ORG ANIU CHEMISTRY. 35 Organic Chemistry. Arrangement in Space of the Atoms in the Molecules of Carbon-compounds. By J . WISLICENJS (Chem. Centr., 188’7, 1005 -1009).--Van’t Hoff and Le Be1 were the first to explain the optical diflerence of certain carbon-compounds by a difference in the relative arrangement of the atoms in space within the mo.lecde ; since their work, however, no serious attempt has been made t o apply their theory t o explain the isomerism of certain compounds, whose com- position, according to present views, is identical. a 236 ABSTRACTS OF CHEMICAL PAPERS. Such peculiar cases as those established by the researches of Fittig on the isomerism of male’ic and fumaric acids, however, and the dis- covery of a third and fourth monobromocinnamic acid, have been classified under the generic term of alloisomerism.Chemists hitherto seem to have contented themselves with a name. Adopting the hypothesis of van’t HoiYand Le Be1 that t.he atoms occupy the solid angles of a tetrahedron, being arranged around a central carbon-atom it is evident that two carbon-atoms, associated together in the parafflno‘id form of combination, would revolve around one common axis, passing through the point of union of the atoms and the direction of attractiou of two associated atoms, such as those of hydrogeu. When two carbon-atoms are combined together, as in the olefines, they can only revolve round an axis which is the straight line connecting the two common carbon-atoms. Supposing all four of the affinities of the saturating atoms are unequal, then six isomerides are possible, in the case of two pairs three isomerides, and three also if two affinities are equal and two unequal.For male‘ic acid, van’t Hoff has proposed the formula CH*COOH II CH-COOH , so that for fumaric acid the formula will be COO*HCH II CH-COOH In order to explain the conversion of malei’c into fumaric acid through the intervention of halogen-derivatives of succinic acid, it is sup- posed that the atoms combined with neighbouring carbon-atoms mutually react on one another according to their chemical affinity. Hence, it follows that two carbon-atoms combined together by one affinity, and being in a poRition by revolution around their axis to give way to this attraction, will so arrange themselves that the associated radicles interchange positions in the syshem.Such a relative arrange- ment will be stable in the cold, but at a higher temperature, as the interoscillation of tbe elements will be more frequent, there is a loosening of the affinities, and a different configuration ensues. When an unsaturated compound passes into one that is saturated, it is in- different to which of the two carbon-atoms each particular radicle attaches itself ; the compounds formed are identical. But if an atom is combined with two different radicles, then by addition an asymmetri- cal carbon-atom results according as the added atoms attach them- selves to one or other position of affinity. This explains the forma- tion of optically inactive compounds under these conditions, since both modifications are produced in equal quantities.As regards the nomenclature of these dieerent geometrically isomeric configurations, it is proposed to call the arrangement aCb aCb 11 the centrally or axially symmetrical, and the arrangement 11 bCa aCb the plane symmetrical. The following examples are given in illustration of the aboveOROANIC GHEMISTRT. 37 views :-Tolane dichloride exists in two modifications ; according to the author's hypothesis, the modification of higher me1 ting point, obtained by the direct chlorination of tolane, is the plane symmetrical Ph*C*Cl Ph*C-Cl 11 , whilst the other is the axially symmetrical 11 As fumaric acid is principally formed by heating malic acid, in which, doubtless, the carboxyl-group has more inclination towards the hydrogen-atom than to the hydroxyl- or other carboxyl-group, its Ph.C*Cl C1.C.Ph C 0OH.C H-OH constitution may be represented by a configuration I HHOC o OH' from which by the abstraction of a molecule of water the formula COOHGH II results.The conversion of ethyl maleate into ethyl fnmarate by iodine is explained by the intermediate formation of diiodosuccinnic acid, an interchange of position of the iodine- and hydrogen-atoms ; the removal of a, molecule of hydrogen iodide gives ethyl iodofumarate, which in its turn is reduced by the hydrogen iodide to ethyl fumarate. The reverse process of conversion of fumaric into male'ic acid through the intervention of dibromosuccinic acid can be explained in like manner. The isomerism of crotonic and isocrotonic acid is also of a similar order, the constitution of the one being expressible by a formula 11 , of the other as 11 .Cinnamic acid should also exist in two geometrically isomeric forms, of which, as yet, only one has been obtained. HC-COOH H*C*Me Me43.H HOCOOH H*C*COOH /it-Coumaric acid has the plane symmetrical arrangement HC CeH,. 0 H as it is easily converted into its lactone, conmarin ; i n its isomeride, the atoms are arranged in the axially symmetrical configuration ; this, by fuming hydrobromic acid, is converted into coumarin, by temporary addition of a, molecule of the acid, and by an inclination towards formation of the lactone. By this theory, the removal of the elements of a halogen acid and simultaneously of carbonic anhydride from the sodium salt' of a p-halogen substituted acid is expiained, as also the foi-mation of anhydrides and lactones when two carbDxyl- or a hydroxyl- and carboxyl-group are in the y-position.The author is engaged on experimental evidence in favour of this theory. V. H. V. Nitrosates, Nitrosites, and their Derivatives. By 0. WALLACH (dnnalen, 241, 288--315).-The crystalline compound which Guthrie38 ABSTRACTS OF CHEMICAL PAPXRS. (Annulen, 116, 248 ; 119, 84) obtained by the direct union of amylene with nitrogen peroxide, is most conveniently prepared by passing the nitrous fumes evolved by the action of strong nitric acid on arsenious oxide into a well-cooled mixture of amylene (1 vol.) and glacial acetic acid (2 vols.). The operation is interrupted when the colour of the liquid changes from blue to green.The crystals are washed with acetic acid, afterwards with water. As commercial amylene is a mixture, the product is not homogeneous. On recrystallisation from chloroform or benzene, two substances having the composition C5H,,N20a are deposited, namely, cubes melting at 96-97', and needles melting a t 89". This compound is not a dinitrite but 8 nitroso-nitrate or nitrosate. On boiling with alcohol and aniline, it yields aniline nitrate and nmyZenenitrolaniZine, NHPh*C5Hg : NOH. The base melts a t 140-141". It dissolves freely in ether, chloroform, warm alcohol, and in dilute acids, and crystallises well. The hydrochloride, CIIHl,N20,HC1, is deposited from a hot aqueous solution in anhydrous crystals. It is best prepared by passing hydrogen chloride into an ethereal solution of the base, when the hydrochloride is precipi- tated in the form of a crystalline powder.The w'troso-compound, NO*NPh*C,H,:NOH, is deposited as a crystalline powder when a solution of sodium nitrite is poured into ail acid solution of tLe base. It melts at 327-128", and is soluble in alcohol and in alkalis. The nitroso-compound is reprecipitated on adding an acid to t,he alkaline solution. The hydrochloride is decomposed by boiling with water, or better with hydrochloric acid, yielding hydroxylamine and a ketond base, NHPh*C,H,: 0. The new base melts a t 61", and is soluble in alcohol, ether, and in hot, 6ater. AmyleiLenitro123ctratolzl.idine, CI2HlsN20, and its hydrochloride and nitrate form well-developed crystals. The base melts a t 111-112", and the nitroso-derivative a t 147-148".The hydrochloride is decom- posed on boiling it with hydrochloric acid, yielding hydroxylamine and the base C,,H,,N20 melting a t 98". The nitroso-derivative melts with decomposition a t 149-150". The hydrochloride is more soluble in water than the corresponding para-salt. Amylenenitrolorthoanisidine melts a t 138-139". The hydrochloride is deposited from its aqueous solution in prisms. Amylene nitrosate and piperidine act on each other very energetically, forming a crystal- line base, C,,H,,N,O. It melts at 95-96", and is insoluble in water and in alkalis. The hydro- chloride is art oily liquid, but the platinochloride (c,,H,oN,0)2,HB,PtC:16, forms beautiful prisms. Arnylenerzitroldiethyla~t~ine crystallises i4 plates and melts a t 71-72".ArnylenenitroEalLylamine is soluble in water. The hydrochloride, C8H16N20,HCl, is crystalline. This base is isomeric with nitrosoconiine. Amylene nitrosate acts on sodium ethoxide, forming a crystalline compound which melts a t loo", and also on ethyl acetoacetate, yielding a crjstalline compound of the composition Amylenenitrolorthotoluidine melts a t 115". The Yalts dissolve freely in water. C,H,,NO*CH(C OMe) *COOEt. Guthrie (bc. cit.) observed that amyl nitrosate acts on potassiumORQANIC CHENISTRY. 39 cjanide, but the author finds that a crystalline compound and potas- sium nitrate, not a liquid and a m i t r i t e , are formed in the reaction. A blue crystalline compound is formed by passing nitrous fumes into brornamylene dissolved in acetic acid, and pouring the crude product into water.This compound acts on piperidine at the ordinary temperature, yielding a colonrlesg, crystalline substance which exhibits neither acid nor basic properties. It is soluble in alcohol, is rich in bromine, and has an odour resembling that of camphor. Synthetical Experiments in the Sugar-group. w. c. w. By E. FISCHEB and J. TAFEL (Ber., 20, 8566-2575).-1t was previously shown (Abstr., 1887, 651) that acraldehyde bromide is converted by baryta into what is probably a glucose. With phenylhydraaine, the product of the reaction yields a- and P-phenlylacrosazones, melting a t 205' and 148" respectively. When isoglucosamine oxalate (Fischer, Abstr., 1886, 934) is dis- solved in ice-water (10 parts) and treated with sodium nitrite, an evolution of nitrogen takes place ; after three hours, the temperature is aliowed to rise to 20".The product is exactly neutralised with aqueous soda, evaporated in a vacuum, and the residue extracted n-ith absolute alcohol. On evaporating the solution, levulose is obtained as a yellowish syrup ; the spec. rotatory power a t 80"=25". It produces strong fermentation with yeast in 10 minutes, gives a precipitate of pheny lglucosazone wit'h phenylhydrazine, and yields Kiliani's levu- lose hydrocyanide when treated with hydrocyanic acid. The consti- t ution of isoglucosamine is probably NH2.C &,*GO. [ CH( OH) I3.CH2.OH. Ledderhose's isomeric glucosamine has possibly the constitution C: 11 0. C H ( N H,) [ C H ( 0 H ) ] BG H i 0 H . a-Phenylncrosazone is obtained in the following manner : A solu- tion of 75 grams of pure, crystallised barium hydroxide in 1-25 litre OF water is cooled with ice-water; 50 grams of freshly-distilled acraldehyde bromide is then added by drops, the baryta solution being kept violently shaken.Eight preparations are united, made slightly acid with sulphuric acid, and treated with a strong solution of sodium sulphate until the barium is completely precipitated. After 12 hours, it is filtered, neutralieed with aqueous soda, and evapo- rated in it vacuum to 18 litre. When cold, a solution of phenyl- hy drazine hydrochloride (50 grams) and sodium acetate (50 grams) in 100 C.C. of water is added, and the whole left for 12 hours; it is then filtered and warmed on it water-bath wikh 150 grams more of phenylhydrazine hydrochloride and 150 grams of sodium acetatre.In the course of foul. hours, a half crystalline and half resinous preci- pitate separates; this is washed with water and extracted with ether, when the greater part of the resin and the /I-phenylacrosazone dissolves, leaving the a-phenylacrosazone. After filtration, the a-com- pound is repeatedly extracted with boiling alcohol, and treated with hot water, after which it is almost pure. The yield from $00 gi*ams of bromide is 18 grams. It melts a t 205" (uncorr.), and is very sparingly soluble. On addiug water to the hot alcoholic solution, it sepwntss in long, slender needles. a-Acrosaniine, Cs&N05, is prepared similarly to isoglucosamino40 ABSTHACTS OF CHEMICAL PAPERS.(Zoc. cit.) by reducing the acrosazone with zinc-dust and acetic acid, and is purified by means of the oxnlate. It shows all the reactions of the glucosamines. When the oxnlate is dissolved in ice-water and treated with sodium nitrite, a-acrose, C6H120,, is formed; this is obtained as a light-brown syrup, having a sweet taste. It reduces Fehling's solution. p-Pheiiy Lncrosazolte, C,aH22N404, is obtained by evaporating its ethereal extract' (obtained in the purification of the a-compound), dis- solving in alcohol, and precipitatiag with water. The dried product is exhausted with cold benzene several times. The yellow crystalline ~esidue is boiled with acetone (2 parts), filtered, and precipitated with ether and light petroleum. It crystallises in slender, yellow nsedles melting at 148", dissolves in alcohol and acetone much more readily than the a-compound, but is almost insoluble in ether when pure.The yield is small. The resemblance of a-phenylacrosazone to phenylglucosazone makes i t probable t.hat a-acrose has the constitution expressed by the formula OH.CH,*[CH(OH)]4*CIEE0 ; the constitution of p-acrose would then be OH*CH,*CEI(OH)*CH(OH)*C(OH) (CH2*OH)GH0 or OH.CH,.CH(OH).CH( OX).CO-CH(OH)*CH2*OH. The lower melting point and more ready solubiIity of the p-osazone point to its being a derivative of a sugar with an abnormal carbon-chain. Isodulcitolphett yllydrazine, CsHl,04 N2H Ph, mystallises from alcohol in colourless plates melting at 159'. It is insoluble in ether, readily soluble in water and in alcohol.The aqueous solution is dextro- rotatory. Lactosephen?