benzenylamidoxime (1 mol.)and sodium ethoxide (2 mols.) and the whole boiled for three hours,sodium benzenylamidoximeglycollate is obtained. This forms whitecrystals very soluble in water moderately so in alcohol.Acids liberatefrom this salt benzenylamidoximeglycollic acid,NH,.C P h N- 0 43 K,*C 0 0 H.It crystallises in white needles melts a t 123-224" and is easilysoluble in alcohol arid et,her sparingly in water. It has both acid andbasic properties dissolving readily in acids and in bases but itsaqueous solution has a strongly acid reaction. When a solution ofthe acid in hydrochloric acid is boiled for some time the ajzh?qdride,CPh<NH N'o*CHz .bo ' is formed. This internal anhydride is hoieyer,Lest obtained by heating the acid for some hours at 130-140". Itis easily soluble in alcohol ether glacial acetic acid and boilingwater ; crystallises in colourless needles and melts at. 148".I t hasno longer basic properties but is still a strong acid and yields wel!-developed salts. It is very stable not being affected by bromine-water or sodium nitrite. Permanganates and analogous oxidisingagents readily attack it benzonitrile being formed. It appears to beanalogous _ _ - in composition and character to bezizenylimidoximecarhonyl,CPh<EE>CO. L. T. T.Oxidation of Paratolyl Benzyl Ketone. By E. RUCHER (Chem.Cenh. 1889 ii 445 ; from Arch. sci. phys. nat. GenBce 22 75-76).-The usual oxidising agents split up the paratolyl benzyl ketone mole-cule ; if however certain of its bromine-derivatives are heated withwater at 180" better resnlts are obtained. By treating the ketonewith bromine in carbon bisulphide the author has obtained the fivebromine subs ti tout ion-deri vati ves parato7yl b rom obenz y 1 ketone,CHPhBr*COCsH,Me melting a t 79" ; paratolyl dibronaobewyl ketone,CPhBr,*CO*CsH,Me melting a t 128.5" ; troinoparatolyl dibrornobenzylketowe CPhBr,*CO*C,iH,*CH,Br melting at 127" ; dibromoparatolyl di-brorntrbenzpl ketone CPhBr,.CO*C6Hd.CHBr melting a t 120" ; and tri-browtoparalolyl dibromobenzyl ketone CPhBi.,.CO.C,H,*CBr meltinga t 124".By heating the dibromo-derivative with water in a sealedtube the diketone COPh-CO*C6H,Me. is obtained and from trhepentabromo-derivative the diketonic acid COPh*CO*CsH4*COOH maybe prepared by the same treatment. J. W. L.Azo-colours from Naphtharesorcinol. By S. v. ROSTANECKK(Ber.22 3163-3168).-Believing that Zincke and Thelen's hydrORGANIC CHEMISTRY. 262oxynaphthaqninonehydrazine (Abstr. 1884 1359) was really n,naphthiwesorcinol-derivative analogous t o the nitroso-derivativeslately described by himself the aut,hor has re-examined it. He 6ndsthat when heated witjh acetic anhydieide and dry sodium acetate for Hfew minutes or even if digested with excess of acetic anhydride forsnme hours a diacet!yZ-deriuati*ue N2Ph*CI,,H5( OAc) is fornied Thiscryst.allises from alcohol in needles melting a t 122- 123". The forma-tion of only a monacetyl-derivative was one of the chief reasons forZincke and Thelen's formula and taking this and its general be-haviour into consideration the author believes this compound to bereally phen ylazonaph tliaresorcinol C ,,H,( OH),*N,Ph.When this compound is dissolved in a litt.le alkali the requisitequnntity of sodium nitrite added and the mixture poured into dilutehydrochloric acid nitroso;pl~e~iylazona~htharesorcinol,NZP h.C,,Hd (,ON*OH)*OH,is formed.This crystallises in glistening brownish-red scales easilysoluble in glacial acetic acid but very sparingly in alcohol and boil-ing water and alkalis. It diwolves in coiicentrated sulphuric acid toa dark-green solution; i t decomposes at 175". It dyes mordantedstuffs but much less intensely than nitrosophenylazoresorcinol. Whenreduced with tin and hydrochloric acid it yields amidonapht halic acidand aniline. This proves that the isonitroso-group has taken theremaining @-position in the nucleus.When pheiiylazoriaphtharesorcinol is dissolved in excess of alkali,and diazo benzene chloride added dip?) eny Idisazonaphtharesorcinol,C,,H4(KzPh)z(OH)2 is formed.This crystallises in long red needles,and is insoluble in alkalis but soluble in chloroform and alcohol ; i tmelts with decomposition a t 225". When reduced with tin andhydrochloric acid it yields amidonaphthalic acid arid aniline like theabove ni troso-compound and has thus the composition[(N,Ph), (OH) = 1 3 2 41.It is very similar in appearance and character t o the analogousresorcinol-derivative. L. T. T.Oil of Camphor. By J. TRIMBLE and H. J. M. SCHROETER (Pharnt.J . Trans. 20,145-148).-A sample of the crude oil oE camphor a sobtained from Japan was found to have a reddish-brown colour sp.gr.0.9632 at 16" ; i t boiled at 180". The odour resembled that ofcamphor and sassafras. By fractional distillation &c. the followingdefinite constituents were isolated from the sample :2ti2 ABSTRACTS OF CHhMlCAL PAP'k:RS.Formula. Boiling point.CloH16.. ...... 150"Cl,H,tj.. ...... 159C,,H,,O.. .... l i 6C:0H160.. .... 204C,nHl,O ..... 213C,nHl,,O ..... 232CloH,,02 ..... %47CioH16.. ...... 168CloH16.. ...... 1 i lCIOI-3[16.. ...... 180Per ceiit,.0.4012.0013-003-0015.004.0010.0030.00i.002.00The highest-boiling fraction (250-280"; 1.60 per cent.) WL~S abluish-green oil ; the quantity was iiisuificient to ascertain if i t wasa definite substmce.These compounds were fragraii t oils usually colourless and havinghigh dextro-rotatory powers. The authors also experimented onseven other samples of oil of camphor which differed considerablyfrom the former in physical properties and also in the proportionateamounts of the several fractions some of these being indeed entirelywanting in certain samples (compare Yoshida Trans.1885 779).R. R.Strophanthus Hispidus. By T. R. FRASER (Pharm. J. Trans.[3) 20 328-835).-l'his paper is a very detailed account of phar-macological processes and of the reactions of the various extractsobtained from seeds and other parts of Strophanthns. The mainresults of the author's investigations have already appeared (Abstr.,1888 €06).Strophanthin melts a t 172*5" dissolves in 55 parts of absolutealcohol 300 parts of acetone and 1000 parts of amyl alcohol and isonly very slightly hjdrolysed by ptyalin.Strophanthidin is phj sio-logically extremely active. R. R..Senegin from Polygala senega L. By A. FUNARO (J. P h ~ m .[ 5 ] 20 450-453 ; from Gazzetta 19 Sl).-Skn&gin extracted byGelhen in 1804 was found by Queveniie to yield a white powder,which he named polygalic acid. Bolley i n 1855 concluded that thesetwo substances were identical and also the same as sapoiain obtainedby Bussy from the root of Saponaria. The author finds five samplesof s6n6gia to give a mean of C = 54.13 ; H = 7.45 ; but these amountsdiffer notably from Bolley and Quevenne's figures and also from theresults published by Rochleder and by Christophson for saponin.Onboiling skndgin with dilute acids glucose is formed and a gelatinoussubstance separates containiiig C = 62.26 H = 8.21. These figuresare very wide of those obtained for sapoghnin prepared in a crystal-line form by Rochleder. The formation of se'ne'!ye'nin C40H3014 andglucose from shn6gin is represented as follows C6,H,01034 + 4H,O =The author evidently considers that saponin and sdnhgin are dif-ferent compounds although closely related.C,OH~,OI~ -k 4C6H1206.J. TORGANIC CHEMISTRY. 263Pyrroline-derivatives. By C. PAAL mid N. P. BKAIKOFF (Ber. 22,3086 -3096). - Et liy I ort hotdy Zdip henylp yrro linecarbox y late,[C6H,Me COOEt Ph = 1 3 2 51,prepared by boiling ethyl phenacylbenzoylacetate with orthotoluidinein glacial acetic acid solution crystiillises from alcohol in long,colourless needles melts at 134 -13.5" and is readily soluble in alcohol,ether glacial acetic acid and benzene.The corresponding acid,C2iH19N02 obtained by hydrolysing the ethyl salt with alcoholic:potash crystallises from hot alcohol in colourless scales melts a t226-227" sublimes undecomposed and is only moderately easilysoluble in ether alcohol and benzene.()rthotoZyldi~hen?l7y~~rr~line G3HI9N is obtained by distilling themid over lime; it crystallises from alcohol in flat colourless needles,melts at 114-115" boils above 300" without decomposition and isreadily soluble in most organic s o l ~ e n t s .E t h y l pnratol~ldiphenylpyr~oli~~ecn,-box~lat~ ci*ystallises from glacialacetic acid in slender coiourless needles melts at 145" and is readilysoluble in hot alcohol benzene and ether but only sparingly in lightpetroleum.The acid crjstallises from hot glacial acetic acid insmall colourless plates melts a t 205-206" sublimes without decoiii-position and is readily soluble in boiling nitrobenzene but only spar-ingly in ether alcohol and benzene and insoluble in light petroleum.Paratolyldiphenylpyrroline can be prepared as described in thecase of the corresponding ortho-compound ; i t crystallises from glacialacetic acid in colourless needles boils without decomposition and isidentical with t h e substance obtained by Bttumaiin (Abstr. 1887 736),by distilling para tolylpyri*olinedibenzoic acid over bargta.Ethyl ?netuxy I~lclipl~en2/Zp~rrolin~ carboxy late [ C,H,Me COOEt Ph,=1 3 2 51 prepared by boiling ethyl yhenacylbenzoylacetate wit11metaxylidine in glacial acetic acid solution is a thick oily compound.The ncid C25H21N02 cry.tallises from glacial acetic acid in c o l o u i ~ l e ~ ~needles mcl ts at 253-254" sublinies umdecomposed and is moderatelyeasily soluble in hot alcohol and benzene.1C~etazllZyZcliphen?/lpyrroline C2,H,,N crystallises i n short colourlessneedles melts at 147-149" distils without decomposition and issoluble in most organic solvents.E t h y l ~-naphth!~ldiphenylpyrrol~necarbox~~late C,,H,,NO crystal Iisesin colourless necdles or plates melts a t 181- 18d" and is readily solu-ble in hot alcohol and glacial acetic acid but only moderately easily inbenzene. The acid C2;H19N02 crystallises from glacial acetic acid incolourless plates melts at 271%- 272" sublimes undecomposcd and issparingly soluble in boiling alcohol and benzene and insoluble inlight petroleum.The potassium salt is sparingly soluble in boilingwater and insoluble in concentrated potash.a-Na~hth?lIdiphen2/lpyrroline C26H 19N crystal lises from hot alcoli 01in small yellowish needles melts at 148-149" distils without de-composition and dissolves freely in most organic solvents whenwarmed therewith.Ethyl /3-nap ht h! ldiphen ylpyrrolinecarbox?lIate cryst a1 lises from hotalcohol and glacial acetic acid in small colourIess needles melting ;i264 ABSTRACTS OF CLtEJIICAL PAPERS.181-182". The acid is obtained by boiling the ethereal salt for a.long time with a large excess of alcoholic potash ; it crystallises fromIiot. glacial acetic acid in coloiirless plates melts above 350" sublimesundeaomposed and is only sparingly soluble in all ordinary solvents.~-Na~hthyIdiphenylpyrl.oline forms fla.t colourless needles or longplates melts a t 207-d08" and is soluble in hot alcohol glacial aceticacid mid benzene.Ethyl orthohydroxyp?ien~ldipheny~~yr~oliii~ca~boxy2ute,OH*C,H,*C,N HPh2.C OOE t,prepared by boiling ethyl phenacylbenzoylacetate with orthamidophenolin alcoholic solution separates from alcohol or acetic acid in colour-less indented crystals melts a t 158-159* and is soluble in alkalisand all organic solvents. The acid C27H17N03 crystallises fromglacial acetic acid in colourless ill-defined needles melts at 24&245",sublimes without decomposition and is readily soluble in ether,alcohol and glacial acetic acid but only sparingly in benzene chloro-form and light petroleum.Ort holr ytll.,,ryphenyldiphenzll/7yrroline C,,H,,NO cry stall ises fromglacial acetic acid i n yellowish needles melts a t 175-176" and isreadily soluble in ether alcohol benzene and alkalis.E t hy 1 pcwapken y lenedi-d ip h en y 1pgrrolin.ecarbox y late,crgstnllises from alcohol in yellowish scales melts a t 249-250" andis soluble in glacial acetic acid and benzene.Thi! acid C40H29N201,Eeparates from hot alcohol in small crystals rnelt,s above 300° sub-limes undecomposed and is moderately easily soluble in alcohol andglacial acet>ic acid but only sparingly in benzene and light petroleum.F.S. I(.Action of Hydroxylamine on Pyrrolines. By G. CIAMICIAYand C. U. ZANETTI (Ber. 22,3176-3179 ; compare Abstr. 1889,1208).-Acetonjlacetoxime NOH:CMe*CH,.CH,.CMe:NOH (m. p. 236.5",cow.) identical with the compound prepared by P a d (Abstr. 1885,505) is formed when 2 5-dimethylpyrroline is boiled for about sixhours with hydroxylamine hydrochloride and sodium carbonate inalcoholic solution. This reaction tends to prove that the compound(m. p. l i 3 " ) obtained by treating pyrroline with hydroxylamine (Zoc.czt.) IS i n reality the oxime of succinaldehyde.When acetonylacetoxime is reduced with sodium and alcohol it isconverted into a base the hydrochloride of which is a colourless,crystalline compound and has the composition CsH16N2,2HC1.Thisbase has the same composition as the dianiidohexane ohtained byTafel (Abstr. 1889 976) by reducing the dihydrazone of acetonyl-acetone.With hydroxylamine metadimethylpyrroline yields a compoundwhich is soluble in water and has powerful reducing properties ; thisnew substance is converted into a base CsHd when i t is reducedwith sodium and alcohol. F. S. KORGAXIC CHEMISTRY. 2G5Derivatives of LHydroxyquinoline. By E. LIPPMANN and F.FLEISSXER (Monatsh. 10 794-797). -Amidohydroxyquinoline hasbeen isolated by Fischer and Renouf (Abstr. 