/Zhyarazine, C16HPBOION2, is prepared by adding phenyl- hydrazine (1 part) to a solution of milk-sugar (2 parts), in hot water (2 parts). After two days, twice the volume of absolute alcohol is added, and the whole treated with much ether. The syrupy preci- pitate after being repeatedly dissolved in alcohol and precipitated with ether, is obtained as a solid mass. I t is filtered, quickly washed with ether, and dried in a vacuum over sulphuric acid. It dissolves readily in water and in alcohol, and is insoluble in ether. It is laevorotatory. N. H. M. Isonitrosogalactose. By P. RISCHBIETH (Bw., 20, 2673-2674). -When galactose (1 gram) and hydroxylamine hydrochloride (0.4 gram) are dissolved in a sniall quantity of water, treated with sodium carbonate (0.65 gram), and allowed to remain for 24 hours, isolzitrosogaZwttose, C6H1,0, : NOH, is obtained as a colourless, crys- talline substance which melts at 175-176", and is readily soluble in hot water, soluble in hot dilute alcohol, and practically insoluble in ether and absolute alcohol.Under similar conditions, no separation could be obtained from dextrose, levulose, or arabinose. w. P. w. By C. WEHMER (Ber., 20, 2614--2618).-Plants which readily produce starch from dextror;le, cane-sugar, mannitol, and glycerd, do not produce starch in any determinable amount from formose. The Carbohydrate Character of Formoee.ORGANIC CHERIISTRY. 41 When 28 grams of formose syrup is boiled with 100 C.C. of wuter and 5 grams of hydrochloric acid (sp.gr. 1.2) for 11 hours, a sepa- ration of humic suhstance (3.5 grams) takes place. The filtrate shows the iodoform reaction distinctly and reduces Fehling's solution. No levulinic acid is formed. 13 per cent. phosphoric acid produced the same decornposition, also without formation of levulinic acid. The author concludes t h a t formose is not a carbohydrate. Saccharification in Vegetable Tissues. By BONDONNEAU and FORET (Compt. rend., 105, 61 7--618).-The amylaceous plant is heated at 90-100" with acid of 1 t o 2 per cent., and the starch is gradually and completely converted into dextrin, glucose, saccharose, &c., and the soluble products thus formed diffuse through the cell- walls into the surrounding liquid. When the proportion of sugar in the liquid ceases to increase, the process is finished. This method is readily applied on a large scale.The exhausted pulp is free from starch, but constitutes a valuable nitrogenous food-stuff for cattle. The pulp from maize has the composition,-Water, i9.15 ; ash, 1.22 ; nitrogenous matter, 8-38 (containing nitrogen, 1.31) ; oil, 5.48 ; cellu- lose and loss, 5-77 = 100. It will be observed that water has been substituted for the starch. N. H. M. C. H. B. Amines of the Paraan and Benzene Series. By MALBOT (Compt. rend., 105, 574-576) .-In the reactions described, unless otherwise stated, the substances were mixed in equal molecular pro- portions. Ethylamine and aqueous ammonia at 100" yield triethylamine, but st 130" tetrethylammoniurn chloride is obtained in considerable quantity.Propyl iodide under the same conditions yields tripropyl- ltmine at loo", snd tetrapropylammonium iodide at 150". Although pure tripropylamine combines but slowly with propyl iodide in the cold, combination becomes complete at 150". Tripropylamine has no action on propyl chloride in the cold, and the reaction takes place slowly at 150", but becomes very rapid at 190", the products being tripropylamine and dipropylamine hydrochlorides and propylene. Rutyl iodide and aqueous ammonia at 160" yield only tributylamine, and the action of tributylamine on butyl iodide is strictly analogous t o that which takes place with the corresponding propyl-derivatives, Tributylamine acts slowly on -butyl chloride at 80°, but at 170" piire dibutylamine hydrochloride and butylcne are obtained.Dibutyl- amine and butyl iodide in the cold yield dihutylamine hydriodide and free tributylamine; at a higher temperature, the reaction is analogous to that obthined with the chloride. Isoamsl iodide and aqueous ammonia at 150" yield tetramyl- ammonium iodide. T'riamylamine acts slowly on amyl iodide in the cold, but at 150" triamylamine hydriodide and amylene are formed. At ZOO", the reaction is very rapid, and the products are diamylamine hydriodide and amylene. With amyl chloride, a salt of trinmylamine is formed at 17O", and undergoes no further alteration even at '210". Dinmy lamine and amyl iodide yield diarnylamine hpdriodide, free trismglamine, and te tramylarnmonium iodide.42 ABSTRACTS OF CHEMICAL PAPERS. Capryl chloride with aqueous ammonia in equal molecular propor- tions at 170" yields monocaprylamine together with a small quantity of the dinmine and caprylene.With twice the proportion of ammonia, the diamine is the chief product,, and no caprylene is formed. Capryl iodide with an equivalent quautity of ammonia a t 160" yields only monocaprylamine, either free or tocether with caprylene, the latter occupying a t 120" a volume equal to half the volume of capryl iodide used. Benzyl and metatolyl chlorides yield the tertiary amines almost exclusively, whilst cinnarnyl chloride yields the secondary amine, The bases are obtained in the form of salts by the action of the correspond- ing alcoholic chlorides. The formation of a bivalent hydrocarbon is especially marked with styrolylamines, cinnamene being obtained in large quantity.It is identical w i t h the synthetical cinnamene of Berthelot, and part of it is obtained in the form of metacinnamene. Whether the products of these reactions are in the free stmate or in the form of salts is determined by the conditions of equilibrium between the rival attractions of the ammonia and the amines for the ethereal salt which is present, and the acid contained in this salt. The increasing complexity of the amines is the result of a series of successive tlransformations, a bivalent hydrocarbon being produced simultaneously. This last fact is i u favour of the ethylene theory of the constitution of amines. C. H. B. Allyl-diguan idine and its Derivatives. By A. SMOLEA (Monatsh.; 8,3i9--390) .-Allyldiguanidine copper silkhate, ( C,H,,N,),Cu,H,S04, is obtained by dissolving dicyandiamide in aqueous copper sulphato and adding allylamine; the mixture is then heated for some hours at 100".This salt is more soluble in alkaline solutions than in pure water ; it separates from boiling solutions in carmine-red, anhy- drous crystals, from cold solutions in pale rose-coloured, microscopic needles with 1 mol. H,O. The other salts were made from the fore- going by double decomposition. The chloride, (C5H,0N,),C~i,2HC,1 + 2H,O, yields groups of rose-red crystals easily soluble in water to an amet hyst-coloured solution. The nitrate, ( C5H1,N5) Jh,2HN 03, forms dark-red crystals easily soluble in water. Other salts were prepared. Copper-allyldiguanidine, ( C6H10N6)2C~, was obtained by precipitating a boiling solution of the sulphate with soda.It crystallises in dark rose-red needles, sparingly soluble in cold, more soluble in boiling water. A solution of this base precipitates metallic hydroxides from solutions of metallic chlorides, the chloride described above remaining i n solution. Allyldiguanidine sulphute, ( C3H,lN5)2,H2SO* + QH20, was obtained by the action of hydrogen sulphide on the copper salt suspended in water. It crystallises in prisms, and is soluble in water, insoluble in alcohol. The acid sukhate, C5Hl,N5,H2SO~ + $H,O, crystallises in scales. The chloride, C5H,lN5,HCI, yields transparent prisms easily soluble in water and alcohol. It yields no precipitate with PtCl,, nor with potassium tartrate. The acid chloride, C5HllN6,2HCl, forms small, transparent prisms easily soluble in water and alcohol.AIZyl- diguanidine, CZH6N5*CBH5, was prepared by treating a solution of the When heated above 130°, the base decomposes.ORGANIC CHEMISTRY. 43 raulphate with the calculated quantity of barium hydroxide and also by the action of hydrogen sulphide on copper all yldiguanidine sus- pended in water. It forms a dightly crystalline, very hygroscopic mass, is strongly alkaline in character, displacing ammonia from its salts and absorbing carbonic anhydride from the air. When heated with potash and chloroform, it yields allylcarbamine (C,H,*NC). In chemical characteristics, the above copper compound somewhat resembles the alkalilie earthy metals, the allyldiguanidine, the alkali metals and especially sodium.Isonitroso-compounds. By E. BECKMANN (Ber., 20,2580-2585 ; compare Abstr., 1887, 826) .-The intramolecular change which takes place when diphenylketoxime is treated with phosphorus pentacliloride or with sulphuric acid, is also produced by hydrochloric acid, acet,ic chloride, acetic anhydride, and acetic acid. When a cooled soluti.on of diphenylketoxime in 10 parts of glacial acetic acid containing acetic anhydride is saturated with hydrogen chloride, and then heated at TOO", the oxime is completely converted into benzanilide; this is precipitated by sodium carbonate, and re- crystallised from alcohol. ~~ethy~phenylk~toxime when similarly treated yields acetanilide, which separates as hydrochloride on coo 1- iiig the solution; the reacfion takes place in the cold, but requires some days.Methylpropylketoxime is converted by hydrochloric acid into the compound NHPr*CMeO,HCl, and not into the compound NHMe-CPrO. When diphenylketoxime is heated with acetic anhydride in presence of hydroxylamine hydrochloride a t 150", acetanilide and benzoic acid are formed. Methylphenjlketoxime when heated with 10 parts of acetic anhydride for six hours a t loo", yields the compound CMePh : N*OAc (Rattner, Rer., 20, 506). This crystallises from light petroleum in forked needles mel6ing a t 55". Glacial acetic acid at 180" acts on diphenylketoxinie with forma- tion of benzanilide, acetanilide, and benzoic acid. Methylphenyl- ketoxime is converted by hot glacial acetic acid into oily products ; acetanilide is not formed.I?. H. M. L. T. T. Oxidation by Means of Hydrogen Peroxide. By C. WURSTER ( B e y . , 20, 2631--263S).-The author showed previously (Centr. fiir Yhysiol., 1887, 33) that organic acids are quickly oxidised by hydro- gen peroxide to carbonic anhydride ; the higher fatty acids and oils, cane- and grape-sugar, are rather stable towards hydrogen peroxide, whilst boiled starch is converted first into crythrodextrin and then into sugar. Hydrogen peroxide (6 mols.) reacts with hydroxylamine sulphate a t 40" with formation of sulphnric acid, nitric acid (2 mols.), and water (12 mols.) . Hydroxylamine hydrochloride is similarly converted into hydrochloric and nitric acids and water. When an aqueous solution of phenol is treated with a hydroxyl- amine salt aud hydrogen peroxide, nitrosophenol is formed.Phenylhydrazine is converted by hydrogen peroxide into benzene and diazobeuzeneiinide. The production of benzene makes it pro- The yield is quantitative.44 ABSTRACTS OF CHEhlICAL PAPERS. bable that free diazobenzene is first formed in the oxidation of the h y drazi ne. By P. RISCHBIETH (Ber., 20, 2669-2673).-Isonitrosovaleric mid (Abstr., 1883, 1129) can readily be obtained by dissolving hydroxylamine hydrochloride (50 grams) and levulinic acid (83 grams) in a small quantity of water and adding a concentrated aqueous solution of sodium carbonate (38 grams) ; a separation of the acid immediately occurs, and this is pi-rrified by recrystallisation froni water. The yield amounts to 90 per cent. of that theoretically possible.When treated with hydrogen chloride, the acid melts and absorbs the gas, and on warming the product, a sudden reaction occurs with the evolu- tion of nitrogen, and production of a black residue. On oxidation with dilute nitric acid, a large volume of gas is evolved, and acetic and succiriic acids are formed; the residue is, moreover, found to be free from nitrogen. If the acid (6 grams) is heated with sulphuric acid( 10 grams) in a vacuum at 150", succinic acid sublimes, and nitrogen is evolved ; when, however, a much larger proportion of sulphuric acid (36 grams) is employed, and the heating is continued jor 6 to 12 hours at 100" at the ordinary pressure, the elements of a molecule of water are withdrawn from the molecule of isonitrosovaleric acid, and the " inner anhydride," npvaleroximidolactone, together with succinic acid, resu1t.s.N. H. M. Isonitrosovaleric Acid and v-Valeroximidolactone. r- Valeroximidolactone, CM&EH<g2>C0, cryskllises from ether and water in long, white prisms; it melts at 69-70" when slowly heated, and at a somewhat higher temperature when the heat'ing ia rapid, and boils at 232" without decomposition. When heated with aqueous alkalis, it yields the corresponding salts of isonitrosovaleric acid, but dilute sulphuric acid, hydrogen chloride, fuming hydrochloric acid, and ammonia are without action on it at 100". O n distillation with nitric acid (sp. gr. = 1*4), a distillate is obtained which contains in addition to unaltered lactone at least two distinct crystalline com- pounds ; these have not yet been further examined.New Source of Capric Acid. By A. BUISINE and P. BUTSINE: ( C o n y t . rend., 105, 61&617).--Capric acid does not exist as such in suint, but au aqueous solution of suiiit undergoes fermentation under the influence of microbes, and the quantity of fatty acids and especi- ally of capric acid is greatly increased, the proportion of the latter rising to 5 per cent. The capric acid ir;; separated by distillation, saponification, and subsequent fractionation, and is finally crystallised from boiling water. It forms a crystalline, buttery mass, with an odour of rancid butter, melts at 31", is soluble in alcohol and ether, and is slightly soluble in boiling water, from which it crptallisea in white needles. The barium salt is soinble in alcohol.C. H. B. W. P. W. Linoleic Acid. By L. M. NORTOX and H. A. RICHARDSON (Ber., 20, 2735--2736).-When endeavouring to dry linoleic acid at 100" in aORQANIC CHEM ISTRT. 45 current of hydrogen, the authors found that a. continued loss of weight occurred even after 28 hours, although no change in composition took place. Linoleic acid can be distilled without any appearance of de- composition at 290" under 89 mm. pressure, and a colourless product is obtained amounting to about three-fourths of the mid taken. This consists of an acid, CmH%O2, which cannot again be distilled in a vacuum without decomposition; its sp. gr. is 0.9108 a t 15", and its vapour-density = 153. Under similar conditions, ricinoleic acid yields an acid agreeing in Butanedicarboxylic Acid.By R. OTTO and A. R~SSING (Ber., 20, 2736-2747).