1884 1370) but maybe more conveniently prepared from the corresponding nitroso-curn-pound which is obtained as hydrochloride by adding sodium nitrite(25 grams) t o hydroxyquinoline (50 grams) in an aqueous solutioncontaining hydrochloric acid (100 grams).The hydrochloride of thenitroso-compound forms an orange-coloured crystalline mass which isonly slightly soluble in water but more soluble in dilute hydrochloricacid; it is decomposed on boiling its aqueous solution but may beobtained in yellow- or brownish-coloured scales or needles by verycareful recrystallisation. With sodium acetate it gives a gelatinousprecipitate which becomes crystalline on standing. Nitrosohydroxy-qninoline NO*C,NH,*OK [= 4 13 crystallises from alcohol inpale-yellow or greenish needles only slightly soluble in benzene,ether and chloroform and decomposes on heating to 230".Theplutinochloride ( C,H,N,O?) H2PtC16 crystallises in brown glisteningscales and is decomposed on boiling with water. In order to deter-mine the relation O F t h e nitroso-group to the hydroxyl-group theauthors converted it by means of nascent hydrogen into amidohydroxy-quirioline which on oxidation with potassium dichromate and sul-phuric acid and reduction with sulphurous anhydride furnished quinol.If the reduction is brought about by means of tin added a little ata time to a solution of the nitroso-compound in hydroc!iloric acid aviolent reaction ensues and a crystalline double salt is obtained. Onfreeing this froin t i n by hydrogen sulphide and adding t o the solutionsodium acetate a dichlornmidohydroxtlquinoline C,NH3C12 (NH?)*OH,separates out as a white crjstalline mass whilst amidohpdroxy-quinoline remains in solution.The dichloro-derivative crystallisesfrom alcohol benzene or chloroforin in slender white silky needles,which decompose at 160" and furnishes a hydrochloride crystallisingfrom dilute hydrochloric acid in yellow needles and readily decom-posed by boiling water. If stannous chloride is substituted for themetal amidohydroxyquinoline is the sole reductiou-product and fromthis a dihydroxyquinoline sulphate decomposing at 2&" and identicalwith the compound described by Fisher and Renouf (Zoc. cit.) maybe obtained. It must therefore be concluded that the nitroso-compound contains the nitroso-group in the para-position relativelyto the hydrox yl -group.By A. C LA US (J.pr. Chem.[ 21 40,444-447) .-Bromoquinolinesuiphonic acids may be obtained :(1) By synthesis from bromamidobenzenesulplionic acid ; (2) bybrominating qninolinesulphonic acids ; (3) by suiphonating broino-quinolines ; (4) by substitutiiig bromine for a hydroxyl- amido- &c.,group in a hydroxy- amino- &c. quinolinesulphonic acid. Of thest:four possible methods the third gives the best results. The orienta-tion of the acid is settled by treatment with tin and hydrochloricacid (Lellmann Ahstr. 1888 296) which produces a hjdroquinuline-sulphonic acid. The hydroquinolinesulphonic acitls are being investi-gated in the author's laboratory.G. T. M.B romoquinolinesulphonic Acids.VOL. LVIII. 266 ABSTRACTS OF CHEMICAL PAPERS.Hydroquinoline-4-sulphonic acid crystallises in large rhombic tahles,or monoclinic leaflets which begin to melt at 318" (uncorr.) withdecomposition.Hydroquinoline-1-sulphonic acid crystallises in pointed needles anddecomposes at 243" (uncorr.).Hy droquinol ine-3-sulp honic acid forms characteristic glassy s h ork,monoclinic prisms the measurements of which are given.It decom-poses a t 277" (uncorr.). A. G. B.Sulphonic Acids of 4'-Bromoquinoline. By A. CLAUS and W.SCHMEISSER (J. pr. Chern. [2] 40 447-454) .-4' 4-Bromoquinoline-sulphonic acid is obtained by heating 4'-bromoquinoline with sulphuricacid for some time at 250"-300"; it crystallises from alcohol inbeautiful silky needles and from water both in long slender needles(with 1 i mols.H20) and in large anhydrous prisms which becomeneedles whcn recrystnllised from hot water. It is insoluble in ether,decomposes above 300" without melting and is stable in alkalinesolutions. When treated with tin and hydrochloric acid it is con-verted into hydroq~iiioline-4-sulphonic acid. The potassium salt (with1 mol. H20) the sodium salt the calcium salt (with 7 mols. H,O),the barium salt (with 3 mols. H,O) the copper salt (with 7 mols.H20) and the silver salt are described. The ethyl salt formstransparent needles melting at 125" (uncorr,). The chloride,C,NH,Br-S02C1 crystallises from chloroform in needles and fromether in thick prisms which melt a t 82" (uncorr.). The amide formssmall slender needles melting at 255" (uncorr.).4' 2-Bromo~uinolinesui$?~or,ic acid is formed together with theabove 4-sulphonic acid when 4'-bromoquinoline (1 part) is heatedwith sulphuric acid ( 5 parts) containing 30-40 per cent. of sul-phuric anhydride for about an hour on the water-bath.If theheating is longer or the temperature higher the 2-sulphonic acidis converted into the 4-sulphoriic acid. The two acids are sepa-rated by crystallising from water and treating with 96 per cent.alcohol when the 4-sulphonic acid dissolves. 4' 2-Bromoquinoline-sulphonic acid crystallises in colourless rhombic tables which aresparingly soluble in cold water and insoluble in other solrents; itcan be heated to 300" without melting or decomposing. It is notacted on bv hot alkalis. Tin and hydrochloric acid convert it intoa hydroquinolinesulphonic acid which melts a t 2,55" and has not yetbeen described ; it is probably hydroquinoline-2-sulpkonic acid.Thesodiura salt the potassium salt (with 1 mol. H20) the barium salt(with 1 mol. H,O) the calcium salt (with 4 mols. HsO) the coppersrrlt (with 1 mol. H20) and the silver salt are described. The ethylsult forms short needle-shaped crystals melting at 100" (uncorr.).The chloride C9NH5Br*S02CI crystallises from chloroform in colour-less needles and from alcohol in beautiful lustrous leaflets ; it meltsat 130" (uncorr.). The amide crystallises from hot water in small,white slender needles melting a t 213" (uncorr.) and soluble inalcohol.When these two acids me brominated they yield different tri-bromoyninolines.The 2-sulphcnic acid yields a tribromoyuinolin0 RGANIC CHEMISTRY. 267which crystallises in colourless lcstrous pi-isms melting at 171"(unvorr.) ; while the 4-sulphonic acid yields a tori bromoquilnolinewhich crystallises in slender colourless needles melting at 300"(uncorr.). A G. B.Sulphonic Acids of 4-Bromoquinoline. By A. CLAUS and 0.WURTZ (J. pr. Chem. [217 40 454460).-Wiien 4-brornoquinoline(1 part) is heated in a flask with sulphuric acid containing 50 percent. of sulphuric anhydride ( 5 parts) a t 130-140" for 6-8 hoiirs,the 1- and 3-sulphonic acids of 4-bromoquinoliue are obtained theformer in considerable quantity the latter in small quantity. Th:yare separated by crystallising from water when the 1-sulphonicacid crystallises first.At higher temperatures disulphonic acids areproduced a t the same time.4 1-Bromoqzcinolineswl~honic acid crystallises (with 2 mols. H,O)in colourless lustrous needles or prisms which dissolve in hot water,but not i n cold water o r in alcohol. The anhydrous acid is uncbangedbelow 300". When reduced by tin aiid hydrochloric acid it yieldshydroquinoline-1-sulphonic acid. The sodium salt (with 2 mols.H,O). the potassixm salt (with 2 mols. H,O) the calcium salt (sbith4 mols. H,O) the bam'um salt (with 3 mols. HLO) the copper snlt(with 5 mols. H,O) the silver salt and the lead suit are described.The ethyl salt melts at 110" (uncorr.). The chloride C,NH,Br*SO,Cl,crystallises from ether in small colourless prisms and from alcoholin tables; it melts a t 125" (uncorr.).The amide forms small needlesmelting at 2 0 5 O (uncorr.) arid soluble except in water.4 3-Bromoquinolinesulpho?iic acid crystallises in small lustrous,colourless anhydrous needles soluble in alcohol and in water. Thesodizm salt (with 1 mol. H20) the calciunz salt (with 7 mols. H20),and the barium salt (witn 2 mols. H,O) are described. The ethyl saltmelts at 130° (uncorr.) ; the chloride melts a t 95" (uncorr.) ; the amideforms small dark-yellow crystals melting at 195" (uncorr.).When the acid is reduced with tin and hydrochloric acid. it yieldshydroquinoline-5sulphonic acid (?) melting a t 171" ; and when brorri-nated it yields a tribromoquinoline melting at 248" (uncorr.).3 LBromoquinolinesulphonic Acid and 4 3-Nitrobromo-quinoline.By A. CLAUS arid G. ZUSCHLAG ( J . pr. Chem. [ a ] 40,460-464).-La Coste (Abstr. 1883 96) obtained several sulphonicacids by sulphonating parabromoquinoline. The authors usingfuming sulphuric acid (30 per cent. sulphuric anhydride) a t 1.20-125",only obtained one sulphonic acid.3 1-Bromoquir~olinesulphonic acid crgstallisees in beautiful Iud,rous,white needles and prisms which are anhydrous do not melt a t 3.5U0,and are moderately soluble in hot water. The potassium salt (with1 mol. H,O) and the silver salt are described; the ethyl salt formslong colourless silky needles melting a t 139". When brominated i tyields a tribrornoquinoline which cryst allisefi in colourless needles andmelts at 185" (uncorr.).Reduction with tin and hydrochloric acidconverts it into hydroquinoline-1-sulphonic acid.La Coste's nitrobrornoquinolitie (Abstr. 1683 91) is 4 3-nitro-A. G. B.t 2ii8 ABSTRACTS OF CHEMICAL PAPERS.Zlromoquinoline; i t melts a t 130" (uncorr.) not 133" ; its hydrochloyide,platiuochlmide and methiodide were obtained.4 3-amidobromoqninoline (Zoo. cit.) melts a t 160" (uncorr.) not 164".Hydroxyquinolinesulphonic Acids. By E. L I m i A s N and F.F L E ISSN ER (Monatsh. 10 798-804) .-When 1-hydroxyquinoline(1 part) is heated with sulphuric acid (3 parts) in a sealed tube forthree hours a t IhO" the product is a light-brown syrup which scarcelvsmells of sulphurous anhydride and cou tains a sulphonic acid,OH*C,NH,.SO,H + l$H,O which crystallises in pale-yellow needles,melts with decomposition a t 275" is only slightly soluble in alcohol,and is insoluble in ether.The aqueous solution is strongly acid givesa green coloration with fewic chloride and an almoht insoluble,crystalline precipitate with lead acetate. The potassium salt isanhydrous and crystallises from water in light rose-coloured,glistening scales. Its aqueous solution gives a green granular prcci-pitate with a solution of cuprie sulphate and a crystalline precipitatewith mercuric chloride; the silver sa!t is a crystalline powder; thebarium salt is an almofit insolu'ble powder.Besides the above-described cornpound l-hydl.oxyquitioZinecEisul~?~-nuic ucid OH*C9PU' H,(SO,H) is simultaneously formed in smallyiiantities. It may be more readily obtained by heating a mixture ofhydroxjquinoline (25 grams) snlphuric acid (7.5 grams) and phos-phoric anhydride (30 grams) a t 200" f o r five hours.It is a veryhygroscopic substance and decompoces a t 200". The hydrogenpotassium salt is a crystalline precipitate; the basic salt,OK.CeNH,( S03K)2 IL compound sparingly soluble in water ; thebasic copper salt Cu[O*CgNH4(S03),Cu] + 10H,O a light-greenpowder. G. T. M.Paradiasine-derivatives. By 9. W. ABENIXJB (J. pr. Chem. [2],40,425-444 ; compare Abstr. 1889 134).Brornacetnnilide NHPh-OO*CH,Br is obtained by mixing benzenesolutions of aniline (2 niols.) and bromaeetic bromide (1 mol.) eva-porating the benzene a t the ordinary temperature and washing theresidue with water which leaves bromacetanilide undissolved.Itcrystallises in slender whiten eedles which melt at 130-131" and aresoluble in alcohol ether and benzene but not in water.Chloracety lphe q L g Z y cine CH,CI*CO*NPh.C H,* C 0 OH is formedwhen phenjlglyciue suspended in ether is shaken with an etherealsolution of chloracetic chloride (eq. mols.) ; the ether is distilled off,and the residue treated with water when .the ehloracetylphenylgly-cine separates as an oil which soon crystallises. It fornis four-sidedtables o r prisms melting a t 132-133O soluble in alcohol aud benzene.A. G. B.Dip Leny ldiket odih ydropnra dimkne N P h < CH,,CO>NPh ' O°CH2 is iden-tical with Meyer's p'henylglycine anhydride (this Journal 1878,294) ; it may also be obtained by the action of alcoholic potash OIIbromacetauilide and by heating chloracetylphenylglycine (1 mol.)with aniline (2 mols.) a.t 143-150' ; this last reaction settles its con-stitution.It melts a t 263"ORGANIC CHEJl ISTRT. 2(;9Phenylglycinylphenylglycine has been described before (Abstr.,1888 854; compare Hausdorfer Abstr. 1889 1014) ; it melts a tl2n-130".Bronzacetoparatoluidide C6H,Me*NH*C0.CH2Br [Me NH = 1 41,obtained in the same way as bromacetanilide crystallises from hotalcohol in long colourless needles which melt a t 164".Dipayato ly ldiketod ihydropnradiazine,is obtained from broniacet,oparatoluidide or from paratolylglycocine int,he same way RS diphenyldiketodihydroparadiazine is obtained fromthe corresponding phenyl compounds. I t crystallises from alcohol inbeautiful long white needles which melt a t 232-253" and aresoluble in glacial acetic acid but only sparingly soliiblc in othersol ve 11 t s.RthylgZycol~lparatoluidide C6H,hle*N HCO-C H,*OEt [Me NH =1 41 is obtained as a bye-product in preparing the above parudiazinefrom bromacetoparatoluidide and alcoholic potash and may be sepa-rated from the mother liquor of the paradiazine by ether which dis-solves it.It crystallises in beautiful transparent prisms which melta t 32" and are soluble except in water.Purahromaceto-z?lZidide C6H3Me2*NH*CO*CH,Br [Me2 NH=l 4 31,prepared by mixing benzene solut,ions of paraxylidinc (2 mols.) andbromacetic bromide (1 mol.) crystallises in slender white needleswhich melt at 14.5".Dipamxy 1 y 1 dike tud i?y drop aradiaxine,C6H3NeZ'N<CH2.C4 Co*cHz>N-C6H,Me2 [Me2 N = 1 4 21,is obtained by the action of alcoholic potash on parabromticeto-xylidide:it crystallises from hot alcohol in beautiful flat needles melting at203" and soluble in benzene and acetic acid but not in water andether.Ethylgl~col~~lya~axylidide C,B,Me,*NH.CO*CH,.OEt [Me NH =1 4 23 is extracted by ether from the mother-liquor of the last-mentioned paradiazine ; it crystallises i n prisms melting a t 50" andsoluble in the usual solvents.Di- a-nap ht hy Id iketodih y droparadiazin e,obtained from chloracetonaphthalide and alcoholic potash crystallisesfrom glacial acetic acid in flat needles melting at 27&275" andsparingly soluble in alcohol benzene and ether.Methyl mdanitrocunzate N02~C,H3Pr*C00Me [ P r Me0 NO2 =4 1 31 is obtained by dissolving nitrocnmic acid in methyl alcoholand saturating i t with hydrogen chloride ; i t forms large crystals likenitre which melt at 64" and are soluble in most aolvents.Methyl metamidoc~~rnnte is obtained by reducing the nitrocumatewith tin and hydrochloric acid ; it crystallises in colourless transpa270 ABSTRACTS OF CHEMICAL 'PAPERS.rent prisms or tables melting a t S1-52" and easily soluble except inlight petroleum.Meth y Z metnchloracet amidocumat e CH,Cl*C O*NH-CsH,Pr*C 0 OMe[Pr COOMe NH = 4 1 31 is prepared by mixing benzene solu-tions of the metamidocumate (2 mols.) and chloracetic chloride(1 niol.) evaporating the benzene at the ordinary temperature andwashing the residue with water which leaves the chloraceto-deriva-tive undissolved.It crystallises from hot dilute alcohol in long,slender colourless needles melting a t 101-102" and easily soIuble Inmost solvents except water and light petroleum. If bromaceticbromide be substituted for chloracetic chloride in the above prescrip-tion methyl metctbromacetamidocumnte is obtained ; it melts a t106-107".Uipl.opyld~phen2/ldiketodihyd?.g,aradiazinedicarboxilic acid,CINzH4(C6H,Pr*COOH) [COOH Pr N = 1 4 31,is prepared by heating alcoholic potash (1 gram) with methyl meta-chloracetamidocumatc (4 grams) in alcohol for half an hour thenadding another gram of potash and heating for another half hour ;the alcohol is now evaporated the residue treated with water and anexcess of hydrochloric acid added ; this throws down a resinous sub-stance which is washed and heated with alcohol. Part dissolves (seebelow) leaving the dicarboxylic acid as an insoluble powder whichdecomposes before melting and dissolves in alkalis being reprecipitatedby acids.The ethyl salt obtained by the action of dry hydrogeiichloride on an alcoholic solution of the acid crystallises in flat lustrous,oblique-ended needles melting a t 192-193" and soluble ill alcohol.2CZetethyZglycodyZanzidocumic acid OEt-CH2*CO*NH-C6H3Pr*COOH[COOH Pr NH = I 4 31 is tEat portion of the above-mentionedresin which dissolves in alcohol ; the alcohol is evaporated the residuedissolved in potash reprecipitated by hydrochloyic acid and crysta 1-lised from weak alcohol.It forms four-sided tables melting a t 140°,and soluble except in water and petroleum.Y h eny lort hot oly 1 dike t odih y dro paradiaxin e,NPh<Co*CRz>N*CsH,Me CHz*CO ,[Me N = 1 21,is obtained by heating chloracetorthotoljlglycine (1 mol.) withaniline (2 mols.) in a sulphuric acid bath a t 160"; the product isheated with water and hydrochloric acid filtered and the undissolvedportion crystallised from alcohol. It forms slender white needlesmelting a t 165-166" soluble in hot alcohol and benzene but insolublei n ether. It forms no platinochloride.Orthotoly lparatoly ldiketodihydroparndiu,z~ne,C H ~ ~ * N < C ~ .~ ~ > N ' C ~ H M ~ CO*CH [Me N = 1 2 and 1 41,is obtained by substituting paratoluidine for aniline in the prepara-tion of the last compound. It crystallises in long white feltedneedles melting a t I79-l8O0 soluble in alcohol and benzene but notin ether. A. G. BORGANIC CHEMISTRY. 271Ditriazole-derivatives. By J. A. BLADLN (Ber. 22 3 1 1 6 . I 3117 ; compare Abstr. 1889 138).N- GEt prepared by boil-SEt-NN*NPh'c'ceNPh*NDi-pheny leth y ltriazo le,ing cyanophenylhydraeine with excess of propionic anhydride crystal-lises from alcohol in prisms melts at 186-5-187" and is readilysoluble in alcohol but insoluble in water. The hydrochloride,C20HLON6,2HCl crystallises in microscopic prisms and is decomposedby- water. The platinochloride crystallises in orange-yellow unstabieprisms.Di-diphenyltriazoZe C29'E3C20N6 prepared by treatinq cyanophenyl-hydrazine with benzoic chloride crystallises from alcohol in colour-less needles witdh 2 mols.H20 loses its water at loo" melts at2.57-258" and is only sparingly soluble-in alcohol very sparingly inether and insoluble in water; it is a very feeble base.Di-paratoZy lmat h y I triaxole Cz0HZON6 is obtained when cyanoparatol y I -hydrazine is boiled for a few minutes with excess of acetic anhydride.It crystallises from alcohol in long prismatic needles melts a t259-260". and is moderately easily soluble in alcohol but onlysparingly in benzene and insoluble in water. The hydrochloride isreadily soluble.Di-para,tolylet?Lyltriazole C22H21N6 prepared from propionic anhy-dride in like manuer separates in crystals from alcohol aqd benzene,in which i t is readily soluble melts at 202-2203" and is ins;oluble inwater.D i-pnmtol y lp JLeny 1 triazol e CMHZ1N6 prepared from benzoic chloridein like manner crystallises from alcohol in microscopic needles with2 mols.H20 and from benzene in small plates with 1 mol. of benzene ;it melts at about 300" is insoluble in water and is only a very feeblebase. F. S. K.Bases formed by the Action of Potassium Hydroxide on theHalogen-klkyl Salts of Papaverine. By A. CLAUS (J. pr. CJhem.r2] 40 465-4T9).-1n this paper the author replies to t h e recentkticisrns of Goldschmiedt (t'his vol. p. 179) on the work which he(the author) and others have already published on this subject (seeAbstr.1885 996 ; 1889 414). A. G. B.Belladonine. By E. D~~RKOPF (Ber. 22 3183-3184).-Thebrown syrup from which atropine has been obtained (commercially)is a mixture of helladonine atropine hyoscyamine hyoscine andtheir decomposition-products tropine pseudot,ropine and tropic acid.When the syrup is boiled with chloroform and ether in acid solution,the hydrocarbons &c. are removed and the atropine in the purifiedbase can by some suitable means be converted into tropine andtropic acid ; the belladonine is not changed by this treatment but thehyoscine (18-20 per cent.) passes into solution and can be easily iso-lated by means of the aurochloride. This salt C17H23N03,A~C19,crystall&es in prisms melts at 200" and is sparingly soluble in water;F.S. K2 i 2 ABSTRACTS OF CHEMICAL PAPERS.Fumarine. By R. REICHWALD (Zeit. am-zl. Chem. 28 622-623).-Fumarine is soluble in 11.2 parts of chloroform and in i8.68 partsof benzene but is only very sparingly soluble in water alcohol ether,and petroleum. When treated with Frohde's reagent it first. turnsviolet then dark-green ; with vanadyl sulphate i t gives an emerald-green colour which after some hours becomes yellowish-green ;with sulphuric acid and sugar it gives a dirty-violet coloration ; withselenosulphuric acid a pure violet. It is not coloured by chlorine-water but becomes violet-brown with bromine-water and sulphuricacid. A crjstal of potassium nitrate thrown into its solution insulphuric acid coloors the liquid as it dissolves first preen thenviolet and lastly yellow. Potassium dichromate added to a fumarinesalt throws down funiarine chromate ; on adding concentratedsulphuric acid intense green and violet streaks are produced passing,after a few minutes into green. M. J. S.Preparation and Properties of Albumin free from Ash. ByE. HABNACK (Ber. 22 3046-3052 ; compare Abstr. 1882 747).-Albumin free from ash can be obtained a s follows:-The copper-compound of albumin prepared as previously described (Zoc. cit.) ispurified by dissolving i t in very dilute soda yeprecipitating withacetic acid and washing well with water the process being repeatedseveral times; the precipitate is then dissolved in a considerablequantity of soda the solution kept for 24 hours the albumin precipi-tated by neutidiuing with hydrochloric acid washed with water anddried at 100".It is thus obtained in the form of a gelatinous transparent brittle.yellowish-red mass which is almost free from ash 1 gram leaving aresidue of about 1 milligram on ignition. I t is free from phosphorusand phosphates and iron could not be detected. When the moistsubetance is treated with pure cold water it gradually swells np anddissolves ; the solvent action being hastened considerably by boiling.The dry substance shows a like behaviour but i t dissolves muchmore slowly. The residue obtained on eraporating the aqueoussolution to dryness seems to have the same properties as the originalsubstance.Albumin free from ash is precipitated from its aqueous solutionby acids the precipitate being insoluble in excess ; also by neutralsalts for example sodium chloride but the precipitate dissolvesagain if the solution is diluted very considerably. The precipitatedalbumin has the same properties as the original substance but if theprecipitate is boiled with the solution it is gradually converted intoa modification insoluble in water,Albumin free from ash is precipitated from its aqueous solutionby salts of the heavy metals phosphomolybdic acid potassium ferro-cyanide &c. ; b u t it is not precipitated by alcohol ether phenol ortannic acid. F. S. I(.Heat Coagulation of certain Proteids. By J. B. HAYCRAFTand C. W. DUGGAN (Brit. Med. J. 1890 i 167-169).-1t is foundthat there are various circumstances that affect the temperature a ORGANIC CHEN ISTRT. 2’73which any prote’id enters into the condition of a heat-coagulum. Ifa solut,ion of a coagulable protei’d is heated quickly the proteid willbe foiind to coagulate a t a higher temperature than if the heat isapplied more slowly. The coagulation point is considerably raised bydiluting the solution and a very dilute solution may not coagulateeven on boiling. The presence of certain neutral salts lowers ofothers raises the coagulation temperature. The presence of acidslowers of alkalis r R ises the coagulation temperature. These factswere ascertained to be true for egg albumin serum albumin vitellei’n,and sernm globulin.Halliburton ( J . Physiol. 5) and Corin and Berarci (Abstr. 1889,1075)attempked to separate proteids by means of fractional heat coagulation.Without doubting the possibility of fractionating some prote’ids,the result of the present experiments seems to cast a doubt on themethod adopted unless other differences be denionst,rated to existbetween the various proteids thus separated. It is thus possible thatserum albumin or egg albumin may be single prote‘ids and the fact thatvarious precipitates at different temperatures are obtainable can beexplained in one of two ways either that the heat when applied foi.a long time (in Corin and Berard’s experiments for upwards of anhour) alters the character of the proteid i n solution so that its tem-perature of coagulation is heightened or that the result is simplythe effect of dilution ; a solution of serum albumin is raised to 73” ; aprecipitate occurs and is filtered off; that left in solution is now morediluted hence its coagulation temperature is higher.Precipitation of Albuminoids from Urine. By - BOYMOND (J.P h a ~ m . [5] 20 481-482).-1n attempting to form a filter of talc(previously washed in hydrochloric acid and water) €or the filtrationof turbid urine the whole of the globulin contained in the urine wasfound to be removed by the so-called neutral substance composing thefilter; whether any serei’n (? serum-albumin) was removed has notyet been determined. Experiments were instituted with other neutralsubstances and i t was found tbat bismuth subnitrate completelyremoved both globulin and “ serein.’’ This research is still being Fro-secuted. J. T.By A. JAQUET (Zeit. physiol. Chem. 14 289-296).-A sample of dog’s h~~moglobin prepared according to Zinoffsky’smethod (Abstr. 1886 ZCS) gave the folloiving percentage composi-tion which may be compared with the results obtained previouslywith dog’s Emmoglobin (Ahstr. 1888 731) and with Zinoffsky’sanalysis of horse’s haemoglobin in the following table :-W. D. H.Haemoglobin.Heemoglobin of dog.r-A-- 7Previous analysis. Present analysis. Of horse (Zinoffsky).C . . .... 53-91 54.57 51.15H.... .. 6.62 7.22 6.76N.. .... 15-98 16.38 17-94S.. .... 0.542 0-568 0.39Fe .... 0.333 0.336 0.335 o...... 22-62 2( 1-93 23.42174 ABSTRACTS OF CHEMICAL PAPERS.The formula for dog’s haemoglobin deduced from this secondanalysis is C,5sH,?,3N,,,SJFe0,18.An analysis of hen’s hEmoglobin wits also made; the percentagecomposit,ion was C 52.47 ; H 7-19 ; N 16.45 ; S 0.8586 ; Fe 0.3353 ;0 22.5 ; P 0.1973.The relation of S E’e = 9 2 ; the relation of Fe P = 1 1.The only other preparation of birds’ blood that has been analysed isthat of goose’s blood by Hoppe-Seyler. He also found phosphoruspresent (0.7- per cent.) and this has generally been regarded as dueto admixture with nucle‘in ; the relation of phosphorus to iron in thepresent research seems to indicate that the phosphorus may beactually in the hEmoglobin-molecule. W. D. H