-By the reduction of dimethylmale'ic acids, two batane- dicarboxylic acids are obtained, the one, melting at 193-194', which has been shown to be symmetrical dimethylsuccinic acid, the other, ethylmethylmalonic acid, melting at 118-120". I n this paper, the anhydrides of these acids are more particularly studied. The former on dry distillation yields an anhydride melting at 87", previously described by Bischoff and Rach ; but thiR substance on rehydration and crystallisation from the aqueous solution yields not only the original or symmetrical dimethylsuccinic acid, but also the above- mentioned isomeric ethylmethylmalonic acid. On the other hand, the symmetrical dimet hylsuccinic acid, when treated with excess of acetic chloride, yields an anhydride isomeric with the above, which crystallises in rhombic tables melting at 38"; this on rehydration yields the original acid only.Again the butanedicarboxylic or ethylmethylmalonic acid, melting at 121", remains unaltered on dry distillation, but when treated with acetic chloride i t yields a n anhydride of the same melting point, 86-87", and crystalline form as the former of the anhydrides mentioned above, but which, however, differs from it in yielding on rehydration the original acid only. Distillation of Citric Acid with Glycerol. By P. DE CLERMONT and P. CHAUTARD (Compt. rend., 105, 520-523).-500 grams of crystallised citric acid mixed with 750 grams of ordinary glycerol of 28" are distilled in a glass retort of 3 litres capacity, and the product redistilled.The first fraction consists of about 250 grams of water contbining a small quantity of acraldehyde, &c. ; some crystals also separate in the colder part of the apparatus. The mass then swells up, and the teriiperature musk be reduced, but it is afterwards gradually raised until the distillation is complete. The distillate during this second stage consists of 650 to 700 grams of liquid. The total products of the decomposition are 950 grams of liquid, 30 grams of a bulky, carbonaceous residue, carbonic oxide and carbonic anhydride, and vapours of acetone and acraldehyde. I n addition to water containing small quantities of acraldehyde, the only products in the distillate are unaltered glycerol and pyruvine or the pyruvic ether of glycide, MeCO*COO-CH,.CH<-O->, which is also obtained by the distillation of glycerol with tartaric acid or glyceric acid.Probably composition with that just described. w. P. w. V. H. V. CH,46 ABSTRACTS OF CHEMICAL PAPERS. the pyruvine is a product of the reaction between glycerol and glyceric acid, the latter being formed as an intermediate product. The pyrnvine thus obtained crystallises in large, prismatic needles, or tables, which melt a t 82" and boil a t 241" under a pressure of 764 mm. C. H. B. Double Lactone of Metasaccharic Acid. By H. KILIANI (Bw., 20,2710-2716) .-The oxidation product of the lactorie of arabinose- carboxylic acid (Abstr., 1887, 465) dissolves readily in aqueous ammonia, and from the solution the diumide of metasaccharic acid, C,H,,O,N,, separates as a white powder, consisting of microscopic, tabular, monoclinic crystals, which become yellow a t 170" and melt a t 189-190" with complete decomposition.The compound has a neutral reaction, and when heated at 100" with potassium hydroxide Fields the potassium salt of metasaccharic acid as a colourless syrup ; this becomes crystalline on stirring, and in aqueous solution does not reduce Pehling's solution. On treatment with a cold solution of phenylhydrazine hydrochloride (1 part) and sodium acetate (1.5 pwt), in water (10 parts), the oxida- tion product yields the monophenylh ydrazide of the lactone of meta- snccharic acid, Cl2HI40,N2 ; this crystallises in colourless, microscopic males with 8 mol. H,O, dissolves readily in hot water and alcohol, and when rapidly heated becomes yellow at 185", and melts a t 130-192" with decomposition. If the mixture w i t h phenylhydrazine (which, to obtain the preceding compound is allowed to remain for 20 minutes for the crysta,llisxtion to take place) is a t once poured into boiling water, the diphenylhydj-azide of metasaccharic acid, CleH2206N,, separate8 after 10 to 15 minutes in yellowish-white, microscopic scales, which become yellow a t 210°, melt at 21 2-213" with decomposition, and are very sparingly soluble in boiling water aiid alcohol.The solution in concentrated sulphuric acid is coloured red or bluish-violet by ferric chloride. When the oxidation product (12 grams) is dissolved in water (300 grams), treated with 3 per cent.sodium amalgam (200 grams), and dilute sulphuric acid added gradually so that the solution never becomes alkaline, allowed to remain fire days with a farther 200 grams of sodium amalgam, then treated with sulphuric acid and alcohol to free the product from sodium sulpliate, and the mother-liquor evaporated, a syrup is obtained which still reduces alkaline copper solution, and from which mannite (2 grams) crystallises on standing over sulphuric acid. The strongly acid mother-liquor seems to consist of the lactone of a bibasic acid (? metasaccharic acid), a strongly acid syrup having similar properties being also obtained by continued heating of the oxidation product with water, or by repeated evapora- tion of its aqueous solution. The oxidation product of the lactone of nrabinose-carboxylic acid dissolves in 18, not, 8, parts of cold water (compare loc.cit.), and readily reduces alkaline copper solution. The aqueous solutions of its potassium and sodium salts, even in the absence of free alkali, become colonred intensely red on heating, or when allowed to evaporate spontaneously (Ber., 20, 343). The author, however, concludes, fromORGASIC CHEhlISTRP, 47 the preceding experiments, that the oxidation product is not the lactone of a ketonaldehydic acid, but is a double lactone of meta- CH(OH)*CH*O.CO - saccharic acid, I ), or which, on account of its peculiar constitution is very labile, and on treatment with alkalis even at the ordinary temperature undergoes molecular change, or perhaps reduction to an aldehyde -compound jielding mannite by the action of nascent hydrogen. Thiohydantoin.By R. ANDREASCH (Monatsh., 8, 407-424).- Loven has recently shown (Abstr., 1885, 241) that a methylene-group situated between a carbonyl-group and a sulphur-atom possesses similar properties to the methylene-group in ethyl malonate and acetoacetate. With the object of ascertaining whether this is the case in hydanto'in, the author has prepared the disilver-derivative, and from that the dimethyl-compound, Disilz~e~-tJ~iohydan.to'i?z, Ag2C3N,H2S0, was obtained by adding a warm aqueous solution of thiohydantoTn to ammoniacal silver nitrate. It forms a white, granular substance, sparingly soluble in nitric acid, insoluble in ammonia. I t blackens when exposed to light. When treated with methyl iodide, the silver compound yields P-dimethyithio- hydantozn, XH C<,,.,,>.This substance is easily soluble in water, sparingly in cold alcohol, crrstallises in hexagonal scales, melts at 114", and decomposes at a slightly higher temperature. When oxidised in hydrochloric solution by barium chlorate, carbonic anhy- dride and mei-captan are evolved, and the residue is found to contain carbamide, and a mixture of barium salts which cannot be separated, but one of which seems to be barium methylsulphonate. When heated wit,h barium hydroxide, the hydantoi'n yields cyanamide and some sulphur compounds which could not be isolated. Witlh the aim of determining the constitution of tlhe above com- pound, the author atternpted to prepare the two isomeric dimethyl- hydanto'ins in other ways.a-Dimethylthiohydan.tozn, W. P. W. S*CMe2 may be prepared by heating together dimethylthiocarbamide and chlor- acetic acid in aqueous solutioi~. It is easily soluble in water, alcohol, ether, and carbon bisulphide, crystallises in long, thin, colourless prisms, melts at 71", and boils a t a rather higher temperature. It volatilises slowly a t ordiuary temperatures. It bas an odour some- what resembling that of nicotine. When heated with aqueous alkalis, it yields thioglycollic acid. The isonitl.oso-derivative, C,H,N,SO,, yields yellowish scales melting at 220". Imidocarbnminethioisobzl,tyri,: anhydride, C5N2H8S0, was prepared by heating together thiocarb- amide and x-bromisobutyric acid. It crystallises in plates, is easily48 ABSTRACTS OF CHEMEIIICAL PAPERS.soluble in alcohol and boiling water, sparingly in cold water, and melts at 242". When oxidised with nitric acid, this substance yields carbamide and sdphoisohufyric mid, SO,EI*C,H,~COOH, which forms a barium salt, BaC,H,SO, + 4H,O, crystallising in needles, easily Roluble in water, insoluble in alcohol. The sodium salt, Na,C,H,SO, + &H20, forms glistening needles eiisily soluble in water, insoluble in alcohol. The same sulpho-acid is obtained by the action of chloro- sulphonic acid on isobutyric acid. The action of ammonium sulphite on a-bromisobutyric acid produces, however, an isomeric sulpho-acid, yielding an easily soIuble barium salt, BaC4H,S05 + 2H20, cryeta1- lising in needles. It is thus clear that this imido-anhydride is not, identical with the /3dimethglthiohydantoYn, as the author had anticipated.As it was possible that in the formation of the imido-anhydride a transformation from the iso- to the normal butvric series had occurred, the author S*CHEt prepared imidocarbaminethiobu~~,yric anhydride, NH : C<NH.co >, by the action of a-bromobutyric acid on thiocarbamide. This crystal- liRes in short, thick needles, easily soluhle in boiling water, and melts at 200". It is not identical with the compound obtained from iso- butyric acid. The constitution of the latter is therefore still doubtful, but its formation may perhaps be due to the action of thiocarbamide on the methacrylic acid formed by the elimination of hydrogen bromide from the bromisobutyric acid, CH,: CMe*COOH + CS(NH2)2 = CHMe<Co.2GH>C 1 NH + H20.The consitution of the ,&compound would then be correctly expressed by the formula given above. Thiohydantok when treated with benzaldehpde yields amidinethio- cinnanzic ( b e n z ~ l i d e n e t h i o h y d n ~ ~ o ~ c ) acid, NH C(NH,)(COOH) CHPh ; this forms white, microscopic needles, insoluble in water, soluble in alcohol. Several salts of thioliydantoin are described. The subphate, (C3H,N,S0)2,H2S04, forms plates soluble in water ; the nitrate, flat needles or prisms ; the ozalate, C,H4N2S0,C2H,04 + H20, prisms ; the pzcrate yellow, microscopic needles. Thiohydantoin is best prepared as follows : 50 grams of thiocarb- amide is dissolved in + litre water, and 62 grams of chloracetic acid dissolved in 50 C.C.of water added. The whole is heated a t 80-90" until reaction has ceased, and when cold it is gradually neutralised with soda, care being taken never to let the solution become alkaline. Orthothioxen and Orthothiophendicarboxylic Acid. By W. GR~NEWALD (Ber., 20, 8585-2587).-0rthothioxen (Paal, Abstr., 1887, 1101) is prepared by distilling an intimate mixture of 10 grams of p-methyllerulinic acid and 17 grams of phosphorus trisulphide in a, capacious retort. 250 gi*ams of methyllevulinic acid yielded 150 grams of pure product. It is a colourless, strongly refractive oil, h%ving an odour of petroleum ; it boils a t 136-137" (corr.). Sp. gr. at 21" = 0.9938. When treated with 1 per cent. solution of potassiizm per- manganate, a monocarboxylic acid only is formed ; this melts a t 134.5".CH S Similar a,cids seem to be produced with other aldehydes. L. T. T.ORGANIC CHEMISTRY. 49 Ort7~othiophendicarboxylic acid, C4SH,(COOH)2, is obtained by the action of 1 per cent. permanganate solution on the monocarboxylic acid ; the product is steam-distilled to remove unchanged mono- carboxylic acid. It crystallises in long needles which do not melt a t 860", but decompose at a higher temperature. When heated with rcsorcinol at 200", a product is obtained which dissolves in strong aqueous alkali with dark-red coloration ; the colour changes to yellow on diluting with water; the solution then shows a yellowish-green fluorescence. The silver salt forms white flakes irisoluble in water ; the barium saZt separates in colourless crystals, readily soluble in hot water.The dimethyl salt crptallises from alcohol in colourless plates melting at 595". N. H. M. Action of Carbonic Anhydride on Aromatic Amines. By A. DITTE (Compt. rend., 105, 612--614).-When an aniline salt is mixed with an aqueous solution of a normal or hydrogen carbonate, carbonic anhydride is given off, and aniline separates in the free state, no aniline carbonate being formed. Carbonic anhydride is not soluble in aniline, and does not combine with i t under ordinary pressure even at -8', the temperature at which aniline solidifies. I€, however, dry carbonic anhydride and aniline are compressed in a Cailletet's apparatus, the auiline dissolves the carbonic anhydride, jncreasiug to about twice its original volume, and a limpid layer of the liquefied gas swims on the surface of the solution and volatilises at 15" under a pressure of 40 atmos.If the compressed liquid is cooled to 8-10", it crystallises in transparent, white needles, and when the aniline and carbonic anhydride are in equal molecular pro- portions, solidification is complete. When the carbonic anhydride is in excess, it forms a, layer above the crystals. When aniline is in excess, it does not at once dissolve the carbonic anhydride, and the fwo liquids form distinct layers, but on gentle agitation the carbonic anhydride is dissolved, and crystallisation takes place a t 8". It is evident that carbonic anhydride and aniline combine in equal molecu- lar proportions to form a compound which crystallises a t 8", and is liquid or remains in superfusion at loo, and decomposes when the pressure is released.The tension of dissociation a t different tempe- ratures is as follows :- Temperature . . . . . . . . . . 0" 2" 5" 7" Pressure in atmos. . . . . 6 9 17 28 Orthotoluidiiie behaves in a precisely similar manner, and the com- pound crystallises in brilliant, white needles. The behaviour of meta- xylidene is similar in that the two liquids mix, but no crjstals form even a t -12". Pyridine and its homoIogues show no tendency to combine with carbonic anhydride ; the two liquids do not mix. C. H. B. Benzylidene Compounds. By L. ROHLER (,4nrzaZen, 241, 358- 362) .-An alcoholic solution of berizylidenepara toluidine is converted into benzylparatoluidine by the action of sodium amalgain. The VOL.LIV. B50 ABSTRACTS OF CHEMICAL PAPEM. base distils at 33.2-313", and solidifies in the course of several weeks. it is freely soluble in alcohol and ether. The hydrochloride is soluble in alcohol and in hot benzene, and the sulphate is soluble in water. The nitroso-compound melts a t 53". Benxyl-~-na~~hthylamime cr;gstallises in prisms, and melts a t 68". The nitroso-derivative forms yellow needles, soluble in alcohol, ether, benzene, and light petroleum. Benzy Zarnidodimethy Zaniline, prepared from the condensation-product of benzaldehyde and smidodimethylaniline, melts st 48", and distils without decomposition. The nitrosnnzins is deposited from alcohol in yellow needles. It melts a t 111-112°. It melts a t 127-128" with decomposition. w. c. w. Reduction Products of Bensylidene Compounds.By 0. FISCHER (AnnaZen, 241, 328-331).-The author has previously pointed out (Abstr., 1886, 546) that 3 per cent. sodium amalgam reduces a solution of hydrobenzamide in absolute alcohol to dibenzyl- amine and monobenzylamine ; ammonia and toluene are always liberated during the reaction. Under similar treatment, benzylidene- aniline is converted into benzylsniline. The salt which is deposited when nit,rosobenzyIa,niline is treated with a,lcoholic hydrogen chloride is a mixture of benzylaniline hydro- chloride and benzylidene aniline. w. c. w. Hydroxybenzyliden 8 Compounds. By 0. EM MERICH (AnmaZen, 241, 343-358) .-Orthohydroxy benzy Zandine, HO*C,H,*CH,-NHPh, is obtained by the action of sodium amalgam on a solution of hydroxy- benzylideneaniline in absolute alcohol.It melts at 106", and is soluble in alcohol and ether. The sulphate and hydrochloride are freely soluble in water. The platinochloride forms reddish-yellow needles, melting a t 184" with decomposition. A tetranitro-derivative, C,H9NO(X02),, is formed when the base is treated with a mixture of sulphuric and nitric acids. It melts a t 66" with decomposition, and is soluble in alcohol, acetic acid, and light petroleum. Orthohydroxz~ber~zyl~aratoZuid~ne, HO.C,H,.CH,.NH.CsH,Me, ob- tained by the reduction of the hydroxybenzylideneparatoluidine, crystallises in white plates and needles, and melts at 116". It is soluble in alcohol and ether. The sulphate and hydrochloride dissolve freely in water. The platinochloride crystallises in needles. The tetranitro-derivative formR yellow needles, soluble in alcohol, benzene, and acetic acid.By the action of methyl iodide, the base is converted into ortl~omethoellben~uy~aratoluidine, It melts a t 168". OMe.CsH4*CH,-NH*C6H4Me, a crystalline compound melting at 110", and soluble in alcohol, ether, hnd benzene. Orthodih ydroxydibenzylarnine is prepared by the action of sodium amalgam on an alcoholic solution of hydrosalicylamide. It crystal- ]ifies in needles, melts a t 170°, and dissolves freely in ether, alcohol, benzene, and light petroleum. The sulphate, nitrate, and hydro-ORGANIC CHEMISTRY. 51 chloride are soluble in water. needles, and is soluble in water. yields on reduction orthoh2/dro;eybe.1~zyl-p-n~ph~h~lam~t~e, The platinochloride crystallises in The condensation compound of salicylaldehgde and p-naphthylemine n crystalline substance melting at 147".It is soluble in alcohol, ether, benzene, and light petroleum. The alcoholic solution exhi bits a reddish-violet fluorescence. The sulphate is liquid, and the platino- chloride crystallises with difficulty. Orthohydrozy benayl-p-n,a~hlhylnitrosamin,e melts at 165" with decom- position. On exposure to the air, the compound decomposes spon- taneously at the ordinary temperature. It is soluble in alcohol and ether. Orthomethoxybenzyl-~-naphthylain,ine crystallises in needles, melts at 92", and dissolves freely in alcohol and ether. Parahydroaybenxy laniline, prepared from parahydroxybenzylidene- aniline, is soluble in alcohol and ether. It melts a t 208", and forms a crystalline platinochloride.Pal.ahydroxybenzyZtol1~idine melts at 186". Parahydroxybenzyl-P- nnphthylamine melts: at 117". The sulphate is soluble in alcohol, but almost insoluble in water. The nitrosamine melts at 142", and dis- solves in alcohol and ether. It is unstable. w. c. w. Anisylamines. By 0. J. STEINHART (AnubaZen, 241, 332-343).- A solution of anishydramide in absolute alcohol is converted into a mixture of mono- and di-anisylamine by the action of sodium amalgam a t the ordinary temperature. Dianis?ylanaine, NH(CH2.C6H,*OMe)2, forms white, needle-shapsd crystals soluble in alcohol and ether, It melts a t 34", and decomposes on distillation. The hydrochloride is soluble i n alcohol, and crystallises in fiat prisms. It melts at 243".The platinochloride is crystalline but unstable. The nitroso-derivative, (OMe-C,H,-CH,),N*NO, crystallises in needles, and melts at 80". Anisyk amine is a colourless liquid boiling at 220-223". It, is miscible with alcohol, ether, and water, and it absorbs carbonic anhydride from the air. It can be separated from dianisylamine by its volatility in a current of st,eam. The hydrochloride forms white plates which are freely soluble in water, and melt at 230". The platinochloride crystal- lises in pale-yellow, glistening needles. An i s y 1 nnil ine, MeO*C6H4*C H,*NH P h , prepared from a nish ydrani lid e, crystallises in prisms, and dissolves freely in the usual solvents. It melts at 64*5", and forms a crystalline hydrochloride, sulphate, and platinochloride. The nitroso-derivative melts a t 104". It crystallises in prisms, and is soluble in alcohol.Anish ydroparatoluide, OM&C6H4-CH NC6RbMe, forms whiLe needles, and melts a t 92". Anisyl~aratoluidilze, OMe.C6H4*CH2*NH2*CsH4Me, forms white prisms, melting a t 68". It is soluble in all the usual solvents with the exception of water. The hydrochloride and platino- chloride are crystalline, but the salts have a tendency to decom- pose when their solutions are evaporated. The rdrosamine melts at 108". Anisaldehyde and orthotoluidine condense, forming anishydrortho- It melts at 210". e 252 ABSTRACTS OF CHEMICAL PAPERS. toluide, which yields orthotoluylanisylamine on reduction. The base melts a t 55". Anis y Zid enenap hi! h y lam ine ( /3) , OMe C6H4* C H N C 1oH7, crys t alli ses in plates, and melts at 98".Anisyl-P-naphthyZa??/,ine is soluble in alcohol, benzene, and in light petroleum. It melts at 101". The salts are sparingly soluble in water, and are rather unstable. The nitros- amine melts at 133", and crystallises in plates. AnisylidenedimethyZ- paraphenylenediamhze forms greenish-yellow needles. It melts at 148", and yields on rednction anisyldimethylpcrr~pheny lenediamine, OMc*CsH4.CH,*NH.CsH4.~Me~. This base crystallises in plates, and melts a t 104". The alcoholic solution decomposes on exposure to the The nitrosamine is an oily liquid. air, and the nitroso-compound is unstable. w. c. w. Salts of Picramic Acid. By A. SMOLKA (Monatsh., 8, 391-398). -The salts of this acid having heen but little studied, the nut,hor has prepared and examined a number of them. Tn some cases they were obtained by the direct action of picramie acid on the metallic carbon- ate, in others by double decomposition.The following table shows the results obtained :-- Formula of salt. Description. Dark red crystals Dark reddish- brown wales Yellow, microsco- pic needles Greenish - yellow needles Scarlet, microaco- pic crystals Dull yellow, mi- croscopic needle Small, reddiuh- brown needles Dark &eel-green needles Greenish- yellow, amorphous powder amorphous powder Dark olive-green, Ratio of solubility in water. I. Boiling. 1 :4Q% at 15 -5' 1 : 19.9 ,, 17 '0 1 : 5890 ,, 23 '0 1 : 1215 ,, 23 *O 1:21010 ,, 17.5 1?3172 ,, 18.0 1 :2632 ,, 20.5 1 : 97 *5 ,, 19 -0 insoluble insoluble 11. Cold -- freely freely 1 : 1842 I : 318 1: 12481 1 : 1151 1 : 1494 freely I : 3292 I : 3538 Tempera- ture of decompo- sition.-- abont 150' 140 140-150° 140° 120 140-145O 140-150 Moo 140 1 a-1 45' If the salt is heated slowly, the decomposition takes place quietly, but if rapidly, explosions occur, especially with the sodium and lead salts. The aqueous solutions vary in colonr from pale orange to dark blood-red. L. T. T.ORGANIC CHEMISTRY. 53 Chlorine and Bromine-derivatives of Citraconanil. By T. MORAWSICI and J. KLAUDY (Monatsh., 8, 399-406) .-Citraconpara- chloranil, C5H402 : N-C6H,C1, is formed (together with chloranilines) when a stream of chlorine is passed into water in which finely-divided citraconanil is suspended. It crystallises in white, glistening needles, soluble in alcohol and melting a t 114,5".With care i t may be sub- limed in long, glass-like needles. When heated with ammonia, it yields parachloraniline and citraconic acid, showing the correctness of the above formula. When bromine acts on citraconil, bronzocitraconprLrabrornani1, C,H,BrO, : N*CsHpBr, is formed. This crystallises in white, shining needles, soluble in alcohol and melting at 178". It can be sublimed, b u t decomposes if heated rapidly. When heated with ammonia, parabromaniline is formed, together with hydrogen bromide, much resinous matter, and an acid of the formiila C7H,BrOa. This acid yields a silver salt, AgzC7€3,B.rO4, crystallising in prisms, and a lead salt, PbC7H7Br04, forming microscopic crystals. It appears, therefore, that the original bromo-derivative contained one bromine-atom in the citraconic nucleus, and that when heated with ammonia this nucleus is converted into a higher brominated homologue of the citraconic series, together with other bye-products. When only enough bromine is employed for the formation of eitraconparabromanil, white, crystalline needles melting at about 11 8" were obtained, but this compound has not yet been obtained in a pure state.L. T. T. Action of Phenylhydrazine on E thy1 Chloracetoacetate. By G. RENDER (Ber., 20, 2747--2752).--Ethyl chloracetoacetate reacts with phenylhydrazine in ethereal solution to form a compound, C12H14N202 ; it is probable that a hydrazine-derivative, NHPh*N CMeCHCl-COOEt, is at first formed, which is subsequently converted into a compound, NPli : N*CHMe*CHCl*COOEt, and finally by abstraction of the elements of hydrogen chloride into NPh : N-CMe : CH-COOEt, or ethy lic P-phenylazocrotonate. This substance crys tallises in long, red needles, meltling at 50*5", very soluble in alcohol ; on saponification, it yields a potassium salt, NPh N*CMe: CH-COOK, which forms reddish-yellow scales, very soluble in water, insoluble in alcohol.The salt on acidification yields the corresponding anhydride as a brownish-yellow powder, whose purification presents considerable difficulty. Ethylic /3-phenylazocrotonate when reduced yields phenyl. rnethylpyrazolone and its first oxidation product or its bis-derivn- tive, together with a substance not further examined. The bis-deri- vative yields with bromine a compound, C2,€€,,NaO,Br, which crystal- lises in colourless needles, melting a t 217" with decomposition.a-Naphthylamine with ethylic chloracetoacetate yields a compound, C,,J316N02C1 ; this crystallises in colourless prisms, meltiiig at 75" ; its formation is due to a change analogous to the first of the reactions given above in the case of phenylhydrazine. V. H. V.54 ABSTRACTS OF CHEMICAL PAPERS. Isomeric Phthalophenylhydrasfnes. By G. PELLIZARI (Gaxnetta, 17, 278--285).-The author has previously described two isomeric phthalyl-derivatives of phenylhydraxine obtained by the action of this base on phthalimide and phthalic anhydride respectively (Abstr., 1886, 125). To the former, melting at 179", the constitution NHPh*N <Co>C6HH", to the latter, melting a t 210°, the constitution GO NPh-CO <NH-CO>CGHa was assigned.If these formule are correct, a methyl-derivative of the former, or anilophthalimide, on separation of the phthalyl grouping, should yield a symmetrical methylphenyl- hydrazine, NPhMe*NH2, that of the latter, or phthalophenylhydrazine, the symmetrical derivative, NHPh-NHMe. Phthalophenylhydrazine, heated with methyl iodide and alcohol, yields a methyl-derivative, crystallising in long, yellowish-white prisms, which melt at 125" without decomposition ; this is decomposed by concentrated hydro- chloric acid, yielding methylphen ylhydraeine, NHPh-NHMe. The constitution of the isomeride has previously been proved by Eotte, but in answer to his criticisms (Abstr., 1887, 770) it is shown that phthalic anhydride and phenylhydrazine, reacting in molecular pro- portions, give either anilophthalimide or phthalophenylhydraxine, according to the temperature ; at ordinary t'emperatures, phenyl- hydrazine-phthalic acid is at first formed, which on subsequent heat.- ing yields ariilophthalimide ; if, however, the reaction proceeds at 163", the melting point of the acid, a t which temperature it is unstable, phthalophenylhydrazine is formed in the greater proportion.Dyes from Aniline Chromates. By S . GRAWITZ (Compt. rend., Azophenine. By 0. N. WITT (Bey., 20, 2659-2660).-A yply to Fischer and Hepp (Abstr., 1887, 1105), in which the author poiiits out that the constitutional formula proposed by them is inadmissible, since azoplienine does not form an acetyl-derivative when heated with acetic anhydride, and yields a considerable quantity of aniline on treatment with tin and hydrochloric acid.On these grounds, the author adheres to his published views on the constitution of azo- By P. BARBIER and L. VIGNON (Compt. rend., 105, 670-672) .-Paranitrosodimethylaniline has no action on aniline at the ordinary temperature in presence of water, glacial acetic acid, or an excess of aniline, but a t 80" there is an extremely violent reaction. If equal molecular proportions of aniline and paranitrosodimethyl- aniline are dissolved in eight times their weight of ethyl alcohol of 92", and heated on a water-bath, a reaction takes place a t 80", with con- siderable development of heat, and is complete in about three hours. When the liquid is cooled, a solid separates, which is washed with dilute hydrochloric acid, and then crystallised from boiling toluene. I'etranaethyZlliumido-azobe.nzene is thus obtained in brilliant, brown, V.H. V. 105, 576--577).-A question of priority and patent right. phenine (Abstr., 1887, 821). w. P. w. Substituted Safranines.OHBAKIC CHEMISTRY. 