ISSN:0368-1769    

DOI:10.1039/CA8905800223

出版商:RSC    

年代:1890

数据来源: RSC

摘要:

2174 ABSTRACTS OF CHEMICAL PAPERS. P h y s i o l o g i c a l Chemistry. Respiration of Entoeoic Worms. By G. BUNGE (Zsit. physiol. Chem., 14, 318--324).-1n an earlier communication (ibid., 8, 48) it was shown that the Ascu~is mystax, the worm that lives in the intestine of the cat, will live four or five days in media quite free from oxygen. Renewed experiments with Ascaris acus, from the intestines of the pike, are confirmatory of the above ; these worms live for four to six days, and exhibit movements, ill. niedia free from oxygen. In the ultimate respiratory processes of these animals there must be a for- mation of energetic reducing substances (nascent hydrogen and easily oxidisable organic: matter) which unite with one atom of the oxygen-molecule, even to a greater extent than in animals which breathe oxygen.I n order to investigate this question more fully, larger varieties of Ascaris were employed. The A . rnegalocephala of the horse was found unsuitable, as it only lived for two dajs after retnoval from the intestine; the A . Zumbricoides of the pig was therefore used; this lived from five to seven days. I n boiled salt solution it gave of€ abundance of gas, which was collected over mercury, and was com- pletely absorbed by potash, consisti~ig of pure carbonic anhydride, and containing no hydrogen. ‘l’he quantity of gas obtained in this time was from 5 C.C. to IU C.C. per gram of the animal’s body-weight. I n three experiments, a small, measured quantity of oxygen was added to t h i s gas artificially, but there was no diminution in its volume after the admixture ; thus not only hydrogen, but othcr reducing substances are absent also.W. L). H. Ttiese animals possess no respiratory apparatus. Heat developed by the Action of Oxygen on the Blood. By BERTHELOT (Compt. rend., 109, 776-781).--The experiments were made w-ith defihrinated fresh sheep’s blood which had been allowed to remain in a closed flask for 24 hours. ‘l’he scai-let colour had changed to purple, the sp. gr. was 1.057 at go, and the specific heat 0.872. ItPHTSLOLOGICAL CHEMISTRY. 2 i 5 was placed in the calorimeter, and a current of nitrogen, saturated with moisture, was passed through for some time. Dry oxygen was then passed in, and the temperature observed at frequent intervals. Before weighing the calorimetric vessel, the oxygen in the empty space was expelled by means of nitrogen.I n one experiment, 100 vols. of blood absorbed 20.2 vols. of oxygen, in another, 18.5 vols. The heat developed per 32 grams of oxygen was 14.63 Cals. in the first case and 14-91 in the second, or a mean of + 14.77 Cals. The formation of silver oxide develops + 14.0 Cals. ; of barium peroxide, + 24.2 Cals. ; of lead peroxide, + 24.5 Cals. per 32 grams of oxygcn ; and it is evident that the heat liberated by the formation of oxyhaemoglobin is of the same order of magnitude as the heat of formation of many true oxides. The combination of carbonic oxide with haemoglobin developed + 18.0 CaIs. and + 19.4 Csk., or a mean of + 18.7 Cals. per 28 giams, a disturbance of the same order of magnitnde as the heat of forma- tion of oxyhamoglobin, but distinctly higher.The heat developed by the action of oxygen on the hlocd is almost exactly one-seventh of the heat which would be liberated by the com- plete oxidation of carbon by the same quantity of oxygen, and hence it follows that of the total animal heat about one-seventh is developed in the lungs by the combination of oxygen with the blood, and the remaining six-sevenths in other parts of the body in consequence of oxidations and hydrations. The development of heat in the lungs is almost exactly compen- sated by the absorption of heat due to the liberation of carbonic anhydride and water vapour, and whether the temperature of the hlood in the lungs rises or falls is determined by the temperatiire of the inspired air, but the variation in oce direction or the other is not greater than the tenth of a degree. Animal Heat and the Heat of Formation and Cnmbustion of Urea.By BERTHELOT and P. PETIT (Contpt. rend., 109,759-764). -See this vol., p. 206. Artificial Digestion of Prote'ids. By A. STUTZER (Landw. Versuchs. Stat., 36, 331-388) .-The method proposed by the author consists in treating the food first with an acid pepsin solution and then with an alkaline pancreatic liquid, and determining the nitrogen in the undissolved substance ; from the relation of the indigestible to the total proteid nitrogen, the digestibility coefficient is calculated. The method gives, according to Pfeiffer (Journ. f. Landw., 34,444), results nearly identical with tliose obtained by means of direct experiments with animals.The pepsin solution is prepared by cutting the mucous skin of a fresh pig's stomach into &mall pieces and keeping it for one or two days with 5 lit'res of water, 100 C.C. of hydrochloric acid (con- taining 10 grams of hydrogen chloride) and 2.5 grams of salicylic acid; it is then poured through a flannel bag and filtered, first through a coarse and then through a dense lilter paper. It is best to prepare several extracts a t once. C. H. B.276 ABSTRACTS OF CHEMICAL PAPF RS. The pancreas extract is obtfiined by cutting up the pancreas (1000 grams) of a bullock, rubbing it np with sand, and exposing it to air for 24-36 hours. It is then treated with lime-water(S00 c.c.), glycerol (sp. gr., 1.23 ; 1 litre), and some chloroform, kept for four t'o six days, filtered, heated for two hours a t 37-40', and again filtered, iE necessarp. Before using the extract, 250 C.O.of it is mixed with sodium carbonate solution (7.50 C.C. containing 5 grams of the an- hydrous salt), heated a t 37 to 40" for one or two hours, and filtered. The determination of digestible substance is made as follows :- the finely powdered food (2 grams) is tied up in paper and extracted with ether from five to six hoiirs to remove the fat. It is then treated with the pepsin solution (650 c.c.) and heated a t 37 to 46" for 24 hours, 10 per cent. hydrochloric acid (2.5 c.c.) being added at intervals of about one hour until the solution contains 1 per cent. of acid. The suhstaiice, wit.h the asbestos, is heated with the alkaline pancreas extract (100 c.c.) for six hours at 37-40', the liquid being stirred some- times.After this it is filkered, washed with water, dried, and the nitrogen determined in the substance. I t was found that if the subst,ance is treated with 400 C.C. of pepsin solution cont,aining 0.2 per cent. of hydrogen chloride, without sub- sequent digestion with pancreas, somewhat less nitlrogen is dissolved than when the less amoant of more strongly acid pepsin is em- ployed. But if the food is aEtervi-ards digested with pancreas, the final result is the same in both cases. N. H. 31. It is then filtered through asbestos. Absorption of Sugar from the Small Intestine. By S. GINS- BERG (PJEuger's drchiv, 44, 306--316).-v. Mering (Arch. Anat. i~hysiol., physiol.Abth., 1877, 379) showed that the chyle from the thoracic duct of the dog contained no more sugar during the diges- tion of carbohydrate than at other times, but that the percentage of sugar in the portal blood was increased under these circumstances. Heidenhain pointed out (Pfliiyer's Arclziv. dupp., 1888, 71) that this is probably due to the fact that the water and substances, like sugar, easily soluble in water are taken up by the blood-vessels as they lie immediately beneath the epithelium, and so do not reach the more centrally situated lacteals of the villi. The present research, undertaken under Heidenhain's superintendence, was directed to ascertaining, whether by greatly increasing the amount of sugar and water in the food, some might not be found even in the chyle.The first experiments were performed on rabbits, wit<h results given in the following table (p. 277). These show that during a normal diet the amount of sugar in both blood and chyle is very constant. The seemingly higher percentage in the latter is due to the fact that the percentage is taken for the total blood, including corpuscles. I n round numbers 100 parts of blood contain 60 volumes of plasma; hence, the per- centage i n the plasma would average 0.28, which is higher than that in tlie chyle. l'he rise of the perccmtage during sugar feeding, both i n blood and chyle, is very marked.PHYSIOLOGICAL CHEMISTRY. 277 Percentage of sugar in Blood. Ch jle. 0 -23 3. ............... 0 -18 0 '25 4. ............... 0 -23 Mean.. .......... 0 '18 0 *24 ;: : : : : : : : : : : : : : : : 1 Ri: 0.23 Food.Kormal diet. J J > ? J ) J 7 5 ................ 0 '22 6. ............... 0'39 7. ............... 0 -33 8. ............. 0 -31 3fean.. .......... 0 31 5 grains sugar in 50 C.C. water. 15 9 ) 100 ? J 15 J ? 100 > J 25 J 150 ,. 0'36 0 -7G 0 *39 0 '46 0 -49 The second series of experiments, made on dogs with a fistula of the thoracic duct', show the same result, and are st'ill more satis- factory, as the same animal could be used in the two experiments. The following table contains the results of a few of the experi- ments performed. 'The sugar solution was injected into the iutestine. - l . . . 2 . .. 3... 4.. . ~~~~ ~ Percevtage of sugar in Chyle. I Blood. Before injection. 0.14 0.07 0.09 0.08 After injection.0 -14 0 '27 0 *18 0 -88 Before injection. 0 -24 0 -25 0 22 0 * 1 G After injection. 0 2 7 0 5 2 0 *35 0 *42 Amouii t injected. 30 grams in 600 C.C. of water. 41) J 9 J J 20 J ) 400 2 ) 30 J J 4uo J J W. L). H. Osmosis with Living and Dead Membranes. By E. W. REID (Brit. Med. J., 1890, i, 165--167).-The process of diiTiisiou cjf fluids through animal membranes i s well known to be influenced by the vit'al condition of such membranes. (CI. Bernard, Matteucci and Cima, &c.j. In the present research the skin of the frog was chiefly employed ; the liquids used were those which do not markedly im- pair the vitality of living tissues, such as physiological saline solution, or a 5 per cent. solution of glucose in t'his solution. The278 ABSTRACTS OF CHEMICAL PAPERS.osmometer used was either the ordinary Dutrochet instrument, or an oil-discharging osmometer in which the pressure was kept con- stant in order to avoid error from the occurrence of filtration. For recording purposes, advantage was taken of the photographic method in order t o avoid friction ; the height of the column of liquid being photographed on a very slowly revolving cylinder covered with sensitive paper. The following conclusions are drawn from the experiments :-(1.) The normal direction of easier osmotic trans- ference of fluid through the living skin of the frog is in the direc- tion from the outer towards the inner surface. (2.) The transference of fluid through the skin in the above direction is intimately associated with the physiological condition of its tissues.Conditions or agents tending to depress vitality dirninish the transfer in the normal direction, while stimulants give rise to augmentation. (3.) The cause of the easier transferof liquid from the outer towards the inner surface is probably to be found in the existence of an absorptive force dependent on protoplasmic activity, and comparable to the secretive force of a gland cell. (4.) In consequence of the absorptive force, acting from without inwards, an alteration of the relations of the surfaces of the skin to the two liquids used in an osmosis experiment modifies the rapidity of the transfer of liquid from one to the other side of the membrane, according as the force exerted by the living tissues is with or against the osmotic stream.Effect 6f Feeding on the Secretion of Amidic Substances. By E. SCHULZE (Ilicd. Centr., 18, 733-734; from PJluger’s Archiv, 25, 401--460).--The following are the results of the author’s experi- ments :-(1.) The nearer the feeding of persons approaches to a puye animal diet, the greater is the amount of nitrogen as urea in propor- tion to the total nitrogen of the urine. (2.) The relation of uric acid to the rota1 nitrogen decreases with meat diet as opposed to feeding with mixed food. This occurs in a still greater degree with a meat diet with use of abundance of alkaline water and absence of alcohol and narcotics, although the absolute amount of uric acid increases. ( 3 . ) The same holds good with regard to the relation of uric acid to urea. (4.) It is very probable t h a t in fever, even in absence of respi- ratory derangement, there is not only an absolutely larger amount of uric acid produced, but also an increased proporlion of uric acid relatively to total nitrogen and to urea.( 5 . ) ‘l’he use of plenty of alkaline water and the disuse of alcohol in treatment of gout are justi- fied by experimental evidence which cannot be deiiied ; these factors seem to be of greater importance than the prohibition of meat. W. D. H. N. H. M. Detection of Nitrous Acid in Saliva. By L. ILOSVAY DE N. ILOSVA (Bull. SOG. Chim. [3], 2, 388-391).-The saliva is boiled with an acetic acid solution of sulphanilic acid, the clear solution is decanted, and naphthylarnine i s added, when a rose coloration indi- cates the presence of nitrous acid, which is increased after ;t meal ; the action of tobacco smoke retards the reaction considerably. Nitrous acid could not be detected in the water moistening a cylinderPHYSIOLOGICAL CHEJl ISTRT.2 i 9 throligh which air had been respired ; when, howeyer, the respired air was passed through bulbs containing a 2 per cent. solution of sodium hydroxide for some time, an indicat.ion equal to that affvrded by ordinary air under similar conditions was obtained, although from experiments made with the air of stables the authors conclude that respired air does contain more nitrous acid than ordinary air. T. G-. N. Reducing Substances in Urine. By H. H. ASHDOWN ( B ~ i t . Med. J., 1890, i, 169--172)’.-The most important substance that reduces an alkaline solution of copper oxide arid that is apt therefore to be mistaken for sugar in urine, is glychronic acid.It can only be identified with certainty by isolating it and examining its properties. A ready distinction, however, between sugar and this substance is that the addition of yeast to the former, even when dissolved in the urine, causes the occurrence of the alcoholic fermentatioii, and to the latter does not. In man, the diagnosis of diabetes must in futuie be always more carefully made, as in one casej the first hitherto recorded, the re- ducing substance was found to be wholly glycuronic acid ; the man in whom this occdrred is in perfect health, and no symptoms of diabetes are present. If this state of things be shown t o occur in other cases, the question becomes important in relation to life assurance. In animals, the appearance of glycurohic acid in the urine is rradily produced by the administration of certain drugs, camphor, phenol, &c.In the present research, the following experiments were made :- The urine secreted after drugging with morphine contains, not sugar, but glycuronic acid ; after the administratioh of chloroform, glgcuronic acid, not sugar, is present. This confirms a previous investigation of Meyer. The so-called glycosuria of curare poisoning does not depend on the presence of sugar; there is no fermentation with yeast. The quantities of urine obtainable under these circumsbances are, however, so small that it was not possible to separate out glyc- uronic acid. The administration of ether does not cause the appear- ance of any reducing substance in the urine.After section of the renal nerves, a paralytic secretion occurs ; this contains a reducing substance, which was found to be glycuronic acid. W. D. H. Nitrogenous Constituents of Dog’s Urine. By L. BLEIRTREU (P’iigsr’s Archiv, 44, 512-5:35).-This investigation was carried out by the methods used by Bohlend (Abstr., 1889, 536), and by Pfluger and Bleibtren (this vol., p. 308). The results when the animal was fed on a meat diet are compared with those obtained when a mixed diet was used; they are given in the following table (p. 280) ; the numbers are percentages. The urea thus increases in proportion when the diet is chiefly dbu- minous, and diminishes on a mixed diet. It is also seen that in filtrate 11, that is, in the urine after the separation of “ extractives ’)880 Nitrogen not in Nitrogen ure&.in urea. = 100. ABSTRACTS OF CHEMICAL PAPERS. Sitrogen in filtrate I1 after subtract- monia. ing am- Total nitrogen (Kjeldahl) . -- 5 ‘155 5 *14 - 0.721 4 *59 4 -931 1 0155 0.6163s 10.96 4-682 4.07 5.0636 - 1 -061 1 4 . 5 0.6841 Nitrogen in filtrate I1 which ia not present. in the form of urea or ammonia. Total N in filtrate = 100. 1 -96 2 -6 4 . 3 9 -9 by means of phosphotungstic acid, there is, in addition to urea and preformed ammonia, a nitrogenous substance which contains about 2 per cent. of the total nitrogen in this filtrate when the diet is albu- iiiinous, but rises to double or quadruple the amount when the diet is a mixed one. W. D. H.Nitrogenous Constituents of Human Urine. By E. SCHULTZE (P’iigeT’s Archiv, 45, 401--460).--This is a research carried out on the same lines as that in the preceding abstract. The investigation was carried out on the human subject, its object being to compare the variations in the amount of urea-nitrogen with t h e non-urea-nitrogen in relation to diet. The fullest details of analysis are given; the methods adopted were those of Pfluger and Bleibtreu. The conclu- sions arrived at are as follows :- 1. ‘l’he urea-nitrogen increases in proportion to total nitrogen as t h e diet approaches a purely albuminous composition. 2. The uric acid increases absolutely, but diminishes relatively, both to total nitrogen and to the urea on a meat diet, especially if large quantities of alkaline water be taken and alcoholic drinks and narcotics be avoided. 3.Probably in fever the same relation of uric acid to total nitrogen and urea holds. 4. The use of abundant qiiantities of water and withdrawal of alcoholic beverages in cases of gout has thus a scientific basis. W. D. H. Action of related Chemical Compounds on Animals. By W. GIBBS and H. A. HARE (Amel.. C‘hem. J., 11, 435--448).-This paper contains an account of the first part of a research having for its object a systematic stutly of the relation between the chemical consti- tution of compounds and their action on the aniirial organism. Dogs and frogs were experimented on, arid a description is given of the action of the nitrophenols, the nitranilines, and t h e amido- and nitfro- benzoic acids on these animals when administered by the stomach or hjpodermicallj.VEGETABLE PHYSIOLOGY AND AGRICTLTURE.281 The nitrophenols cause death by paralysing the heart, and not by a respiratory action ; the nervous system is unaffected by them, except that the vagus nerves are slightly stimulated by the ortho- and meta- compounds, but depressed by the para-compound. The lethal dose per kilo. of body weight is 0.1 gram of the ortho-, about 0.1 gram of the meta-, or 0.01 gram of the para-compound, when injected into the jugolar vein. The nitranilines all act by stimulating the peripheral vagi, and so producing a very marked slowing of the pulse. I n the case of the ortho-compound, the lethal dose is 0.3 gram per kilo. ; methEmoglobin is produced in the blood, and the sensory side of the spinal cord is slightly affzcted, but this is probably caused indirectly by the changes in the blood.Given by the stomach it produces cnrious paroxysms of sneezing. The meta-compound has but a very feeble effwt on the nerves, and this depends on the development of met- hzmoglobin in the blood, all the symptoms being those of aniline poisoning. The para-compound is the most poisonous, the lethal dose being 0.04 gram per kilo. of body weight when injected into the jugular vein. The amidobenzoic acids and the nitrobenzoic acids were found to be without effect on the animal organism. C. F. B. Is Potassium Ferrocyanide Poisonous? By P. CARLES (J. Pharm. [ 5 ] , 20, 486-489).