35 crystalline plates, which melt imperfectly a t 218-220" without vola- tilisation, and when reduced with zinc and salphuric acid, yield dimethylparaphenylenediamine in almost theoretical quantity. It. is almost insoluble in water, and only slightly soluble in dilute acids, but dissolves in concentrated acids forming deep red solutions. The alcoholic liquid separated from the tetramethpldiamido-azo- hneene has a deep, violet-red colour, and when evaporated leaves a viscid residue, which dissolves almost completely in water.When this solution is mixed with sodium carbonate, a precipitate is formed, and if the filtrate is mixed with sodium chloride, dimethylphenosafra- nine Beparates, and is purified by repeating the treatment with sodium carbonate and chloride. The equation representing the reaction is- ZNHzPh + ~C~EIANO*NM~~,HC~ = ClsHZON, + CWHIgNdCl + 3H20 + 2HC1. C. H. B. Action of Acid Amides on Bromacetophenones. By M. LEWY (Ber., 20, 2576-2580) .-When bromacetophenone is heated with acetamide (2 parts) a t l't0-130", for one hour, a base, C,,H,NO, is ob- tained. This forms long, colourless needles, readily soluble in alcohol and ether; it melts a t 45", and boils a t 241-242'; it has slightly basic properties.The hydrochloride, CloH9N0,HCl, crystallises in small needles ; when treated with an excess of hydrogen chloride, it yields a heavy, fuming oil, possibly an acid salt. The platino- k&m&, (CloN,NO),,H,PtC16 + 2Hz0, separates in dense, yellow flakes, consisting of' orange-coloured needles, which melt a t 130-140 with decomposition. The subhate forms white, lustrous plates, which decompose in contact with water. The picrate crystallises in lemon- coloured needles, melting at 133-134'. The formamide base, CgH,NO, prepared by heating bromaceto- phenone with formamide, is a thick, colourless oil, which becomes yellow when exposed to air ; it solidifies when cooled with a freezing mixture, melts at 6", and boils at 220-222'. The hydrochZoride melts at 80".The pZutinochZoride (with 2 mols. HzO) crystallises in slender, yellow needles. The hermawtide base, CIBHIINO, is prepared by heating bromacetophenone and benzamide a t 140-150" ; the product is extracted several times with boiling water, and the residue fractionally distilled. It crystallises from alcohol in large, colourless plates, readily soluble in the usual solvents, melts a t 102-103", and boils a t 338-340". The hydrochloride crystallises in slender, matted needles ; it is slowly decomposed by boiling water. N. H. hL Isonitroso-compounds : Isobenzaldoxime. By E. BECKMANN (Ber., 20, 2766-2768) .-When benzaldoxime is mixed with sulphuric acid in presence of ice, a solid, white substance separates out under certain conditions ; sometimes an oil is obtained.The former, pro- bably a poly rneride of benzaldoxime, crystallises in glistening needles, melting at 128-1.30"; it is distinguishable from benzamide by its crystalline form. The oil is benzaldehyde, produced by the re-forma-56 ABSTRACTS OF CHEMICAL PAPERS. tion of the oxime and its subsequent decomposition by the acid present. V. H. V. Condensation of Cinnamic Acid with Gallic Acid. By E. JACOBSEN and P. JULIUS (Bey., 20, 2,588-25,89).--St?lrogaZZo7, CI6Hl0O5, is prepared by heating cinnamic acid (10 parts), gallic acid (12 parts), and sulphuric acid (150 parts) at 45-55', for two to three hours. The product is poured into water, filtered, and the precipitate washed with slightly acidified boiling water. It crystallises in bright- yellow, microscopic needles, which do not melt a t 350"; it is very sparingly soluble, except in boiling alcohol, aniline, and glacial acetic acid, and sublimes when carefully heated in large, yellow, lustrous needles. Alkalis dissolve it with green colour, which changes to blue, and then red, when the solution is heated.The solution in sulphuric acid is yellowish-red. When oxidised with dilute nitric acid, it yields a large amount of phthalic acid. The triacetyl-cleri~nfive, C22H1606, crystallises in pale-yellow needles. With mordants, styrogallol yields shades similar to those obtained with nitroalizarin. N. H. M. Paradiphenoldicarboxylic: Acid. By R,. SCHMITT and C. KRETZSCHMAR (Bey., 2 0, 2 703-2 704) .-Pu~*adiphenoZdicarboayl~c acid, COOH-C6H,( OH).C6H,( OH)*COOH, is obtained when sodium para- diphenol is heated in an autoclave with liquid carbonic anhydride at 200" for nine hours, and the resulting product is treated with an acid.It crystallises in small, microscopic needles, melts at 131" with the evolution of carbonic anhydride, is not volatile with steam, has a slightly bitter taste, and is readily soluble in ethyl and methyl alcohol and in ether, sparingly soluble in water (100 C.C. of water at 15" dis- solving 0*0052 gram of the acid), and insoluble in benzene and chloro- form. Suspended in water, it is coloured bluish-violet with ferric chloride, the colour changing to a dull brown on heating, whilst the sodium salt when similarly treated yields a deep blue solution, from which indigo-blue flocks separate. w.P. nT. Orthamidotriphenylmethane. By 0. FISCHER and A. FRANKE L (Annalen, 241, 362-368) .--The preparation of diphenylquinolyl- methane has been previously described by the authors (Abstr., 1886, 561). The sulphate and picrate are precipitated on the addition of sulphuric or picric acid to alcoholic solutions of the base. The nitro- derivative melts a t 213" with decomposition, and the amido-compound on oxidation forms a riolet-coloured solution. Triphenylmethaneorthocarboxy lic acid is prepared by slowly adding a solution of the hydrochloride of the diazo-compound of amidotri- phenvlmethane to a solution of potassium cyanide and copper sulphate a t 9d". The crude product is sa,ponified with alcoholic potash, and the acid precipitated from the aqueous solution of the potassium salt by hydrocliloric acid.Alcohol, ether, acetic acid, and benzene dis- solve the acid freely. It melts a t 162" and volatilises without decom- position ; i t is identical with the acid Baeyer (Abstr., 1880, 650) obtained f r o n phthalophenone. Orthoh ydrozytri~he?zylmet}~ane is formed by passing air through aORGANIC CHENISTRY. 57 solution of dia zoamidotrip henylmet hane sulp hate, and boiling the product in a current of carbonic anhydride. It is soluble in alcohol and ether, and melts a t 118". The acetic derivative of amidotriphenylmethane melts a t 168-169", and is freely soluble in alcohol, benzene, and acetic acid. The thio- carbamide melts a t 12fjo, and dissolves readily in ether, carbon bisul- phide, and hot alcohol. w. c. w. Two Dihydroxynaphthalenes. By A.EMMERT (Anna.len, 241, 368-373) .-$-Naphthol yields t w o sdplionic acids on treatment with sulphuric acid, and each acid is converted into a dihydroxynaphtha- lene by fusion with potmh. ~-~-DihydroxynapJ~tl~alene melts a t 615-216", and dissolves freely in alcohol and et,her. Ferric chloride produces a yellowish-white precipitate. A t 120" alcoholic potash and ethyl iodide coiivert the dihydroxynaphthalene into an ethyl ether, Cl0H6( OEt,). It forms silky plates and melts at 162". The diacetate, C,oHt-I,(OAc)2, melts a t 175". P-a- Dihydroxynaphthalene is soluble in alcohol, ether, benzene, and water. It melfs a t 1 7 8 O , and gives a blue precipitate with ferric chloride. The dietliyl ether crystallises in prisms, melting at, 67", and the diacetate forms rhombic plates and melts at 108".W. C. W. Derivatives of Di-p-naphthylamine. By C. RIS (Ber., 20, 261 8-2628). -Crude di-/3-nap hthylamine is purified by distillation and crystallisation from benzene ; it melts at about 471". Met7&yldi-P-naphlh?/Inmine, NMe( C1,H7)2, is prepared by heating di- naphthylamine and methyl iodide (equal molecular weights) for five hours at 150", and ci-ystallises from alcohol in nearly colourless needles melting a t 139-140". It dissolves rather readily in warm alcohol, glacial acetic acid, benzene, and ether, and is almost insoluble in light petroleum. The alcoholic solution shows a bluish-violet fluorescence. It is insoluble in dilute mineral acids; the hydrochZoride forms slender, lustrous crystals, which decompose quickly in presence of water.The solution in strong sulphuric acid is yellow, and acquires an intense brown colour on addition of a trace of a nitrite or nitrate. Ethyldi-/3-naphthyZamine, NEt(C&€,),, crystallises in almost colour- less prisms melting a t 231"; it resembles the methyl compound in solubility ; the hydi-och Zoride is a white, crystalline powder. H e t h y l di-~-)taphth!iZcarba;lriate, N( CloH,),.COOMe, is obtained by heating di-/3-naphthylamine and methyl chloroformate (equal weights) at 150-160" for two and a half hours. It crystallises from alcohol in slender, white needles, melting at 113-114", dissolves readily in alcohol, ether, and benzene. It crystallises from benzene with $ mol. CcH6. Tetrabromodi-p-naph tJyEamine, C20H,,Br,N, is prepared by the action of bromine (4 mols.) on a well-cooled solution of di-p-naphthylamine in glacial acetic acid.It crystallises in long, white, matted needles, which melt a t 245-2246". It dissolves rather readily in hot benzene and cumene, very sparingly in ether, light petroleum, and alcohol. It distils almost without decomposition.58 ABSTRACTS OF CHEMICAL PAPERS. It is not attacked by boiling concentrated aqueous potash ; bromine does not act on it. Octobromodi-P-?taphthyZanzine, CzoH,Br,N, is formed when /3-dinaph- thylamine, as dust, is added to an excess of bromine in presence of alnminium bromide. The product is stirred well, and the yellow pre- cipit'ate, after being treated with alkali and with boiling hydrochloric acid to remove adhering bromine and aluminium, is crystallised from cumene.It forms slender, white needles, which melt at about 300", and dissolve readily in boiling nitrobenzene, less in boiling cumene ; in other solvents it is sparingly or not at all soluble. is prepared by adding the calculated amount of sodium nitrite dissolved in a little water to it mixture of alcohol and sulphuric acid containing di-P-naphthylamine in the form of dust. It crystallises from benzene in groups of white needles, melting at 139-lPO", sparingly soluble in alcohol, readily in benzene. Dinit.l.odi-P-naphthy~amin.e, Cz0H,3N(N0z)2, is formed when strong nitric: acid is slowly added to a cooled solution of the amine in glacial acetic acid; it separates after some time as a yellow powder. It crystallises in yellowish-red needles, melting at 224-225", readily soluble in boiling cumene, less soluble in benzene, and almost in- soluble in alcohol and ether.T~tran.itrorZi-p-na~hthz/Z~zmine, CzOHllN(N02)P, is obtained by gradu- ally adding nitric acid (3 pn.rts) mixed with glacial acetic acid to a solution of dinaphthylamine (1 part), in glacial acetic acid. It crystallises from nitrobenzene in grains, which melt at 285-286", and detonate when more strongly heated. It is sparingly or not at all soluble in the ordinal-y solvents, readily soluble in boiling nitro- benzene. Hexanitrodi-P-naphthylamine, CzoH9N( NOz),, prepared by heating the finely-powdered amine with fuming nitric acid, could not be ob- tained in crystals. It dissolves readily in alcohol, less in glacial acetic acid, and is almost insoluble in ether, benzene, cumene, and nitrobenzene.Alkaline carbouahes dissolve it readily. When mixed with excess of copper oxide, it decomposes with explosive violence, and was therefore not analysed. The potassium and ba&m salts were aualysed ; they are both amorphous. Benzoylortko?iitrodi-P-n~phthylscmine, C2THlsNO*N02, is prepared by adding a mixture of fuming nitric and sulphuric acids to a solution of benzoyldi-p-naphthylamine in cold glacial acetic acid, and subse- quently heating the whole at 50-60". It crystallises from benzene in well-formed, yellow, transparent crystals (with 1 mol. C6H6), melt- ing at 95". Crystallised from alcohol it melts at 168". It dissolves readily in warm benzene, less in alcohol. Benzenylriap?~thyle7Leanzidine, N< CPh >NGlaH,, is obtained by re- GoH, ducing benzoylnitrodinaphthylamine dissolved in glacial acetic acid with excess of tin and hydrochloric acid.It crystallises from benzene in transparent, slender needles (with 1 mol. c,H6) melting at 113- 114" ; when crystallised from other solvents it melts at 163". It sub- limes when carefully heated in small, colourless plates, and distils Nitrosodi-P-naphthyZn?nine, M0.N ( C1,ORGANIC CHEMISTRY. 59 with slight decomposition. I t is readily soluble. The hydrochloride forms slender, matted needles which decompose in contact with water. Naphthaphenaaine. By P. BRUNNER and 0. N. WITT (Ber., 20, 2660-2663). - Naphthaphenasinesulplzowic acid is obtained when naphthaphenazine is heated with 10 times its weight of 35 per cent.fuming sulphuric acid at 100" for 12 hours. It crystallises in orange- red needles, melts above 290°, and is soluble in water and alcohol. In concentrated sulphuric acid it dissolvss with a deep orange-brown colour, which becomes orange-yellow on dilution. The sodium salt,, C16H,N2*SOsNa + 2H,O, was prepared. On fusion with potassium hydroxide, a ewrhodol is obtained which differs from that previously described (Abstr., 1887, 153), since it dissolves in hydrochloric acid with a red colour, and in concentrated sulphuric acid with A dark- green colour changing to red on dilution. A similar compound has been prepared by diasotising the eurhodine formed by the reduction of nitronap h t haphenazin e. Cy artowph thaph enazine, C16H9N2* CN, is obtained when sodium naphthaphenazinesulphonate is distilled with potassium cyanide or dry potassium ferricyanide.Crystallised from cumene, it melts at 236-5237', and dissolves in concentrated snlphuric acid with a cherrj- red colour, which changes through orange to yellow on dilution. If heated with hydrochloric acid under pressure, it is decomposed into naphthaphenazine and formic acid, but when heated with alcoholic potash at 220-250" it is partially converted into naphthaphenaxine- carboxylic acid. This is sparingly soluble in the ordinary solvents, melts above 360", and dissolves in concentrated sulphuric acid with a deep-red colour, changing to yellow on dilution. The potassium salt crystallises in white needles and is sparingly soluble in water.N. H. M. w. P. w. Naphtholcarboxylic Acids. By R. SCHMITT and E. BURKARD (Ber., 20, 2699-2704) .-a-NnpIit?~olcarbo~l~c acid (m. p. 187") can be prepared by heating sodium a-naphthol with liquid carbonic anhy- dride in an autoclave at 130°, and is a comparatively stable compound (compare Abstr., 1887, 732), since it is only partially decomposed by prolonged boiling with water, in which it is very sparingly soluble. The aqueous solution is coloured greenish-blue by ferric chloride. The sodiurn salt, with 3 mols. HzO, crystallises in large, thin, nacreous scales; the ammoniurri salt forms long needles; the calcium and barium salts crystalhe in long needles. The methyl salt, OH*CloH6*COOMe, melts at 78", the ethyl salt at 49', and the phenyl salt at 96". The acetgl-derivative, OAc.Cl~~6*COOH, melts at 158" ; the bromo-deriva- tive, OH*CloH&r*COOH, melts at 238" ; the nitro-derivative, melts at 202", and yields P-nitro-a-naphthol when 'heated with lime ; the amido-derivative melts above 200", and its acetyl-compound at 183".paraxobenzenesulphonic acid-a-naphtholcarboxylic acid, OH.C1&L,( NO,) .C 0 OH, Metadiazonaphtholcarboxylic acid, OH*CloH5<, CO@ N>, and S03H*C6H4*N2* C~oH~(OE€) *C 0 OH,60 ABSTRACTS OF CHEMICAL PAPERS. were also obtained, and the latter on reduction with zinc and hydrochloric acid yields an amido-a-naphtholcarboxylic acid which crystallises in colourless, prismatic needles, is very sparingly soluble in water, and melts above 200", but differs from the amido-derivative just described since its acet y I-compound melts at 195O.When sodium P-naphthol is similarly heated with liquid carbonic anhydride in an autoclave at 130", /I-naphtholcarboxylic acid is ob- tained, and is sepnrahed by treating the product with ammonium carbonate and precipitating with hydrochloric acid. This acid readily decomposes on heating, and shows all the properties of Kauffmann's acid (Abstr., 7 882, lOtj8). Ferric chloride colours its aqueous solu- tion a pure blue. The ammoniim salt crystallises in yellow needles, whilst the barium, calcium, and silver salts. resemble the corresponding salts of the a-acid. The methyl salt melts at 76", and the ethyl salt a t 5 5 O . When sodium P-napht,hol is heated a t 280-290" in a current of carbonic anhydride, absorption of the gas rapidly takes place, and a product is obtained consisting of &naphthol, undecomposed sodium &naphthol, and ~-?LaphthoZcarboxylic acid.This acid is extremely stable, and crystallises from water in lustrous, rhombic, Tellow scales, which melt a t 216" without decomposition, and are readily soluble in alcohol and ether, soluble in tolnene, benzene, and chloroform, and sparinrrlv soluble in hot water. Ferric chloride colours the aqueous solution blue. w. P. w. Terpenes. Part VI. By 0. WALLACH (Annulen,, 241,315-328). -The compound which the author (Abstr., 1887, 967) recently de- scribed as terpene nitrite is terpinene nitrosite. It forms monoclinic crystals ; a : b : c = 1.0103 : 1 : 0.66978 ; /3 = 80" 31'. Terpinene nitroZeth,yZarnine, NHEt2*CIoHl, : NOR, is obtained by boiling for a short time an alcoholic solution of the nitrosite with a strong aqueous solution of ethylamine.The crude product is poured into water, the precipitate dissolved in hydrochloric acid, and the base reprecipitated by ammonia, The base melts a t 130-131", and dis- solves in boiling alcohol, ether, chloroform, and in warm dilute solutions of alkalis. The hydrochloride, C12H,N,0,HC1, is crystalline, and dissolves freely in water and alcohol. The nitroso-compound melts a t 133-133". It is decomposed by boiling with an excess of hydrochloric acid, yielding hydroxylamine. Terpinene nitroldiethylamine, NEt2*CloHl, : NOH, melts at 11 7-1 18". Terpinene gzitrohethylarnirze, NHMe.CloH15 : NOH, crystallises in prisms and melts at 141". The dimethylamine, NiNe,*CloHl, NOH, melts a t 160-161". It dissolves in chloroform.The amylamine-compound is less soluble in alcohol and ether than the preceding substances. It melts a t 118-119". The piperidiwe, CloHlsNO,NCsHlo, melts a t 153-154'. It is insoluble in alkalis, but its salts are freely soluble in water. The hydrochloride is obtained as an oil on passing dry hydrogen chloride into an ethereal solution of the base. Terpinene rritrolamine is formed by adding ammonia to a hotORGANIC CKEiWSTRT. G1 alcoholic solution of terpinene nitrosite. After recrystallisation from hot water it melts at 116-118". By adding a mixture of nitric acid and amyl nitrite to carvene or citronene saturated with dry hydrogen chloride, Maissen (Gazzettu, 13, 99) obtained a crystalline compound melting with decomposition a t 1 1 ~ 1 1 5 " .The author has obtained the same or similar deriva- tives from cinnamene and dipentene. They melt at 109" and 110- 111" respectively, and act oh organic am"ines, yielding crystalline bases. vv. c. w. Constitution of some Pyrroline-derivatives. Ry G. CIAMICIAN and P. SILBER (Ber., 20, 2594-2607 ; compare Abstr., 1887, 597). -Uibromodiacetyl~~rrol~ne, C4NHAc,Pr2, is prepared by the action of bromine vaponr on a warm solution of 2 grams of pyrrylenedimethyl- diketone in 700 C.C. of water. It crystallises from alcohol in white needles melting a t 1'71-1 72", insolrible in waber, soluble in alcohol, ether, and in alkaline carbonates. Nitric acid oxidises it readily a t the ordinary temperature t o dibromomale'irnide ; the constitution of the base is therefore [Br, : Ac, = 3 : 4 : 2 : 51.C4NHBr2Ac*NOZ [Br2 : Ac : NO, = 3 : 4 : 2 : 51, is formed when dibromodiacetylpyri-oline (8 grams) is dissolved in fuming nitric acid (80 grams), and crystallises from alcohol in long, white needles melting at 206". It is soluble in alcohol, ether, ethyl acetate, hot glacial acetic acid, and benzene, very sparingly soluble i n water, insoluble in light petroleum. Alkalilie carbonates dissolve it readiiy with intense yellow colour. Dinitrodibromopyrroline, C4NHBr,(N02)2 [= 3 : 4 : 2 : 51, is ob- tained by the action of a well-cooled mixture of sulphuric and fuming nitric acids on the mononitro-compound. It crystallises from water in large, yellow plates (with 1 mol. €LO), which melt at about 169" with decomposition ; it is readily soluble in ether, alcohol, hot.water, and hot benzene, and dissolves in alkaline carbonates with evolution of carbonic anhydride, If the mixed acids are allowed to act on the mononitro-compound at the ordinary temperature, dibromo- maleamide, melting at 227", is formed. The latter is also formed when dinitrodibromopyrroline is heated at 165" ; nitric oxide is evolved. When dinitrodibromopyrroline is heated with sulphuric acid (20 parts) it is converted quantitatively into dibroniomaleic acid. It is probable that the imide of dibromomale'ic acid, and. therefore, maleic ~-itr~dibromacetyI'PYrO'o liire, Lcid also, are symmetrically rather than unsymmetrically constituted : CBr*CO CBr *CO <Csr.Co>NH, rather tha,n <C.c&NH>.(Compare Anschutz, Abstr., 1887, 916). Dibromopyrrolinedicarboxylic acid behaves towards fuming nitric acid in a manner similar to dibromodiacetylpyrroline ; dinitro- dibromopyrroline is formed identical with that obtained from dibromodiacetylpyrroline. The reaction shows that the two carboxyl-groups in pyrrolinedicarboxylic acid have the positions 2 : 5. Methyl dibromopyrrolinedicarbox2/late, CJYHBr,(COOMe)?, is ob- [NO, : NO, : B r : Br = 2 : 5 : 3 : 41G2 ABSTRACTS OF CHEMICAL PAPERS. tained by dissolving methyl pyrrolinedicarboxylate (3 grams) in water (1 litre), and saturating the lukewarm solution with bromine vapour. The yield is 4.5 grams of pure product. It crystallises from alcohol in long, white needles, melting a t 222", soluble in ether, almost insoluble in water.When 2 grams of the salt is a,dded to 40 grams of fuming nitric acid a t -Is", and the whole poured into 400 C.C. of ice-wa,ter, and treated with potash (30 grams), the compound C4H,BrNOa is obtained. It is a crystalline compound, melting a t 168-171" with deconiposition, soluble i n ether, alcohol, and hot benzene, rather sparingly soluble i n water, and insoluble in light petroleum. It dissolves in alkaline carbonates with evolution of car- bonic anhydride. The constitutional formula CBrO*C(NOH)*COOMe is suggested for it. Methyl dibromacetylcnrbopyrrolate, C*NHBr,Ac*COOMe, is pre- pared in a manner similar to the methyl salt of the bromodicarboxylic acid, which it completely resembles in its behaviour towards fuming nitric acid.Dibromacety lmeth y lpyrroline, C7H7Br,N0, is prepared by treating a solution of 2 grams of acetylmethylpyrroline, melting a t 85-86' (Abstr., 1886, 719), with an excess of bromine. It crystallises from dilute alcohol in long, white needles, of a silky lustre, melts at 161- 162", dissolves in ether, carbon bisulphide, and chloroform, and is sparingly soluble in boiling water. When the finely-powdered compound is warmed with fuming nitric acid, dibromomalejimid e (m. p. 227") is formed. The constitution of acetylmethylpyrroline is therefore [Ac : Me = 2 : 51. In order to obtain further evidence as to the constitution of pyrnvyl methyl ketone and Schwanert's carbopyrrolic acid, tribromacetyl- pyrroline and methyl tribromocarbopyrrolate were converted into dibromomaleimide by the action of nitric acid.C4NHBr2Ac..N0, [Br : Br : Ac : NO, = 2 : 3 : 5 : 41, is prepared by the action of bromine on nitracetyl- pyrroline, melting at 197" (Abstr., 1885,810 and 992). It crystal- lises from alcohol in needles melting a t 1 7 5 O , soluble in ether, warm dcohol, and glacial acetic acid, sparingly soluble in warm water, insoluble in light petroleum. The non-identity of this compound with the dibromo-derivative described above, and the probabili t y that in the nitracetyl-compound (m. p. 197") the acetyl-group has the a-position, make it probable that the nitracetyl-compound has the constitution [NO2 : Ac = 3 or 4 : 2 or 51. A table of all pyrroline-derivatives (halogen-derivatives and ethers excepted) of known constitution is given.Synthesis of Pyridine and Piperidine-derivatives. By C. PAAL and C. STRASSER (Ber., 20, 2756--2766).-Diphenacylacetic acid (Abstr,, 1887, 261) when treated with alcoholic ammonia yields the ammonium salt of ad-dip heny ldi~y~ropyridine-cy-carboa y l i c acid, C,NH,Ph,*COONH*. This salt is soluble in water and concentrated hydrochloric acid ; on acidification with sulphuric acid, the corre- sponding acid separates, but is quickly decomposed. On dry distilla- tion, ammonia is given off, and aa'-di~heny~yridir~ecnrboxyl,ic acid, liibrornon;tracefy.?pyrroline, N. H. M.ORGANIC CHEMISTRY. 63 C5NH,Ph,.COOH, is produced, which after purification crystallises in delicate, white needles or prisms, melting at 275', soluble i n alcohol, sparingly soluble in chloroform.The acid is not altered by nitrous acid, acetic chloride, or oxidising agents. Its ammonium salt does not exist in the free state ; the silver salt is a heavy, white precipitate ; the chromate a dark-red, amorphous precipitate ; the aurochloride is crystalline. Dip heny Zppiperidine- y-carboz y Zic acid, C5NH8P h,CO 0 H, obtained together with the above mid, and separated from i t by its greater solubility, forms crystalline crusts; it melts at 339', and sublimes without decomposition, its alkaline salts are very soluble, the barium and silver salts are white precipitates. Its nitroso-derirative crystal- lises in pale-yellow, glistening needles melting at l59", and is soluble in ether and alcohol. aa-Diphenylpyridine, C5NH3Ph, obtained by the distillation of the calcium salt of the carboxylic acid with lime, crystallises in long, glistening needles melting at 81-82" ; its platinochloride forms yellow needles, and the auroclzloride a crystalline precipitate ; the rnethiodide crystallises in needles melting at 203". aa-Diphen.ti~iperinine, C5NH9Ph,, obtained by the hydrogenation of the above base, is a thick, pale-yellow oil ; its ?ydrochZoride crystallises i n white needles; the platimchloride and the aurochloride and the nitroso - deriunt ive cry stallise with difficulty .V. H. V. 3-Methylpyridine and 3-Methylpiperidine. By C. STOEHR (Ber., 20, 2727--2733).--The picoline obtained by distilling strych- nine with lime (Abstr., 1887, 604) proves on further examination to be p-picoline, since nicotinic acid is found to be the sole pr-d uct on oxidation with 2 per cent.permanganate solution. Some quantity of the base was prepared to enable an examination of its properties to be made, and the results are compared with those of previous observers. P-Picoline thus obtained boils at 14.5-150" after two fractionations ; by conversion of this product into the mercurochloride and regenera- tion of the base, i t gives a product which mostly passes over between 148' a n d 149" (compare Hesekiel, Abstr., 1885, 812). The platino- chloride, (C6H,N)2,H,PtC16 + H,O, has the properties of' the salt described by Baeyer (AnnaZen, 155, 285), melts when dry at 195(: loses 1 mol. H,O when allowed to remain i n a desiccator, and when heated at 120" loses in addition I mol. HCI, the compound thus obtained, (G',H7N),,HCl,PtC14, melting at 211-212".The aiirochloride melts at 182-1 83". The mercuroch loride, C6H7N, H C1,2HgCl, (com- pare Hesekiel, Abstr., 1886, 256), crystallises from hot water in slender, ramifying needles, from dilute hydrochloric acid in indented scales, or long, compact needles, and from concentrated hydrochloyic acid, in which it is very soluble, in small, well-formed prismatic crystals melting at 139-140". The picrate crystallises in six-sided scales melting at 142-143". 3-Methylpiperidine, obtained by reduction of the P-picoline in alco- holic solution with sodium, is readily soluble in water, and yields a hydrochloride, crptallising in dazzling, white needles. w. P. w.64 ABSTRACTS OF CHEMICAL PAPERS. 2 : 6 Methylethylpyridine and 2 : 4 Methylethylpyridine.By M. SCHULTZ ( R e r . , 20, 2729-2727) .--Picoline ethiodide, when heated at 280-300" for 1 to 1 i hours, yields a mixture of bases. To separate these, the product is treated with water, acidified, dis- tilled to remove a small quantity of an arornhtic oil, then rendered alkaline and again distilled. The mixture of bases so obtained, which boils between 100" and 200", is fractionated, and the fractions boiling at 1 56-16(j0, 166-172", and 172-182" repeatedly refractionated ; in this way fractions boiling at 138-163" and 169-174'are obtained, and these consist chiefly of 2 : 6 methylethylpyridine and 2 : 4 methyl- e thy1 pyridine respectively. 2 : 6 ~feth?