-T he evidence here collected from various sources leads to the conclusion that this salt is not poisonous.J. T.2174 ABSTRACTS OF CHEMICAL PAPERS.P h y s i o l o g i c a l Chemistry.Respiration of Entoeoic Worms. By G. BUNGE (Zsit. physiol.Chem., 14, 318--324).-1n an earlier communication (ibid., 8, 48) itwas shown that the Ascu~is mystax, the worm that lives in the intestineof the cat, will live four or five days in media quite free from oxygen.Renewed experiments with Ascaris acus, from the intestines of thepike, are confirmatory of the above ; these worms live for four to sixdays, and exhibit movements, ill. niedia free from oxygen. In theultimate respiratory processes of these animals there must be a for-mation of energetic reducing substances (nascent hydrogen andeasily oxidisable organic: matter) which unite with one atom of theoxygen-molecule, even to a greater extent than in animals whichbreathe oxygen.I n order to investigate this question more fully, larger varieties ofAscaris were employed.The A . rnegalocephala of the horse wasfound unsuitable, as it only lived for two dajs after retnoval from theintestine; the A . Zumbricoides of the pig was therefore used; thislived from five to seven days. I n boiled salt solution it gave of€abundance of gas, which was collected over mercury, and was com-pletely absorbed by potash, consisti~ig of pure carbonic anhydride,and containing no hydrogen. ‘l’he quantity of gas obtained in thistime was from 5 C.C. to IU C.C. per gram of the animal’s body-weight.I n three experiments, a small, measured quantity of oxygen was addedto t h i s gas artificially, but there was no diminution in its volume afterthe admixture ; thus not only hydrogen, but othcr reducing substancesare absent also.W. L). H.Ttiese animals possess no respiratory apparatus.Heat developed by the Action of Oxygen on the Blood. ByBERTHELOT (Compt. rend., 109, 776-781).--The experiments weremade w-ith defihrinated fresh sheep’s blood which had been allowed toremain in a closed flask for 24 hours. ‘l’he scai-let colour had changedto purple, the sp. gr. was 1.057 at go, and the specific heat 0.872. IPHTSLOLOGICAL CHEMISTRY. 2 i 5was placed in the calorimeter, and a current of nitrogen, saturatedwith moisture, was passed through for some time. Dry oxygen wasthen passed in, and the temperature observed at frequent intervals.Before weighing the calorimetric vessel, the oxygen in the emptyspace was expelled by means of nitrogen.I n one experiment, 100 vols.of blood absorbed 20.2 vols. of oxygen,in another, 18.5 vols. The heat developed per 32 grams of oxygenwas 14.63 Cals. in the first case and 14-91 in the second, or a mean of + 14.77 Cals. The formation of silver oxide develops + 14.0 Cals. ;of barium peroxide, + 24.2 Cals. ; of lead peroxide, + 24.5 Cals. per32 grams of oxygcn ; and it is evident that the heat liberated by theformation of oxyhaemoglobin is of the same order of magnitude asthe heat of formation of many true oxides.The combination of carbonic oxide with haemoglobin developed + 18.0 CaIs.and + 19.4 Csk., or a mean of + 18.7 Cals. per 28 giams,a disturbance of the same order of magnitnde as the heat of forma-tion of oxyhamoglobin, but distinctly higher.The heat developed by the action of oxygen on the hlocd is almostexactly one-seventh of the heat which would be liberated by the com-plete oxidation of carbon by the same quantity of oxygen, and henceit follows that of the total animal heat about one-seventh is developedin the lungs by the combination of oxygen with the blood, and theremaining six-sevenths in other parts of the body in consequence ofoxidations and hydrations.The development of heat in the lungs is almost exactly compen-sated by the absorption of heat due to the liberation of carbonicanhydride and water vapour, and whether the temperature of thehlood in the lungs rises or falls is determined by the temperatiire ofthe inspired air, but the variation in oce direction or the other is notgreater than the tenth of a degree.Animal Heat and the Heat of Formation and Cnmbustionof Urea.By BERTHELOT and P. PETIT (Contpt. rend., 109,759-764).-See this vol., p. 206.Artificial Digestion of Prote'ids. By A. STUTZER (Landw.Versuchs. Stat., 36, 331-388) .-The method proposed by the authorconsists in treating the food first with an acid pepsin solution andthen with an alkaline pancreatic liquid, and determining the nitrogenin the undissolved substance ; from the relation of the indigestibleto the total proteid nitrogen, the digestibility coefficient is calculated.The method gives, according to Pfeiffer (Journ.f. Landw., 34,444),results nearly identical with tliose obtained by means of directexperiments with animals.The pepsin solution is prepared by cutting the mucous skin of afresh pig's stomach into &mall pieces and keeping it for one or twodays with 5 lit'res of water, 100 C.C. of hydrochloric acid (con-taining 10 grams of hydrogen chloride) and 2.5 grams of salicylicacid; it is then poured through a flannel bag and filtered, firstthrough a coarse and then through a dense lilter paper. It is best toprepare several extracts a t once.C. H. B276 ABSTRACTS OF CHEMICAL PAPF RS.The pancreas extract is obtfiined by cutting up the pancreas(1000 grams) of a bullock, rubbing it np with sand, and exposing itto air for 24-36 hours.It is then treated with lime-water(S00 c.c.),glycerol (sp. gr., 1.23 ; 1 litre), and some chloroform, kept for four t'osix days, filtered, heated for two hours a t 37-40', and again filtered,iE necessarp. Before using the extract, 250 C.O. of it is mixed withsodium carbonate solution (7.50 C.C. containing 5 grams of the an-hydrous salt), heated a t 37 to 40" for one or two hours, and filtered.The determination of digestible substance is made as follows :-the finely powdered food (2 grams) is tied up in paper andextracted with ether from five to six hoiirs to remove the fat. It isthen treated with the pepsin solution (650 c.c.) and heated a t 37 to46" for 24 hours, 10 per cent. hydrochloric acid (2.5 c.c.) beingadded at intervals of about one hour until the solution contains 1 percent.of acid. The suhstaiice,wit.h the asbestos, is heated with the alkaline pancreas extract(100 c.c.) for six hours at 37-40', the liquid being stirred some-times. After this it is filkered, washed with water, dried, and thenitrogen determined in the substance.I t was found that if the subst,ance is treated with 400 C.C. of pepsinsolution cont,aining 0.2 per cent. of hydrogen chloride, without sub-sequent digestion with pancreas, somewhat less nitlrogen is dissolvedthan when the less amoant of more strongly acid pepsin is em-ployed. But if the food is aEtervi-ards digested with pancreas, thefinal result is the same in both cases. N. H. 31.It is then filtered through asbestos.Absorption of Sugar from the Small Intestine. By S.GINS-BERG (PJEuger's drchiv, 44, 306--316).-v. Mering (Arch. Anat.i~hysiol., physiol. Abth., 1877, 379) showed that the chyle from thethoracic duct of the dog contained no more sugar during the diges-tion of carbohydrate than at other times, but that the percentage ofsugar in the portal blood was increased under these circumstances.Heidenhain pointed out (Pfliiyer's Arclziv. dupp., 1888, 71) thatthis is probably due to the fact that the water and substances, likesugar, easily soluble in water are taken up by the blood-vessels asthey lie immediately beneath the epithelium, and so do not reach themore centrally situated lacteals of the villi. The present research,undertaken under Heidenhain's superintendence, was directed toascertaining, whether by greatly increasing the amount of sugar andwater in the food, some might not be found even in the chyle.The first experiments were performed on rabbits, wit<h resultsgiven in the following table (p.277).These show that during a normal diet the amount of sugar inboth blood and chyle is very constant. The seemingly higherpercentage in the latter is due to the fact that the percentage istaken for the total blood, including corpuscles. I n round numbers100 parts of blood contain 60 volumes of plasma; hence, the per-centage i n the plasma would average 0.28, which is higher than thatin tlie chyle. l'he rise of the perccmtage during sugar feeding, bothi n blood and chyle, is very markedPHYSIOLOGICAL CHEMISTRY.277Percentage of sugar inBlood. Ch jle.0 -233. ............... 0 -18 0 '254. ............... 0 -23Mean.. .......... 0 '18 0 *24;: : : : : : : : : : : : : : : : 1 Ri: 0.23Food.Kormal diet.J J> ?J )J 75 ................ 0 '226. ............... 0'397. ............... 0 -338. ............. 0 -313fean.. .......... 0 315 grains sugar in 50 C.C. water.15 9 ) 100 ? J15 J ? 100 > J25 J 150 ,.0'360 -7G0 *390 '460 -49The second series of experiments, made on dogs with a fistula ofthe thoracic duct', show the same result, and are st'ill more satis-factory, as the same animal could be used in the two experiments.The following table contains the results of a few of the experi-ments performed.'The sugar solution was injected into the iutestine.-l . . .2 . ..3...4.. .~~~~ ~Percevtage of sugar inChyle. I Blood.Beforeinjection.0.140.070.090.08Afterinjection.0 -140 '270 *180 -88Beforeinjection.0 -240 -250 220 * 1 GAfterinjection.0 2 70 5 20 *350 *42Amouii t injected.30 grams in 600 C.C. of water.41) J 9 J J20 J ) 400 2 )30 J J 4uo J JW. L). H.Osmosis with Living and Dead Membranes. By E. W.REID (Brit. Med. J., 1890, i, 165--167).-The process of diiTiisiou cjffluids through animal membranes i s well known to be influenced bythe vit'al condition of such membranes. (CI. Bernard, Matteucci andCima, &c.j. In the present research the skin of the frog was chieflyemployed ; the liquids used were those which do not markedly im-pair the vitality of living tissues, such as physiological salinesolution, or a 5 per cent.solution of glucose in t'his solution. Th278 ABSTRACTS OF CHEMICAL PAPERS.osmometer used was either the ordinary Dutrochet instrument, oran oil-discharging osmometer in which the pressure was kept con-stant in order to avoid error from the occurrence of filtration. Forrecording purposes, advantage was taken of the photographic methodin order t o avoid friction ; the height of the column of liquid beingphotographed on a very slowly revolving cylinder covered withsensitive paper. The following conclusions are drawn from theexperiments :-(1.) The normal direction of easier osmotic trans-ference of fluid through the living skin of the frog is in the direc-tion from the outer towards the inner surface.(2.) The transferenceof fluid through the skin in the above direction is intimately associatedwith the physiological condition of its tissues. Conditions or agentstending to depress vitality dirninish the transfer in the normaldirection, while stimulants give rise to augmentation. (3.) Thecause of the easier transferof liquid from the outer towards the innersurface is probably to be found in the existence of an absorptive forcedependent on protoplasmic activity, and comparable to the secretiveforce of a gland cell. (4.) In consequence of the absorptive force,acting from without inwards, an alteration of the relations of thesurfaces of the skin to the two liquids used in an osmosis experimentmodifies the rapidity of the transfer of liquid from one to the otherside of the membrane, according as the force exerted by the livingtissues is with or against the osmotic stream.Effect 6f Feeding on the Secretion of Amidic Substances.By E.SCHULZE (Ilicd. Centr., 18, 733-734; from PJluger’s Archiv,25, 401--460).--The following are the results of the author’s experi-ments :-(1.) The nearer the feeding of persons approaches to a puyeanimal diet, the greater is the amount of nitrogen as urea in propor-tion to the total nitrogen of the urine. (2.) The relation of uric acidto the rota1 nitrogen decreases with meat diet as opposed to feedingwith mixed food.This occurs in a still greater degree with a meatdiet with use of abundance of alkaline water and absence of alcoholand narcotics, although the absolute amount of uric acid increases.( 3 . ) The same holds good with regard to the relation of uric acid tourea. (4.) It is very probable t h a t in fever, even in absence of respi-ratory derangement, there is not only an absolutely larger amountof uric acid produced, but also an increased proporlion of uric acidrelatively to total nitrogen and to urea. ( 5 . ) ‘l’he use of plenty ofalkaline water and the disuse of alcohol in treatment of gout are justi-fied by experimental evidence which cannot be deiiied ; these factorsseem to be of greater importance than the prohibition of meat.W. D.H.N. H. M.Detection of Nitrous Acid in Saliva. By L. ILOSVAY DEN. ILOSVA (Bull. SOG. Chim. [3], 2, 388-391).-The saliva is boiledwith an acetic acid solution of sulphanilic acid, the clear solution isdecanted, and naphthylarnine i s added, when a rose coloration indi-cates the presence of nitrous acid, which is increased after ;t meal ;the action of tobacco smoke retards the reaction considerably.Nitrous acid could not be detected in the water moistening a cylindePHYSIOLOGICAL CHEJl ISTRT. 2 i 9throligh which air had been respired ; when, howeyer, the respiredair was passed through bulbs containing a 2 per cent. solution ofsodium hydroxide for some time, an indicat.ion equal to that affvrdedby ordinary air under similar conditions was obtained, although fromexperiments made with the air of stables the authors conclude thatrespired air does contain more nitrous acid than ordinary air.T.G-. N.Reducing Substances in Urine. By H. H. ASHDOWN ( B ~ i t .Med. J., 1890, i, 169--172)’.-The most important substance thatreduces an alkaline solution of copper oxide arid that is apt thereforeto be mistaken for sugar in urine, is glychronic acid. It can only beidentified with certainty by isolating it and examining its properties.A ready distinction, however, between sugar and this substance is thatthe addition of yeast to the former, even when dissolved in the urine,causes the occurrence of the alcoholic fermentatioii, and to thelatter does not.In man, the diagnosis of diabetes must in futuie be always morecarefully made, as in one casej the first hitherto recorded, the re-ducing substance was found to be wholly glycuronic acid ; the manin whom this occdrred is in perfect health, and no symptoms ofdiabetes are present.If this state of things be shown t o occur inother cases, the question becomes important in relation to lifeassurance.In animals, the appearance of glycurohic acid in the urine isrradily produced by the administration of certain drugs, camphor,phenol, &c.In the present research, the following experiments were made :-The urine secreted after drugging with morphine contains, not sugar,but glycuronic acid ; after the administratioh of chloroform, glgcuronicacid, not sugar, is present. This confirms a previous investigationof Meyer.The so-called glycosuria of curare poisoning does notdepend on the presence of sugar; there is no fermentation withyeast. The quantities of urine obtainable under these circumsbancesare, however, so small that it was not possible to separate out glyc-uronic acid. The administration of ether does not cause the appear-ance of any reducing substance in the urine. After section of therenal nerves, a paralytic secretion occurs ; this contains a reducingsubstance, which was found to be glycuronic acid. W. D. H.Nitrogenous Constituents of Dog’s Urine. By L. BLEIRTREU(P’iigsr’s Archiv, 44, 512-5:35).-This investigation was carried outby the methods used by Bohlend (Abstr., 1889, 536), and by Pflugerand Bleibtren (this vol., p.308). The results when the animal wasfed on a meat diet are compared with those obtained when a mixeddiet was used; they are given in the following table (p. 280) ; thenumbers are percentages.The urea thus increases in proportion when the diet is chiefly dbu-minous, and diminishes on a mixed diet. It is also seen that infiltrate 11, that is, in the urine after the separation of “ extractives ’880Nitrogennot inNitrogen ure&.in urea.= 100.ABSTRACTS OF CHEMICAL PAPERS.Sitrogenin filtrateI1 aftersubtract-monia.ing am-Totalnitrogen(Kjeldahl) .--5 ‘1555 *14-0.7214 *594 -9311 01550.6163s10.96 4-6824.07 5.0636- 1 -0611 4 . 5 0.6841Nitrogen in filtrateI1 which ia notpresent. in theform of urea orammonia.TotalN in filtrate =100.1 -962 -64 . 39 -9by means of phosphotungstic acid, there is, in addition to urea andpreformed ammonia, a nitrogenous substance which contains about2 per cent. of the total nitrogen in this filtrate when the diet is albu-iiiinous, but rises to double or quadruple the amount when the diet isa mixed one. W. D. H.Nitrogenous Constituents of Human Urine. By E. SCHULTZE(P’iigeT’s Archiv, 45, 401--460).--This is a research carried out onthe same lines as that in the preceding abstract. The investigationwas carried out on the human subject, its object being to compare thevariations in the amount of urea-nitrogen with t h e non-urea-nitrogenin relation to diet. The fullest details of analysis are given; themethods adopted were those of Pfluger and Bleibtreu.The conclu-sions arrived at are as follows :-1. ‘l’he urea-nitrogen increases in proportion to total nitrogen ast h e diet approaches a purely albuminous composition.2. The uric acid increases absolutely, but diminishes relatively,both to total nitrogen and to the urea on a meat diet, especially iflarge quantities of alkaline water be taken and alcoholic drinks andnarcotics be avoided.3. Probably in fever the same relation of uric acid to total nitrogenand urea holds.4. The use of abundant qiiantities of water and withdrawal ofalcoholic beverages in cases of gout has thus a scientific basis.W. D. H.Action of related Chemical Compounds on Animals. ByW. GIBBS and H. A. HARE (Amel.. C‘hem. J., 11, 435--448).-Thispaper contains an account of the first part of a research having for itsobject a systematic stutly of the relation between the chemical consti-tution of compounds and their action on the aniirial organism. Dogsand frogs were experimented on, arid a description is given of theaction of the nitrophenols, the nitranilines, and t h e amido- and nitfro-benzoic acids on these animals when administered by the stomach orhjpodermicalljVEGETABLE PHYSIOLOGY AND AGRICTLTURE. 281The nitrophenols cause death by paralysing the heart, and not by arespiratory action ; the nervous system is unaffected by them, exceptthat the vagus nerves are slightly stimulated by the ortho- and meta-compounds, but depressed by the para-compound. The lethal doseper kilo. of body weight is 0.1 gram of the ortho-, about 0.1 gram ofthe meta-, or 0.01 gram of the para-compound, when injected into thejugolar vein. The nitranilines all act by stimulating the peripheralvagi, and so producing a very marked slowing of the pulse. I n thecase of the ortho-compound, the lethal dose is 0.3 gram per kilo. ;methEmoglobin is produced in the blood, and the sensory side of thespinal cord is slightly affzcted, but this is probably caused indirectlyby the changes in the blood. Given by the stomach it produces cnriousparoxysms of sneezing. The meta-compound has but a very feebleeffwt on the nerves, and this depends on the development of met-hzmoglobin in the blood, all the symptoms being those of anilinepoisoning. The para-compound is the most poisonous, the lethaldose being 0.04 gram per kilo. of body weight when injected into thejugular vein. The amidobenzoic acids and the nitrobenzoic acidswere found to be without effect on the animal organism.C. F. B.Is Potassium Ferrocyanide Poisonous? By P. CARLES (J.Pharm. [ 5 ] , 20, 486-489).-T he evidence here collected fromvarious sources leads to the conclusion that this salt is not poisonous.J. T