/lethyZpyridi.lze, C8HIIN, is a colourless, hygroscopic, oily liquid, having a sweet, aromatic! odour recalling that of picoline, and when moist, an alkaline reaction.It is sparingly soluble in water, readily volatile with steam, and yields salts which readily deliquesce in air: The platinochboride, (C8H1,N),,H,PtCl,, crptallises in tabular, triclinic crystals, melts at 173-174" (after drying a t 110"), and is readily soluble in hot water, insoluble in alcohol and ether ; the auro- clzloride, CsHllN,HAuC14, crystnllises in yellow needles, melts at 1 lo", and is sparingly soluble in water, readily soluble in ether alcohol. On reduction with sodium in hot alcoholic solution, copellidine, C,H,,N [Me : Et = 2 : 61, is obtained; this is a colourless, oily liquid, which boils a t 147-151", fumes slightly in the air, has the characteristic odour of piperidine bases, and a strongly alkaline reac- tion. The nitroso-derivative is a brown oil 5 the hydrochloride, C,H,N,HCl, crystallises in white needles, and though readily soluble in water and alcohol is only slightly hygroscopic.When oxidised with 2 per cent. permanganate solution, 2 : 6 methplethylpyridine is con- verted into a dicarboxylic acid melting a t 226", and identical with Ladenburg and Roth's dipicolinic acid (Abdtr., 1885, 557). 2 : 4 Nethybethylpyridine, [Me : Et = 2 : 41, is a hygroscopic, colourless, oily liquid, which in its properties closely resembles the 2 : &derivative. The pZntinochZoride, (C8Hl1N),,H2PtCI,, forms red- dish-yellow, tabular crystnla, which after drying a t 110" melt a t 190" ; the aurochloride, C8HI1N7HAuC14, crystallises in yellow needles, begins to fuse a t 83", melts a t 90", and is soluble in hot water, readily soluble in alcohol and ether.When the base is reduced with sodium in hot alcoholic solution, i t is converted into copeblidine, [Me : E t = 2 : 41 C,Hl,N; this is a colourless, oily liquid, which boils a t 155-160", has a strongly alkaline reaction, and an odour similar to that of the 2 : 6 base. The hydrochloride, C8HITN,HCI, crystallises in white needles, is readily soluble in water and alcohol, and is slightly hygroscopic. 011 oxidation with 2 per cent. perman- ganate aolution in the cold or on heating, 2 : 4 methylethylpyridine yields a dicarboxylic acid whose melting point rose from 204" to 211" after three crystallisations. This author regards this acid as being identical with Ladenburg and Roth's lutidinic acid (Abstr., 1885, 815), and ascribes its lower melting point to the presence of a small qnarltity of pioolinic acid.w. I?. w.ORGANIC CHEMISTRY. 65 Phenylated Piperidine and Pyridine Bases. By 0. BALLY (Ber., 20, .2590-2594).--r-Phenylpi~eridil~e. C,NH,,Ph, is prepared from r-phenylpyridine and purified by distillation. It melts at 57*5-58", and boils a t 255-2S7" under 727 mm. pressure; it is a strong base, almost insoluble in water. The salts are readily soluble. The hydrochloride crystallises in needles ; the platitrochloride forms orange-coloured plates, melting a t 204-207". It gives no precipitate with picric acid ; the original base gives a precipitate even i n vcry dilute s o h tion. C,NH,Me2Ph [Me : P h : Me = 2 : 4 : 61, is ob- tained by distilling potassium plienyllutidinegarboxylate (prepared from benzaldehyde, ethyl acetoacetate, and ammonia) with lime, a t the lowest possible temperature.It is purified by means of the hjdro- chloride, and crystallises from ether in prisms melting a t 54.5-55". I t boils a t 287" under 731 mm. pressure. The salts are generally sparingly soluble ; the hydrochloride (with 3 mols. H20) crj stallises in slender, matted needles which do not melt at 300" ; tlie platino- chloride, (C,,H,,N),,H2PtCl, + 4H20, forms orange-coloured needles ; the rzitmte and chromate melt at 177" and 228" respectively, both crystallise in needles. yPhenyZlupefidine, C,NH,PhMe,, is prepared by the action of sodium (2.5 parts) on phenyllutidine (1 part) dissolved in absolute alcohol ; it is separated from unchanged phenyllutidine by distilla- tion.It is a colourless oil of a peculiar odour, boiling a t 274" under 73L mm. pressure. The hydrocltloride and iritrate cryhtallise in prisms ; the dinitrate melts at 210" ; the platinochloride crystallises in gold-coloured plates melting a t 237". Besides pheriyliupetidine, a compound, probably hepty Zbenzene, CHPh( CH,*CH,Me),, is produced in the reduction of phenyllutidine. When .I-phenyllu~idylilcna nzethiodide (prepared by digesting the base with methyl iodide in a reflux apparatus) is treated with stroiig aqueous potash, a base is obtained which jields a hydrochloride id;Jntical with that formed by the action of silver chloride on methylpheuyl- In tidylium iodide.Methyl-yphenyllutidylium iodide is a crystalline substance s p r ingly soluble in hot water. Phenyllutidine, N. H. M. &innamylpyridine. By H. BAURATH (Ber., 20,2719-2720).- When a-piuoline and benzaldehyde in equimolecular proportions are heated with zinc chloride at 220-225" for six hours, a-cinnamylpyri- &be, C5NH,*CH : CHPh, is obtained, and after removal of unalteled benzaldehyde by steam distillation can be separated by rendering the product alkaline and distilling with superheated steam. Tlie base, already prepared but not described bF Jacobsen and Reimer (Alnstr., 1884, 335), is crystalline, melts at 90.5-91", boils at 313-314O (uncorr., under 733 mm. pressure), and is readily soluble i n carbon bisulphide and ether, soluble in alcohol, benzene, and light petro- leum, and practically insoluble in water.The salts generttlly crystal- lise in needles : the platinochloride, (C13H3,~N)z,HzPtCI, + d H 2 0 , decomposes when heated to expel the water of crptallisation. On treatment with bromine in carbon bisulphide solution, the base yields VOL. LlV. f66 ABSTRACTS OF CHEMICAL PAPERS. an additive compound, C,,H,,NBr,, which crystallises from alcohol in compact needles melting at 166-167" ; this derivative yields a. new base when heated with alcoholic potash. Derivatives of a-cinna,myl- pyridine have also been obtained by the action of hydriodic acid and by redilction of sodium and alcohol, and will be described in a later communication. w. P. w. Ethylquinoline. By L. REHER (Ber., 2 0 , 2734-2735).-Doehner having found the boiling point of n-ethylquinoline to be 24,5-246" (Abstr., 1887, 504), the author has redetermined the boiling points of a- and y-ethylquinoline (ihid., 279) by converting the bases into the platinochlorides, recrystallising these repeatedly from concentrated hydrochloric acid, and regenerating the bases from the pure salts by means of hydrogen sulphide.a-Ethylquinoline boils a t 256-6-258.6" (corr.) and y-ethylquinoline boils a t 271-274" (corr.), and the pure platinochlorides melt a t 189" and 203" respectively. From the pure bases, c3Lromates were prepared crystallising in red needles, and crys- talline zincochlorides were also obtained, that of the y-base forming white, concentrically-grouped needles melting a t 195". DiethyZquirLoZinP, obtained by the decomposition of the mercuro- chloride (Zoc.c i t . ) , is a colourless liquid having it quinoline-like odour, and boiling a t 282.8-284%0 (corr.). The plutinochloyide, (CqH,NEt,),,H,PtC1,, crystallises in orange-red needles, and melts a t 217" after previous blackening. On oxidation with chromic acid, the base yields a fimall quantity of an acid which crystallises in asbestos- By R. SCHMTTT and F. ENGELMANN (Ber., 20,2690-2695).--Further examination of ortho- hydroxyqainolinecarhoxylic acid (Abstr., 1887, 738) shows that it begins to fuse at 137", that carbonic anhydride and orthohydroxy- qninoline are formed a t 144-145", and that the decomposition is complete a t 150". The ammonium salt, OH*CgNH5*CO@NH, + H2Q, crystall ises in glistening, pnle-yellow needles, and is soluble in water ; the bal-iwn salt, (OH*C,NH,*COO),Ba + 2H20, crystallises in long, silky needles, and is sparingly soluble in water ; the caZciunz salt cry+ tnllises in stellate groups of prisms ; a basic barium salt, C10NH50aBa, and a basic calcium salt were also prepared; the former is very sparingly soluble in water.The phew$ salt, OH*CgNH5*COOPh, obtained by heating equimolecular proportions of the acid and phenol at 170", forms colourless, short prisms and melts a t 225-226". The hydrochloride of the acid, OH-C9NH,-COOH,HC1, crystallises in large prisms, and the mitrute in yellow needles ; both salts are decomposed by water. On treatment with strong nitric acid, a dinitrohydroxy- quinoline is obtained which is probably identical with that described by Bedall and Fischer (Abstr., 1881, 613 ; Ber., 14, 1368) ; it crystal- lises in golden-yellow scales, melts a t 276" with blackening and the evolution of gas, is sparingly soluble in most solvents, and readily decomposes alkaline carbonates, forming the corresponding salts.2\il.trohydroxyquinoZinecurboxZllic ncid, N02*C,NHa(OH).COOH, is prepared by heating the nitrate of orthohydroxyquinolinecarboxylic coloured needles melting a t 190". w. P. w. Orthohydroxyquinolinecarboxylic Acid.ORGANIC CHEMISTRY. 67 acid with rtcetic acid at 100" ; the resulting brown mass is extracted with acetic acid until it becomes yellow, and is then purified by soliition in hydrochloric acid and subsequent precipitation with water. It crystallises from water in yellow needles showing a vitreous lustre, decomposes at 200" with the evolution of carbonic anhydride, and dis- solves readily in concentrated hydrochloric acid, in alkalis and in alka- line carbonates, but is sparingly soluble in acetic acid.When heated above 200°, nitrohydroxyquinoline, NO,*C,NH,*OH, is formed ; this crystallises in yellow needles, melts at 173", is readily soluble in acetic acid and hot, hydrochloric acid,less so inalcohol and ether. On treatment with bromine (2 mols.) a t loo", a dibromohydroxyquinoline identical with that prepared by Bedall and Fischer (Zoc. cit.) is obtained together with bromohydroxyquiiiolinecnrboxy1l:c acid, OH*C9NHdBr*COOH ; this crystallises in matted, citron-yellow needles, melts at 233-235" with the evolution of carbonic anhydride, a,nd yields a hydrochloride which crystallises in well-formed tables, and decomposes when boiled with water.BromohydroxlJqwinoline, CgNHBByOH, formed quanti- tatively when the bromo-acid is heated a t 200°, crystralIises in white needles, melts at 119-120", and is readily soluble in the ordinary solvents except water. w. P. w. Parahydroxyquinolinecarboxylic Acid. By R. SCHMITT and J. ALTSCHUL (Ber., 20, 2695-2698).- When potassium parahyd coxv - quinoline is heated with liquid carbonic anhydride in an autoclave at 170" for six to seven hours, a quantitative yield of potassium para- hydroxyquinolinecarboxylate is obtained ; the sodium-compound cannot be substituted for the potassium-derivati.ce in this reaction. Parahydroxy~uin,r,linecarbozylic acid, OH*C9NT3,.COOH, crystallises from water in yellowish-white flocks consisting of microscopic prisms, melts at 203-204" with the evolution of carbonic anhydride and formation of parahydroxyquinoline, and is sparingly soluble in alcohol, ether, benzene, and hot water.Ferric chloride colours the aqueous solution red. The hydrochloride, OH*CgNH,~COOH,HCl, crystal- h e s in long, colourless needles, G r from concentrated hydrochloric acid in short, thick prisms, is decomposed by water, and yields a well-crystallised platinochloride ; the mitrote, formed by digesting the acid with nitric acid (sp. gr. = 1*35), crystallises in large, white needles, and is decomposed by water. The ammonium salt, with 4 mol. HzO, crystallises in long, colourless needles, and is soluble in water, the solution evolving ammonia when boiled ; the barium salt, with 2 mols.HzO, crystallises in colourless tufts of needles, and does not form a basic salt when treated with barium hydroxide. If the nitrate of parahydroxyquinolinecarboxylic acid is heated with nitric acid, yellowish-red prisms separate on cooling, which when treated with water decompose into nitric acid and nitrohydroxyquino- line ; this crystallises in yellow needles, melts a t 136", and is probably identical with Skraup's nitrohydroxyquinoline (Abstr., 1882, 92). w. P. w. Constitution of Glutazine. Ry R. V. PECHMANN (Rer., 20, 2655 -2658 ; compare Abstr., 1887, 155).--Nitroglutazina, C5H N 0 *NO*, f i 268 ABSTRACTS OF CHEMICAL PAPERS. is obtained together with dinitroglutazine when nitrous oxide is passed into a cold aqueous solution of glutazine.It crystallises from water in orange-yellow plates which decompose a t 170 -180" withon t melting. Dinitroglutazine, C5H4N,02(N0,),, crystallises from water in yellow plates. Both compounds give colourless solutions with acetic acid and zinc-dust which become red when exposed to air. When heated with alkali, they are converted, with evolution oE am- monia, into sparingly soluble salts whicb crystallise in sulphur-colonred, matted needles and explode when heated. These results make it improbable that glutazine contains an amido-group. The nitronitrosamine, N02.C5H4Wz02.N0, is obtained when glutnzine (1 part) dissolved in the smallest amount of dilute aqueous soda is treated with sodium nitrite (1 part); water is added (so that the whole amounts to 30 parts), and the whole is poured into a mixture of glacial acetic acid (5 parts) and water (30 parts). I n a short; time it solidifies to an orange-coloured magma.The sodium saZt, C5H3NaN405, so obtained ci-ystallises in yellow needles with water of crystallisation. Acids precipitate greenish-yellow needles from the solution. When the sodium salt dissolved i n glacial aeetic acid is warmed with excess of sodium nitrite, the sodium salt of the dinitronitrosamine, C5H2NaN5O7, separates as a, cinnabar-coloured, crystalline powder. This dissolves sparingly in water, readily in alkalis. When warmed with dilute acids nitrous acid is given off. Dibes7xoylgZutazine, C5H4N202Bz2, is obtained by heating glutazirie with benzoic chloride on a water-bath f o r two to three hours, and cryst,allises from glacial acetic acid in lustrous, brownish plates melting at 215-5216'.It is insoluble in water and in alkalis, sparingly soluble in alcohol. The above results show that there are only two hydrogen-atoms in glutazine displaceable by acid radicles, and that these are present as iniidoliydrogen as shown by the formula NH< c0'cH2>C NH. CO-CH, N. H. M. Reactions of Caffe'ine and Caffe'idine. By &I. WERNECKE (Chem. Cenfr., 1887, 1082--1084j .