ISSN:0368-1769    

DOI:10.1039/CA8905800274

出版商:RSC    

年代:1890

数据来源: RSC

摘要:

VEGETABLE PHYSIOLOGY AND AGRICTLTURE. 281 Chemistry of Vegetable Physiology and Agriculture. Influence of Yeast on the Bouquet of Wines. By A. ROMMIER (Bull. SOC. Chim. [3], 2, 297-300) .--Having previously shown that cultivated yeast determined the non-development of the cells occur- ring naturally on the grape when the former was added to juice in which the latter existed, the author fermented the juice of an inferior grape and of hothouse grapes respectively with yeast cultures ob- tained from the Champagne, Cate d’Or, and Buxy districts, and found that in each case the resulting wines had the bmquet of the wines from whence the yeasts were derived. T. G. N. Influence of Carbonic Anhydride on the Products of Fer- mentation. By L. LINDET (BUZZ. SOC. Chim. [3], 2, 195).-The car- bonic anhydride evolved during fermentation by means of yeast was not allowed to escape, but retained in the x-essels under pressures of 20, 200, 430, and 600 mm.of mercury respectively, without affecting the amount of alcohol produced or the weight of yeast formed. Inverting Ferment. By 0. KELLNER, Y. MORT, and M. NAGAOKA (%it. physio2. Chen7., 14, 297--31T).-Koji is the name of tt sub- stance uspd in China and Japan in $he preparation of rice wine and T. G. N. VOL. 1.7111. zc282 ABSTRACTS OF CHEMICAL PAPERS. alcohol. It consists of the mycelium and spores of a fungus. When investigated, i t was found to contain a powerfnl inverting ferment which changes cane sugRr into dextrose and levulose, maltose into dextrose, and sta,rch into dextrin, maltose, and dextrose ; it prob- ably does not alter lactose or inulin.The invertin of yeast acts on cane sugar only, and the name suggested for the ferment of Koji is invertnse. Its action is much hindered by the presence of common salt, but it is not wholly destroyed even by 20 per cent. of that salt. W. D. H. Nitrification of Ammonia. By T. ScHLoEsrNG (Compt. rend., 109, 88:?-887).-Under normal conditions, nitrification of ammonia takes pla.ce without any loss of free nitrogen, but when a large excess of ammonium salt is present, there is a very distinct loss of nitrogen in this manner. This loss is due to the formation of a small quantity of nitrite, owing to absence of an excess of oxygen. The nitrite interacts with the smmoninm salt, with production of free nitrogen ; it also petards nitrificstion, and is itself but slowly oxidised.It is possible that the free nitrogen is not the result of interaction between the nitrite and the ammonium salts, but is liberated as a result of limited oxidation of the ammonia; this point, however, can only be determined by further experiment. C. H. B. Fermentation of Manure in Absence of Oxygen. Bg T. SCHLOESIKO (Conzpt, rend., 109, 835--840).-When fresh manure from cows is kept at 42" to 5 2 O in an atmosphere of carbonic anhy- dride, it undergoes fermentation with evolution of hydrogen, methane, and carbonic anhydride, but no free nitrogen is evolved. Hydrogen is only liberated in the early stages of the change, and disappears from the gases as ferment,at,ion progresses. The mtio of methane to carbonic anhydride approaches unity only towards the end of the proces8, and varies irregularly throughout the fermentation.No nitrogen is evolved at any stage, but the quantity of ammonia present increases. The quantity of oxygen and hydrogen in the evolved gases is greater than the quantity lost by the manure, and it is evident that the water which is present plays an active part in the fermentation, the oxygen combining with carbon to form carbonic anhydride, whilst the hydrogen is converted into methane. C. H. B. Formation of Cane Sugar in Etiolated Plant Shoots. By E. SCHULZE (Chem. Centr., 1889, ii, 694-695 ; from B e y . Ueut. hot. G'esell., 7, 280- 281) .-The etiolated shoots of Lupinus Euteus were examined, by means of the method described by the author (compare Abstr., 1888, 624), for cane sugar, of which 30 grams (crystallised) wa,s obtained from 800 grams of air-dry shoots, besides a consider- able amount which must have been lost in the separation and purifi- cation.Before germination, not the least trace of sugar was detectable in the lupins. As is already known, starch is also formed during the process of germination of this seed in the absence of light, the other nitrogen-free substance which is present in the seeds asVEGETABLE PHYSTOLOGY ASD AGRICULTURE. 283 reserve material disappearing as the formation of sugar and stiirch proceeds. J. w. rJ. Living Vegetable Protoplasm. By T. BOKORSY (PJiigev’s Arnhiv, 45, 199-2 19).-The difficulty of applying chemical reagents to living structures in many cases consistsin the fact that the reagent destroys the life of the material under investigation.Weak solu- tions of alkalis have not, however, this objection ; they produce changes in the cells, but these are considered to be vital changes, t h a t is, evidence of the living activity, and not of the death of the protoplasm. These changes may be grouped together under the general term “ aggregation.” This term was first used by Darwin to express the change that occurs in the tentacles of Droswa on the application of weak solutions of ammonium carbonate ; this consists in the collec- tion of the protoplasm into separate particles. The term has since been extended to somewhat similar phenomena in other plants ; De Vries (Botan. Zeit., 1886, l), however, limits i t to the contritction of the vacuole wall, and does not speak of the formation of proteid granules in the vacuole coutents as aggregation.Pfeffer distinguishes between an outer and inner cell-membrane, the former lining the cell wall proper, the latter surrounding the vacuole fluid, and betweeen the two is what he terms granule-plasm (Koi-ner-plasma), but which does not necessarily always contain granules. In the present research, a large number of careful niicroscopic observations are recorded. The plants, the cells of which were ex- amined were Spirogyra, Drosera, TuEipa, C~ocus, Cotyiedon coccinea, &c. The weak alkalis chiefly used were ammonia (1 : 5000) and caffeine (1 : 1000). Weak potassium hydiboxide, various amines, tetrethylammonium hydroxide, tolnylenediamine, quinine, atropine, &c., were also used in some experiments.The following cases of aggregation could be distinguished :- (I.) The whole protoplasm contracts equally ; this is somewhat different from, but very similar to plasmolysis ; it is seen in crocus papilltz. (2.) The vacuole wall (inner cell-membrane of Pfeffer) contracts alone, or to a much greater extent than the rest of the cytoplasm ; this is well seen in the red epidermal cells of the petals of tulips and primulas. (3.) The “ granule-plasm ” collects i i i t 4 ) granules or discs ; these are exceedingly minute from the action of ammonia on h’pirogyra cells, but much larger from the action of solution of caffeine on sections of the leaves of Cotyledo~ coccinea and Echeveria gebt$lora.(4.) The vacuole-fluid, that is, the cell-sap with active albumin either in solution or in a greatly swollen condition, becomes pervaded with larger or smallar granules; this is seen in Drosera, Xpiroyyra, and several other plants. W. D. H. Vegetable Cell-membranes. By E. SCHULZE, E. STEJGER, and W. MAXWELL (Zeit. physiol. Chem., 14, 227-273 ; compare Abstr., 1889, 916) .-This investigation shows that the membrane o vegetitble cells contains in addition to cellulose several other carl)otiydi*ar es which differ from it widely iu their properties. They are all insoluble u d284 ABSTRACTS OF CHEMICAL PAPERS. in cuprammonium hydroxide, b u t differ in certain other ~eactions ; by hydrolysis, howerer, they all yield pentaglucoses (arabinose, xylose, &c.) ; by warming with phloroglucinol and hgdrochloric acid give a chwry-red colour ; and by treatment with very dilute mineral acids differ from cellulose in b h g quickly converted into sugar; the varieties of sugar formed being galactose, mannose (seminose), and pentaglucoses.The term cellulose as used by Reiss (Abstr., 1889, ti8T) evidently includes these carbohydrates ; i t is, however, advisab:e to restrict the word cellulose to those constituents of the cell-wall which are but little affected by strongly diluted mineral acids, which a r e soluble in cupramnionium hydroxide, which further are colouyecl blne by chloride of zine and iodine, o r iodine and sulphuric acid, and nhich lastly are converted by strong sulphuric acid into dextrose. 1 he term proposed f o r these other carbohydrates is that of “para- g;.lactan-like substances.” I t appears doubtful as to whether cellu- I( se is a single substance, but this was -not specially investigated.The paragalactan-like constituents of the cell-wall appear to be of some physiological importance; they seem to be more soluble than cellulose, and enter into solution d u r i n g germinat,ion, function- i v p a s a reserve material before that process commences. It is very donhtful if triie cklhlose acts in this way. The nutritive value of these substances in tlw animal economy appears, like that of cellulose, to be small, as they are not digestible by the various digestive juices. On oxidation with nitric acid, they yield mucic acid. From the point of view of analyses of starch in vegetable substances, these paragalactan-like materials are of some importance, as they, like starch, pass into solution on treatment with dilute mineral acids.W. D. H. Non-Nitrogenous Reserve Substance of the Seeds of Lupinus luteus. By E,. PCHULZE and E. STEIGER (Lumdzo. Ver.suChs.- stat., 36, 391-478).-1 he ethercal extmct of the seeds of Lupinvs Iute7i.s contained :-Glycerides, fatty acids, and wax 5.99, cholesterin O.l,!i,and lecithin 0.17 per cent. in the dry matter of the seed (freed from the shells). A further amount of lecithin can be extracted from the seed by alcohol, making a total of 2.10 per cent. (in dry seed). After being dlowed to germinate for 14 days, 78.7 parts of dry matter remained and yielded an ethereal extract containing :-Glycerides, &c., 1-50 part, bholesteiin 0.25 part, and only a trace of lecithin, The amount of lecithin extracted by alcohol was 0.44 part./?-Galactan (Steiger, Abstr., 2886, 603) is a white, amorphous powder, consisting of microscopic globules. The aqueous solution is not coloured by iodine, and only reduces Fehling’s solution when i t has been heated with an acid. New determinations of rotatory power gave the mean :--[a]= = + 148.6”. When P-galactan (100 parts) is heated with nitric acid, mncic acid (41.16 parts) is formed. The acetyl-derivative is a white powder melting at 101-102”. The amount of p-galactan contained in tho dry seeds (without shells) was determined indirectly (1) as glucose, (2) as mucic acid. The first method gave in different samples :--(a) 10.20, ( b j 10.02, (c) 0.48 and ( d ) 6-36 per cent.; the second method gave in sample ( u ) 8.5VEGETABLE PHYSIOLOGY ASD AGRICULTURE.285 and in ( e ) 7-65 per cent. With regard to the first method, i t is shown that the seeds contain no cane-sugar which would affect tbe results. Paragalactan (paragalnctin, Abstract, 1887, 460)) C6H,,0, (?), could not be obtained free from cellulose. It dissolsves partly in water when heated under a pressure of 16 or 2 atmospheres; tlie filtered solution, when heated with hydroch!oric acid, reduces Fehling's solution, and the residue obtained by evaporating the solution yields muck acid when oxidised by nitric acid. It is not soluble in diastase solution. When haat.ed with phloroglucinol and hydrochloric acid, a cherry colour is produced.5 per cent. aqueous potash dissolves it partly ; a salt seems to be formed. Paragalactan is contained not only in the cotyledons, but also in tlie seed-shell. A carbohydrate probably identical with paragalactali was found in the seeds of Soja hiqida, Pisum sativum, and F d a vulgai*is. When lupin seeds are allowed to germinate in the dark for six days, all the /?-galactman is used up, whilst n great part of the para- gJactan dissolves ; glucose (not galactose), cane-sugar, and cellulose are formed. N. H. hi. By ARNAUD (Conzpt. rend., 109, 911- 914).-The proportion of carrotene in leaves varies with the spe4e.; of the plant, but oscillates between 0.1 and 0.2 per cent. of the dried leaf. It varies with the age of the plant, is at a maximum during inflorescence, and then gradually diminishes, but never entirely dis- appears.Its quantity is affected by light, and, like chlorophjll, it tends to disappear in the dark. Carrotene can absorb 24 per cent. of its weight of oxygen, but remains unaltered in the living leaf, and very probably undergoes alternate cxidation and reduction in such a manner that its quantity remains almost constant for short intervals of time, It is highly probable that carrotene is of very great physiological importance. C. H. B. Musscenda Coffee. By W. R. DUNSTAN (Phann. J. Tram. [ 3 ) , 20, 381).-It has been asserted by Lapeyrhre, that the seeds of a plant which he considers to be a new species of Musscenda, and calls Mussmndu borbonica, may be employed as a substitute for coffee. The plant grows in the island of Rbunion, and its seeds are said to contain 0.3-0-5 per cent.of caffe'ine. An examination of the plant a t Kew showed that it is not a Mztsscetida, bnt Gmrtnera vaginata, which belongs to the natural order Logaiiiacece. The author found that the seeds contained neither caffe'ine nor theobromine ; strychnine and brucine were also absent, and the only alknlo'id that could be detected was a trace of choline. W. R. D. (Zeit. U I ~ U ~ . Chem., 28, 525- 580).-The analyses of wines and musts here given, in continuation of those published in Zeit. am,?. Chem., 27, 729, et seq., include numerous brands from the wine districts of Rhein-Hesse, Rheingilu, Rhine Palatinate, Baden, W iirtemberg, Lower Franconia, Alsace, and Lorraine, and of vintages from 1884 to 1888.Carrotene in Leaves. Wine Statistics of Germany. M. J. S236 ABSTRACTS OF CHEMICAL PAPERS. Gra-s ..................... Iiay ....................... Silage (sour) ............ Experiments on Ensilage conducted at Crawley Mill Farm, Woburn, 1884-87. By J. A, VOELCKER (Joum. Roy. Agr. Soc. [2], 22, 483-513, and 23, 403--417).-The object of the expe- riments was to determine the relative feeding values of silage as com- pared with roots and hay-chaff. The method employed was to feed four bullocks with weighed amounts of hay-chaff and swedes, and four more with an amount of silage containing the same quantities of di-y matter, woody-fibre, and nitrogen as the hay-chaff and swedes con- tained ; all the animals had, besides, weighed amounts of decorticated cotton-cake and maize-meal.In the first year's experiments, grass silage of inferior quality and clover silage which was of' thoroughly good quality were employed. I n both cases a much greater increase was obtained wibh roots and hay-chaff than with silage. In the second year the following series of experiments were made :- (1) sour silage against roots and hay-choff; (2) sweet silage against roots and hay-chaff; (3) oat silage against roots and straw-chaff'; (4) oat silage against hay. This time the grass employed was of T-eyy fair quality. The bullocks fattened well on both sour and sweet grass silage of good quality, but still not so well as with roots and hay-chaff ; whilst oat silage proved, in this instance, to be superior t o either straw-chatf with roots or to hay.It was found that the oat silage when well made keeps perfectly for a t least two years. The following table shows the percentage of nitrogen, albuminold nitrogen, and non-albuminoid nitrogen in the silage :-- 0'31 1'16 C'L4 In dry. I In fresh. I 1-1 I I I I Albumino'id Non-albumi- Albumino'id Xon-albumi- Total 1 nitrogen. I noydnitrogen. I niEi:n. I nitrogen. 1 ntiid nitrogen.! nitrogen. Sweet silage (grass).. 0 '45 Sour silage (grass .... 0.28 Oat silage ............ ..., 0 -15 Hay ........................ 1 '37 The object of the third year's experiments was to determine the value of grass made into hay as agzainst that of the same grass con- verted into silage. The grass employed was of very fair quality, and the silage wits extremely good and well made.The percentage of nitrogen, albuminold nitrogen, and non-alhu- minoi'd nitrogen in the grass, and in the hay and silage prepared from it, was as follows :- I- 1 Allruininoi'd 11 it rogen. ____--- I__-- In dry. I In fresh. I Non-albnmi- 1 Total 1 Altuminoyd 1 Non-albumi- 1 Total noid nitrogen. nitrogen. nitrogen. noId nitrogen. nitrogen. 0 '08 0 -4'' 1 *29 0 '30 1 '59 0'19 1 1.35 1 1 - 4 1 1 0.23 1'6.1 0 '27 0 '51 0 *a7 0 *9n 1 Y.5VEQETABLE PHYSIOLOQY AND AQRICULTURE. 2157 100 parts of grass gave :-Good silage 87.15 parts, inferior and mouldy silage 4.56 parts, loss by fermentation, &c., 7.29 phrts. The produce in hay was:-good hay 29.77 parts, inferior hay 2.61 parts, water and loss 67.62 parts. The experiments show that the silage from 28,995 lbs.of grass (the produce of 2.4 acres) and the hay from 34,442 lbs. of grass (the produce of 2.8 acres) gave equal feediiig results. The results of similar experiments made at Wilmington, near Shrewsbury, showed a slightly larger gain with silage than with hay prepared from the same grass. Ammonia and the Nutrition of Plants. By A. M u m z ( J . Pharm. [ 5 ] , 20, 489-492).-Experimerits were made to ascer- tain whether salts of ammonia could be utilised by the roots of plants without first being converted into nitrate. Seeds of bean, horse-bean, maize, barley, and hemp were freed from nitrification germs, and sown in soil freed from nitrates and germs, and placed in glazed boxes supplied with sterilised air. Ammouia in the form of sulphate was supplied.A similar set of pots was prepared containing germs of the nitric ferment. The sterilised soil contained no nitrates either at the beginning or eud of the experiment; the non-sterilised soil contained no nitrates at beginning, but yielded 91.2 and 420.0 milli- grams per kilo, at the end of the trial. In the sterilised pots, the plants grew well, and assimilated all the nitrogen required from the ammonicm salt, showing that nitrification is not essential. Effect of Manuring with Ammonium Sulphate and with Sodium Nitrate. By &I. MAERCKER (Bied. Cmtr., 18, 724-729).- In order to determine the effect of calcium carbonate on the rnanuriaJ action of ammonium sulphate, six plots of land, supplied with phos- phoric acid, or kainite, received the following :-(a) Nothing ; ( c ) ammonium sulphate (87 to 130 lbs.per acre) ; (e) twice the amount of ammonium sulphate supplied to c . b, d, andf were treated in the same way as a, c, and e respectively, except that calcium car- bonate (15.6 cwt. per acre) was added. The crops grown were : oats, barley, winter wheat, beetroot, mangel-wurzel, and potatoes. The plots with the larger amounts of nitrogen gave much more produce than the others, and the addition of calcium carbonate was beneficial in every case, with the exception of the beetroot, which had no ammonia. Experiments were also made on the comparative manurial values of ammonium sulphate and sodium nitrate on barley, oats, potatoes, and beetroot. When smaller amounts of the two manures were used, the same increase of crop was obtained in all cases.The same holds good for corn crops when greater amounts of the manures were applied ; whilst in the case of the root crops, a heavy manuring with sodium nitrate was found to be superior t o an eqiial amount of nitro- gen in the form of ammonia. Amount of 'Mineral Matter and the Manurial Value of the Cupules of the Beech from Different Soils. By R.. HORNBERGEE N. H. M. J. T. N. H. M.288 ABSTRACTS OF' CHEMICAL PAPERS. ( L a d w . Versuchs-Stat., 36, 329--335).-The beech cupules which were examined were from trees grown on two different soils, the Buntsandstein and the Muschelknlk. The cnpules from the Muschelkalk are generally the larger and sti*onger, 1000 containing 614.4 grams of dry substance, whilst 1000 cupnles from the Bunt- sandstein yield only 500.5 grams of dry matter.The following are the analytical results :- Pure ash Nitrogen p. c. in dry. p. c. in dry. I. Cupules from Buntsandstein.. .. 2.582 0.330 11. > 2 ,, Muschelkalk .... 1.825 0.379 The pure ash contains, per cent. :- K,O. Na20. CaO. MgO. Fe203. Mn,O,. P20,. SO,. Si02. I. 32-09 2.26 8.44 3.38 7.84 3-22 5.05 1.63 34.43 11. 98-87 1.83 29.04 3 59 4-44 1-21 7-29 4-56 1021 The manurial value of the cupules differs very little for the two kinds, and is relatively small, owing to the low percentage of nitro- gen. The following analyses show the percentage composition of the dry matter of (1) the shells ; (2) the seeds ; and (3) the whole beech-nuts fkom trees grown in t,he Buntsandstein. 1000 of the beech-nuts con- tained 159.86 grams of dry matter, 105.82 grams of which belonged to the seeds, and 54.04 grams to the shells. Pure ash.Nitrogen. 1. Shells .............. 1.5160 0.4930 2. Seeds ............... 3.9900 3.9400 3. Whole beech-nuts.. ... 3.1536 2.7747 The pure ash contained, per cent. :- K20. N+O. CaO. MgO. Fe203. Mn304. P20,. SO,. Si02. 1. 2.744 0.462 6.949 1'092 0.344 1.475 0.572 0.467 0.865 2. 14.597 0.243 4.301 4.180 0.320 1-824 11.291 2221 0.159 3. 10.590 0.317 5-196 3.136 0.368 1.706 7.668 1.628 0.397 N. H. M.VEGETABLE PHYSIOLOGY AND AGRICTLTURE. 281Chemistry of Vegetable Physiology and Agriculture.Influence of Yeast on the Bouquet of Wines. By A. ROMMIER(Bull. SOC. Chim. [3], 2, 297-300) .--Having previously shown thatcultivated yeast determined the non-development of the cells occur-ring naturally on the grape when the former was added to juice inwhich the latter existed, the author fermented the juice of an inferiorgrape and of hothouse grapes respectively with yeast cultures ob-tained from the Champagne, Cate d’Or, and Buxy districts, and foundthat in each case the resulting wines had the bmquet of the winesfrom whence the yeasts were derived.T. G. N.Influence of Carbonic Anhydride on the Products of Fer-mentation. By L. LINDET (BUZZ. SOC. Chim. [3], 2, 195).-The car-bonic anhydride evolved during fermentation by means of yeast wasnot allowed to escape, but retained in the x-essels under pressures of20, 200, 430, and 600 mm. of mercury respectively, without affectingthe amount of alcohol produced or the weight of yeast formed.Inverting Ferment.By 0. KELLNER, Y. MORT, and M. NAGAOKA(%it. physio2. Chen7., 14, 297--31T).-Koji is the name of tt sub-stance uspd in China and Japan in $he preparation of rice wine andT. G. N.VOL. 1.7111. z282 ABSTRACTS OF CHEMICAL PAPERS.alcohol. It consists of the mycelium and spores of a fungus. Wheninvestigated, i t was found to contain a powerfnl inverting fermentwhich changes cane sugRr into dextrose and levulose, maltose intodextrose, and sta,rch into dextrin, maltose, and dextrose ; it prob-ably does not alter lactose or inulin. The invertin of yeastacts on cane sugar only, and the name suggested for the ferment ofKoji is invertnse. Its action is much hindered by the presence ofcommon salt, but it is not wholly destroyed even by 20 per cent.ofthat salt. W. D. H.Nitrification of Ammonia. By T. ScHLoEsrNG (Compt. rend., 109,88:?-887).-Under normal conditions, nitrification of ammonia takespla.ce without any loss of free nitrogen, but when a large excess ofammonium salt is present, there is a very distinct loss of nitrogenin this manner. This loss is due to the formation of a small quantityof nitrite, owing to absence of an excess of oxygen. The nitriteinteracts with the smmoninm salt, with production of free nitrogen ;it also petards nitrificstion, and is itself but slowly oxidised.It is possible that the free nitrogen is not the result of interactionbetween the nitrite and the ammonium salts, but is liberated as aresult of limited oxidation of the ammonia; this point, however, canonly be determined by further experiment.C. H. B.Fermentation of Manure in Absence of Oxygen. Bg T.SCHLOESIKO (Conzpt, rend., 109, 835--840).-When fresh manurefrom cows is kept at 42" to 5 2 O in an atmosphere of carbonic anhy-dride, it undergoes fermentation with evolution of hydrogen, methane,and carbonic anhydride, but no free nitrogen is evolved. Hydrogenis only liberated in the early stages of the change, and disappearsfrom the gases as ferment,at,ion progresses. The mtio of methane tocarbonic anhydride approaches unity only towards the end of theproces8, and varies irregularly throughout the fermentation.No nitrogen is evolved at any stage, but the quantity of ammoniapresent increases.The quantity of oxygen and hydrogen in theevolved gases is greater than the quantity lost by the manure, and itis evident that the water which is present plays an active part inthe fermentation, the oxygen combining with carbon to form carbonicanhydride, whilst the hydrogen is converted into methane.C. H. B.Formation of Cane Sugar in Etiolated Plant Shoots. ByE. SCHULZE (Chem. Centr., 1889, ii, 694-695 ; from B e y . Ueut. hot.G'esell., 7, 280- 281) .-The etiolated shoots of Lupinus Euteus wereexamined, by means of the method described by the author (compareAbstr., 1888, 624), for cane sugar, of which 30 grams (crystallised)wa,s obtained from 800 grams of air-dry shoots, besides a consider-able amount which must have been lost in the separation and purifi-cation.Before germination, not the least trace of sugar wasdetectable in the lupins. As is already known, starch is also formedduring the process of germination of this seed in the absence of light,the other nitrogen-free substance which is present in the seeds aVEGETABLE PHYSTOLOGY ASD AGRICULTURE. 283reserve material disappearing as the formation of sugar and stiirchproceeds. J. w. rJ.Living Vegetable Protoplasm. By T. BOKORSY (PJiigev’sArnhiv, 45, 199-2 19).-The difficulty of applying chemical reagentsto living structures in many cases consistsin the fact that the reagentdestroys the life of the material under investigation. Weak solu-tions of alkalis have not, however, this objection ; they producechanges in the cells, but these are considered to be vital changes,t h a t is, evidence of the living activity, and not of the death of theprotoplasm.These changes may be grouped together under the general term“ aggregation.” This term was first used by Darwin to express thechange that occurs in the tentacles of Droswa on the application ofweak solutions of ammonium carbonate ; this consists in the collec-tion of the protoplasm into separate particles.The term has sincebeen extended to somewhat similar phenomena in other plants ; DeVries (Botan. Zeit., 1886, l), however, limits i t to the contritction ofthe vacuole wall, and does not speak of the formation of proteidgranules in the vacuole coutents as aggregation. Pfeffer distinguishesbetween an outer and inner cell-membrane, the former lining the cellwall proper, the latter surrounding the vacuole fluid, and betweeenthe two is what he terms granule-plasm (Koi-ner-plasma), but whichdoes not necessarily always contain granules.In the present research, a large number of careful niicroscopicobservations are recorded.The plants, the cells of which were ex-amined were Spirogyra, Drosera, TuEipa, C~ocus, Cotyiedon coccinea,&c. The weak alkalis chiefly used were ammonia (1 : 5000) andcaffeine (1 : 1000). Weak potassium hydiboxide, various amines,tetrethylammonium hydroxide, tolnylenediamine, quinine, atropine,&c., were also used in some experiments.The following cases of aggregation could be distinguished :-(I.) The whole protoplasm contracts equally ; this is somewhatdifferent from, but very similar to plasmolysis ; it is seen in crocuspapilltz.(2.) The vacuole wall (inner cell-membrane of Pfeffer)contracts alone, or to a much greater extent than the rest of thecytoplasm ; this is well seen in the red epidermal cells of the petalsof tulips and primulas. (3.) The “ granule-plasm ” collects i i i t 4 )granules or discs ; these are exceedingly minute from the action ofammonia on h’pirogyra cells, but much larger from the action ofsolution of caffeine on sections of the leaves of Cotyledo~ coccinea andEcheveria gebt$lora. (4.) The vacuole-fluid, that is, the cell-sap withactive albumin either in solution or in a greatly swollen condition,becomes pervaded with larger or smallar granules; this is seen inDrosera, Xpiroyyra, and several other plants. W.D. H.Vegetable Cell-membranes. By E. SCHULZE, E. STEJGER, andW. MAXWELL (Zeit. physiol. Chem., 14, 227-273 ; compare Abstr.,1889, 916) .-This investigation shows that the membrane o vegetitblecells contains in addition to cellulose several other carl)otiydi*ar eswhich differ from it widely iu their properties. They are all insolubleu 284 ABSTRACTS OF CHEMICAL PAPERS.in cuprammonium hydroxide, b u t differ in certain other ~eactions ; byhydrolysis, howerer, they all yield pentaglucoses (arabinose, xylose,&c.) ; by warming with phloroglucinol and hgdrochloric acid give achwry-red colour ; and by treatment with very dilute mineral acidsdiffer from cellulose in b h g quickly converted into sugar; thevarieties of sugar formed being galactose, mannose (seminose), andpentaglucoses.The term cellulose as used by Reiss (Abstr., 1889,ti8T) evidently includes these carbohydrates ; i t is, however, advisab:eto restrict the word cellulose to those constituents of the cell-wallwhich are but little affected by strongly diluted mineral acids, whicha r e soluble in cupramnionium hydroxide, which further are colouyeclblne by chloride of zine and iodine, o r iodine and sulphuric acid, andnhich lastly are converted by strong sulphuric acid into dextrose.1 he term proposed f o r these other carbohydrates is that of “para-g;.lactan-like substances.” I t appears doubtful as to whether cellu-I( se is a single substance, but this was -not specially investigated.The paragalactan-like constituents of the cell-wall appear to beof some physiological importance; they seem to be more solublethan cellulose, and enter into solution d u r i n g germinat,ion, function-i v p a s a reserve material before that process commences.It is verydonhtful if triie cklhlose acts in this way.The nutritive value of these substances in tlw animal economyappears, like that of cellulose, to be small, as they are not digestibleby the various digestive juices. On oxidation with nitric acid, theyyield mucic acid. From the point of view of analyses of starch invegetable substances, these paragalactan-like materials are of someimportance, as they, like starch, pass into solution on treatment withdilute mineral acids.W. D. H.Non-Nitrogenous Reserve Substance of the Seeds ofLupinus luteus. By E,. PCHULZE and E. STEIGER (Lumdzo. Ver.suChs.-stat., 36, 391-478).-1 he ethercal extmct of the seeds of LupinvsIute7i.s contained :-Glycerides, fatty acids, and wax 5.99, cholesterinO.l,!i,and lecithin 0.17 per cent. in the dry matter of the seed (freed fromthe shells). A further amount of lecithin can be extracted from theseed by alcohol, making a total of 2.10 per cent. (in dry seed). Afterbeing dlowed to germinate for 14 days, 78.7 parts of dry matterremained and yielded an ethereal extract containing :-Glycerides, &c.,1-50 part, bholesteiin 0.25 part, and only a trace of lecithin, Theamount of lecithin extracted by alcohol was 0.44 part./?-Galactan (Steiger, Abstr., 2886, 603) is a white, amorphouspowder, consisting of microscopic globules.The aqueous solution isnot coloured by iodine, and only reduces Fehling’s solution when i thas been heated with an acid. New determinations of rotatory powergave the mean :--[a]= = + 148.6”. When P-galactan (100 parts)is heated with nitric acid, mncic acid (41.16 parts) is formed. Theacetyl-derivative is a white powder melting at 101-102”. Theamount of p-galactan contained in tho dry seeds (without shells)was determined indirectly (1) as glucose, (2) as mucic acid. Thefirst method gave in different samples :--(a) 10.20, ( b j 10.02, (c) 0.48and ( d ) 6-36 per cent.; the second method gave in sample ( u ) 8.VEGETABLE PHYSIOLOGY ASD AGRICULTURE.285and in ( e ) 7-65 per cent. With regard to the first method, i t isshown that the seeds contain no cane-sugar which would affect tberesults.Paragalactan (paragalnctin, Abstract, 1887, 460)) C6H,,0, (?),could not be obtained free from cellulose. It dissolsves partly inwater when heated under a pressure of 16 or 2 atmospheres; tliefiltered solution, when heated with hydroch!oric acid, reducesFehling's solution, and the residue obtained by evaporating thesolution yields muck acid when oxidised by nitric acid. It is notsoluble in diastase solution. When haat.ed with phloroglucinol andhydrochloric acid, a cherry colour is produced. 5 per cent. aqueouspotash dissolves it partly ; a salt seems to be formed.Paragalactan is contained not only in the cotyledons, but also in tlieseed-shell.A carbohydrate probably identical with paragalactaliwas found in the seeds of Soja hiqida, Pisum sativum, and F d avulgai*is.When lupin seeds are allowed to germinate in the dark for sixdays, all the /?-galactman is used up, whilst n great part of the para-gJactan dissolves ; glucose (not galactose), cane-sugar, and celluloseare formed. N. H. hi.By ARNAUD (Conzpt. rend., 109, 911-914).-The proportion of carrotene in leaves varies with the spe4e.;of the plant, but oscillates between 0.1 and 0.2 per cent. of the driedleaf. It varies with the age of the plant, is at a maximum duringinflorescence, and then gradually diminishes, but never entirely dis-appears.Its quantity is affected by light, and, like chlorophjll, ittends to disappear in the dark.Carrotene can absorb 24 per cent. of its weight of oxygen, butremains unaltered in the living leaf, and very probably undergoesalternate cxidation and reduction in such a manner that its quantityremains almost constant for short intervals of time, It is highlyprobable that carrotene is of very great physiological importance.C. H. B.Musscenda Coffee. By W. R. DUNSTAN (Phann. J. Tram. [ 3 ) ,20, 381).-It has been asserted by Lapeyrhre, that the seeds of aplant which he considers to be a new species of Musscenda, and callsMussmndu borbonica, may be employed as a substitute for coffee.The plant grows in the island of Rbunion, and its seeds are said tocontain 0.3-0-5 per cent.of caffe'ine. An examination of the planta t Kew showed that it is not a Mztsscetida, bnt Gmrtnera vaginata,which belongs to the natural order Logaiiiacece. The author foundthat the seeds contained neither caffe'ine nor theobromine ; strychnineand brucine were also absent, and the only alknlo'id that could bedetected was a trace of choline. W. R. D.(Zeit. U I ~ U ~ . Chem., 28, 525-580).-The analyses of wines and musts here given, in continuationof those published in Zeit. am,?. Chem., 27, 729, et seq., includenumerous brands from the wine districts of Rhein-Hesse, Rheingilu,Rhine Palatinate, Baden, W iirtemberg, Lower Franconia, Alsace,and Lorraine, and of vintages from 1884 to 1888.Carrotene in Leaves.Wine Statistics of Germany.M.J. 236 ABSTRACTS OF CHEMICAL PAPERS.Gra-s .....................Iiay .......................Silage (sour) ............Experiments on Ensilage conducted at Crawley MillFarm, Woburn, 1884-87. By J. A, VOELCKER (Joum. Roy. Agr.Soc. [2], 22, 483-513, and 23, 403--417).-The object of the expe-riments was to determine the relative feeding values of silage as com-pared with roots and hay-chaff. The method employed was to feed fourbullocks with weighed amounts of hay-chaff and swedes, and four morewith an amount of silage containing the same quantities of di-ymatter, woody-fibre, and nitrogen as the hay-chaff and swedes con-tained ; all the animals had, besides, weighed amounts of decorticatedcotton-cake and maize-meal.In the first year's experiments, grasssilage of inferior quality and clover silage which was of' thoroughlygood quality were employed. I n both cases a much greater increasewas obtained wibh roots and hay-chaff than with silage.In the second year the following series of experiments were made :-(1) sour silage against roots and hay-choff; (2) sweet silage againstroots and hay-chaff; (3) oat silage against roots and straw-chaff';(4) oat silage against hay. This time the grass employed was ofT-eyy fair quality. The bullocks fattened well on both sour and sweetgrass silage of good quality, but still not so well as with roots andhay-chaff ; whilst oat silage proved, in this instance, to be superiort o either straw-chatf with roots or to hay. It was found that the oatsilage when well made keeps perfectly for a t least two years. Thefollowing table shows the percentage of nitrogen, albuminoldnitrogen, and non-albuminoid nitrogen in the silage :--0'311'16C'L4In dry.I In fresh. I1-1 I I I IAlbumino'id Non-albumi- Albumino'id Xon-albumi- Total 1 nitrogen. I noydnitrogen. I niEi:n. I nitrogen. 1 ntiid nitrogen.! nitrogen.Sweet silage (grass).. 0 '45Sour silage (grass .... 0.28Oat silage ............ ..., 0 -15Hay ........................ 1 '37The object of the third year's experiments was to determine thevalue of grass made into hay as agzainst that of the same grass con-verted into silage. The grass employed was of very fair quality, andthe silage wits extremely good and well made.The percentage of nitrogen, albuminold nitrogen, and non-alhu-minoi'd nitrogen in the grass, and in the hay and silage preparedfrom it, was as follows :-I- 1 Allruininoi'd11 it rogen.____--- I__--In dry.I In fresh.INon-albnmi- 1 Total 1 Altuminoyd 1 Non-albumi- 1 Totalnoid nitrogen. nitrogen. nitrogen. noId nitrogen. nitrogen.0 '08 0 -4'' 1 *29 0 '30 1 '590'19 1 1.35 1 1 - 4 1 1 0.23 1'6.10 '27 0 '51 0 *a7 0 *9n 1 Y.VEQETABLE PHYSIOLOQY AND AQRICULTURE. 2157100 parts of grass gave :-Good silage 87.15 parts, inferior andmouldy silage 4.56 parts, loss by fermentation, &c., 7.29 phrts. Theproduce in hay was:-good hay 29.77 parts, inferior hay 2.61 parts,water and loss 67.62 parts.The experiments show that the silage from 28,995 lbs.of grass (theproduce of 2.4 acres) and the hay from 34,442 lbs. of grass (theproduce of 2.8 acres) gave equal feediiig results.The results of similar experiments made at Wilmington, nearShrewsbury, showed a slightly larger gain with silage than withhay prepared from the same grass.Ammonia and the Nutrition of Plants. By A. M u m z( J . Pharm. [ 5 ] , 20, 489-492).-Experimerits were made to ascer-tain whether salts of ammonia could be utilised by the roots of plantswithout first being converted into nitrate. Seeds of bean, horse-bean,maize, barley, and hemp were freed from nitrification germs, andsown in soil freed from nitrates and germs, and placed in glazedboxes supplied with sterilised air. Ammouia in the form of sulphatewas supplied.A similar set of pots was prepared containing germsof the nitric ferment. The sterilised soil contained no nitrates eitherat the beginning or eud of the experiment; the non-sterilised soilcontained no nitrates at beginning, but yielded 91.2 and 420.0 milli-grams per kilo, at the end of the trial. In the sterilised pots, theplants grew well, and assimilated all the nitrogen required from theammonicm salt, showing that nitrification is not essential.Effect of Manuring with Ammonium Sulphate and withSodium Nitrate. By &I. MAERCKER (Bied. Cmtr., 18, 724-729).-In order to determine the effect of calcium carbonate on the rnanuriaJaction of ammonium sulphate, six plots of land, supplied with phos-phoric acid, or kainite, received the following :-(a) Nothing ;( c ) ammonium sulphate (87 to 130 lbs.per acre) ; (e) twice theamount of ammonium sulphate supplied to c . b, d, andf were treatedin the same way as a, c, and e respectively, except that calcium car-bonate (15.6 cwt. per acre) was added. The crops grown were :oats, barley, winter wheat, beetroot, mangel-wurzel, and potatoes.The plots with the larger amounts of nitrogen gave much moreproduce than the others, and the addition of calcium carbonate wasbeneficial in every case, with the exception of the beetroot, which hadno ammonia.Experiments were also made on the comparative manurial values ofammonium sulphate and sodium nitrate on barley, oats, potatoes, andbeetroot. When smaller amounts of the two manures were used, thesame increase of crop was obtained in all cases. The same holdsgood for corn crops when greater amounts of the manures wereapplied ; whilst in the case of the root crops, a heavy manuring withsodium nitrate was found to be superior t o an eqiial amount of nitro-gen in the form of ammonia.Amount of 'Mineral Matter and the Manurial Value of theCupules of the Beech from Different Soils. By R.. HORNBERGEEN. H. M.J. T.N. H. M288 ABSTRACTS OF' CHEMICAL PAPERS.( L a d w . Versuchs-Stat., 36, 329--335).-The beech cupules whichwere examined were from trees grown on two different soils,the Buntsandstein and the Muschelknlk. The cnpules from theMuschelkalk are generally the larger and sti*onger, 1000 containing614.4 grams of dry substance, whilst 1000 cupnles from the Bunt-sandstein yield only 500.5 grams of dry matter. The following arethe analytical results :-Pure ash Nitrogenp. c. in dry. p. c. in dry.I. Cupules from Buntsandstein.. .. 2.582 0.33011. > 2 ,, Muschelkalk .... 1.825 0.379The pure ash contains, per cent. :-K,O. Na20. CaO. MgO. Fe203. Mn,O,. P20,. SO,. Si02.I. 32-09 2.26 8.44 3.38 7.84 3-22 5.05 1.63 34.4311. 98-87 1.83 29.04 3 59 4-44 1-21 7-29 4-56 1021The manurial value of the cupules differs very little for the twokinds, and is relatively small, owing to the low percentage of nitro-gen.The following analyses show the percentage composition of the drymatter of (1) the shells ; (2) the seeds ; and (3) the whole beech-nutsfkom trees grown in t,he Buntsandstein. 1000 of the beech-nuts con-tained 159.86 grams of dry matter, 105.82 grams of which belongedto the seeds, and 54.04 grams to the shells.Pure ash. Nitrogen.1. Shells .............. 1.5160 0.49302. Seeds ............... 3.9900 3.94003. Whole beech-nuts.. ... 3.1536 2.7747The pure ash contained, per cent. :-K20. N+O. CaO. MgO. Fe203. Mn304. P20,. SO,. Si02.1. 2.744 0.462 6.949 1'092 0.344 1.475 0.572 0.467 0.8652. 14.597 0.243 4.301 4.180 0.320 1-824 11.291 2221 0.1593. 10.590 0.317 5-196 3.136 0.368 1.706 7.668 1.628 0.397N. H. M

ISSN:0368-1769    

DOI:10.1039/CA8905800281

出版商:RSC    

年代:1890

数据来源: RSC