-Hydriodic acid, like hydrochloric acid, decomposes caffeine into carbonic oxide and anhydride, formic acid, sarcosirie, ammonia, and methy lamine ; if phosphorus is added, glycocine is formed instead of sarcosine, whilst hydrogen phosphide and pliosphoninm iodide are evoliied.Although methyl iodide readily combines with cafleine to form, the methiodide, the formation of the cor- respoiiding ethyl-compound presents considerable difhulty. Phenyl- hydrazine will not combine with caffeine; from this it would seem that in this casa, as an an;~loqiie of carbamide, the carbonyl-group is directly combined with the nitrogen-atom. Ca-ft h e ch lo?-iodide, CsHI,N4O2,CI1, is produced when sodium nitrite and potassium iodide are added to a, hydrochloric acid solution of this base ; it forms golden needles melting a t 182--183", and is decom- posed into it.: const,itnents by ammonia or by boiling with water. The method proposed by Mdy and Andreasch for the preparation of caffei- dine presents no advantage over that of Strecker.Caffeine sulphateORQANIC CHEMISTRY. 69 differs from the hydroiodide in that the farmer, when heated, turns purple-red, whilst the latter yields a green mass ; the anrochloride of caffeine cannot be isolated. The base is best separated from the sulphate by means of basic lead carbonate. Methy leafezdine hydr- iodide is not a well-defined substance, but the free base is crystalline and melts at 86-88' ; dimethy Zccrflei'dine forms leaflets melting at 123". The author ascribes the following constitution to cdeidine, "<NMe*C(NH) NM+CHy.~~~e. V. H. V. Hydroquinine. By 0. HESSE (Annalen, 241, 255-287) .-Hydro- quinine, C2OH26N~02, exists ready. formed in cinchona bark, and is present in varying quantities in commercial quinine.It is COII- veniently prepared from the mother-liquor obtained in the manu- facture of the acid sulphate of quinine. The mother-liquor is neutralised and the neutral salt dissolved in sulphuric acid, quinine xionosulphate crystallises, and the mother-liquor containing the hydro- quinine is again neutralised. By repeating these operations a salt is obtained containing 30 per cent. of hydroquinine sulphate. The quinine is removed by oxidising the solution in sulphuric acid with potassium permanganate, the mixture is filtered and the hydroquinine liberated by the addition of an alkali and extracted with ether. The base is deposited from its solution in chloroform in needles and from hot acetone in long plates. Many of the properties of the compound have been previously described by the author (Abstr., 1882, 1113). It is laevogyrate [a]= = -1142.2" for a 2.4 per cent.solution in 95 per per cent. alcohol at 20", and [a]= = -227.1" for an aqueous solution of the same strength under similar conditions. (40 C.C. normal hydro- chloric acid were contained i n each 100 C.C. of water used for the solu- tion.) When ammonia is added to a solution of equal molecular propor- tions of cupre'ine and hydroquinine in water containing sulphuric acid, and the acid mixture extracted with ether, a crystalline compound of cupre'ine and hydroquinine is obtained, C,oH2,N20,,C,~H2~N,02 + 2H20. Hydroquinine forms similar compounds with conchinine and hydro- conchinine. It also unites with two and with three molecules of cinchonidine, forming crystalline compounds which do not contain any water of crystallisation. Analogous compounds are formed with hydrocinchonidine and with homocinchonidine. Anethoillztldroq~inine, (CJI&zO2)2, C&,,O + 2H20, is deposited in quadratic prisms from a solution of 5 parts of hydroquinine and 1 part of anethoil in warm dcohol.Hydroquinine forms three series of salts, which are as a rule more soluble than the corresponding salts of quinine. The normal sulpl~at~e, ( Cz~H~6N20z)2,H2S04 + 6Hz0, has been previously described (Zoc. cit.). It forms a crystalline compound with phenol, ( CzoH26~zOZ),S03, C6H60 + 2H20, which is spayingly soluble in cold water. The acid sulphate, C20H26N202,S0& + 3Hz0, is freely soluble in water and alcohol. At 140°, the anhydrous salt is converted into hydroquinine sulphate.The disulphate is amorphous. Dichroic crystals resembling hydro-70 ABSTRACTS OF CHEPolICAL PAPERS. quinine herepathite are obtained by adding potassiiim iodide (2 mols.) to an alcoholic solution of the acid sulphate (4 mols.), and acting on the product with an alcoholic solution of iodine. Hydroquinine hyposulphite, ( CzOH26NzOz)a,H2Sz0, -f- 2H20, forms white prisms sparingly soluble in water. The hydrochloride, CmH26Nz02HC1 + 2Hz0, crystallises in prisms, andis freely soluble in alcohol and water. The plntinochlorides, ( C20H26Nz02)z,H2PtC16 + 3H20 and C20Hz6Nz02,~zPtCI, -t- 2Hz0, are amorphous and are sparingly soluble in water; the mercurochloride, ( CzoHz6Nz~zH~1)zH~CI,, crystallises in needles. The hydrobromides, CzoHzaN20z,HBr + 2Hz0 and C20Hz6N20R,2HBr + 3H20, also form needles.The neutral hydriodide is a colourless oily liqnid which solidifies to an amorphous mass. Potassium iodide produces in acid solutions of hydroquinine salts a yellow, crystalline precipi- tate of the acid hydriodide, CzoHz6NzO2,2HI + 4H20. On the addition of iodine to the alcoholic solution of this salt, dichroic, ueedle-shaped crystals of the composition C2,,H2,N20,2(IH,IZ) are deposited. The acetate, CmH26N202,C2H402 + 5Hz0, crystallises in needles and is freely soluble in alcohol and water. The benzoate and sdicylate dissolve freely in alcohol. The benzoate is anhydrous. The piperonate, CzoHz6NzOz,C8~604, is soluble in water and in chloro- form. Thc oxalate is deposited from hot alcohol in prisms containing 6 mols.H20. The tartrate also crystallises in prisms containing 2 mols. H,O. It is soluble in alcohol, water, and in a mixture of alcohol and chloroform. The citrate and arssnate crystallise with 10 rnols. HzO, the phosphate with 7 mols. H,O. The chromate, ( Cz0H26NzOz)zHzCr04 + 6Hz0, forms golden needles. The dichromate is an oily liquid. Hydroquinicine dissolves freely in ether, alcohol, chloroform, and in dilute acids. The solution in dilute sulphuric acid is yellow; the colour changes to green on the addition of chlorine water and ammonia, b u t the mixture is not fluorescent. An ethereal solution of oxalic acid produces in an ethereal solution of hydroquinicine an amorphous precipitate soluble in chloroform. The normal sulphate cryst,allises in needles and dissolves freely in alcohol and in water.Hydroquinine platinockloride, C20Hz6N202, HzPtCI, + HzO, forms orange-coloured crystals. Hydroquinine unites with methyl iodide, forming the compound CzoH26Nz0z,MeI + CzH60. It crystallises in prisms of a yellow colour and dissolves in hot alcohol. It melts at 218". On treatment with silver chloride, it is converted into the chloride CzoHz6Nz0z,MeCl + 2Hz0. The acid platinochlol"ide, C,Hz6N,0z,Me*HPt Cl6 + 2H20, forms orange-coloured crystals, and the normal salt, (C~OEIZ~N,O,M~),,P~CI,, pale-yellow needles. Hydro- quinine methylhydroxide is amorphous. It is soluble in alcohol and water. The solutions are caustic and absorb carbonic anhy- dride. AcetyEhy droquinhe, Cz0R25N202Ac, is amorphous. It melts at 40" and dissolves freely in alcohol, ether, benzene, and in acids.The solution is laevogyrate, and the solution in sulphuric acid is fluorescent. The platinockloride contains 2 mols. H20, and the normal sulphate,ORGANIC CHEMISTRY. 71 which is soluble in hot water and alcohol, crystallises with 9 mols. Hydroquinine is converted into hydrocupreyne dihydrochloride by the action of hydrochloric acid, sp. gr. 1.125, a t 150". Hydrocuprezize, C,9H,,N,0, + 2H20, exists as a crystalline powder freely soluble in ether, alcohol, and chloroform. It melts at 168-170°, and exhibits a strong basic reaction and forms crystalline salts. Solutions of the normal salts have a greenish-yellow colour, the acid salts are colour- less. The sulphate, ( ClgH,,N,O,),,H2SO4, is sparingly soluble in water and in alcohol.The tartrate is sparingly soluble in water, but the dihydrochloride, CleH2iNz02,2HCl + HzO, is freely soluble i n water. The acid platinochloride, C19HzrNz0z,H~PtC16, is crystalline and in- soluble in water. ~ydroquininesulpponic acid, C,oH,N,O,*SO,H + H,O, is prepared by dissolving hydroquinine in sulphuric acid a t the ordinary tempera- ture. The solution is poured into water and mixed with excess of ammonia. The acid crystallises in cubes and is soluble in boiling water, alcohol, and hot solutions of alkalis. It dissolves freely in acids, with which it forms crystalline compounds. The anhydrous acid inelts a t 239". The presence of hydroquinine in cinchona bark vitiates the results obtained in the estimation of quinine by the ordinary polariscopic met hod. w.(3. w. H,O. Apocinchine and Apochinine. By W. J. COMSTOCK and W. KOENIGS (Ber., 20, 2674-8689).-Analyses of salts and bromo- derivatives of apocinchine show that the formula, previously assigned to the base (Abstr., 1882, 224) must be altered to C19H19NO; the formula ascribed to ethylapocinchinic acid (Abstr., 1885, 1248) ig, huwever, retained. The authors now attribute the formation of the combustible, gaseous halogen compound (? methyl chloride) in the preparation of apocinchine to some secondary change in the reaction. Apocinc hine hydro bromid e, C19Hlg N 0, HBr, crystal lises from alcoholic hydrogen bromide in small, yellow needles, and melts at about 256'; the hydriodide, C1gH1gNO,HI, is a yellow, cryst'alline salt ; the PZutinG- chloride, (C,gHlgNO),,H2PtC16, forms orange-yellow crystals and melts at about 235".The acetyl-derivat,ive, ClyHI8NOAc, forms practically colourless crystals, and melts a t 118-119" ; the double phosphates of apocinchine and ammonium, barium, acd potassium, were also pro- pared, and crystallise well. Bronaapoci?i,chine, CI9H,,NOBr, is prepared by gradually adding bromine to apocinchine hydrobromide dissolved in equal parts of chloroform and acetic acid until the yellow perbromide begins t3 separate; sodiiim hydrogen sulphite is then added and the base obtained from the chloroform and aqueous layers by evaporation and precipitation. It is crystalline, melts at 186-188", and is readily soluble in aqueons soda, benzene, chloroform, and ethyl acetate, less so in alcohol, carbon bisulphide, ether, and light petroleum.Brom- apocinchine is not altered by prolonged boiling with alcoholic soda, and yields bromoform and cinchonic acid on oxidation with 4 per cent. chromic acid solution.72 ABSTRACTS OF CHEMICAL PAPERS. Dibroniethylapocinchine, ClgH,,NBr2*OEt, is prepared by adding ethyl- apocinchine (10 grams) to well-cooled bromine (15 c.c.), digesting the product after 12 hours with sodium hydrogen sulphite. and extracting with alcoholic ammonia; the deposit from the alcoholic solution is then boiled with dilute sutphnric acid, the resulting solution treated with ether and aqueous soda, and the base obtained from the ethereal layer by evaporation. It melts at 116-118". The alkaline solution, after separation from the ether, is found to contain dibromapocin- chine. Ethylapocinchinic acid forms a crystalline hydrochloride and hydro- bromide. The silver salt, C,,H,,NO?Ag, is a white, crystalline salt unaffected by light ; the platinochlorzde, (C,,H,gN0,),,H,PtC16, is pre- cipitated in volumiiious, slender, straw-yellow needles, which are con- verted into small, compact, orange-yellow crystals, when the salt is heated on a water-bath for a short time. Homupocinchina, C,H,,NO, the compound formed together with carbonic anhydride and ethyl chloride when ethylapocinchinic acid is heated a t 130" with hydrochloric acid (Zoc.cit.), crystallises from dilate alcohol in colourless crystals which contain water of crystallisa- tion and melt a t 184-185'. It is sparingly soluble in water, ether, benzene, and chloroform, readily soluble in hot alcohol, and differs from apocinchine, to which it shows much similarity, in its ready solubility in dilu te aqueous soda.The kydrob romide, CI,H,,NO,HBr + H20, crystallises in glistening, transparent, yellow needles or prisms, melts at 221-222", and is sparingly soluble in water and in excess of dilute hydrobromic acid. The ethyl-derivative yields a crystalline, yellow sulphate. On fusion with potassium hydroxide, homapocinchine is converted into a compound which probably corre- sponds to oxyapocinchine. When oxidised in very dilute solution with permangmate, ethylapocinchine yields a mixture of solid acids which dissolve in dilute sulphuric acid and alkalis. Ethylapocinchinic acid is one constituent of the mixture.To effect a separation, the product is boiled with hydrobromic acid (sp. gr. 1-49>, and the solution treated with aqueous soda which precipitates homapocinchine ; careful ncidifi- cation of the filtrate then precipitates a mixture of a t least two acids, of which the one of lower melting point is the more soluble in alcohol. The more soluble acid, C,,H,,NO, or ClgHJVO,, dissolves in dilute mineral acids, melts at 230" with the evolution of gas, and at 240" yields carbonic anhydride and a compound, CliH,,NO,. This crystallises from dilute alcohol in colourless, silky needles, melts a t 0,23", is not volatile without decomposition, and is soluble in dilute araids and alkalis. The hydrobromide, sulphate, and nit rate are crystalline, and sparingly soluble.AcetyZoxya23ocinchilzcl, CI9Hl,NO2Ac, melts at 201--203", and is soluble in alcohol, benzene, and light petroleum. From considerations based on analyses of its salts, the authors have adopted the formula Cl9H,,NO, for chinine, instead of that previously proposed (Abstr., 1885, 910). Chinine h!/ldrobrowide, C19H19N02,HBr, crys tallises in long, sulphur-yellow needles, and is decomposed by water. The remainder of the paper is devoted to a discussion of the con-ORQ AKIC CHEMISTRE'. 73 stitution of these alkalo'ids, in which the authors adhere t o the views already put forward wit>h regard to apocinchine (Abstr., 1885, 1248 ; 1887, 600), and suggest that cinchine niay possibly be a dialkyl- amidophenylquinoline, and t,hat the second benzene nucleus is present in a partially hydrogenated form.w. P. w. Strychninesulphonic Acids. Bp C. STOEHR (Ber., 20, 2i33- 2734).-A note calling attention to the fact that the results obtained by Guareschi (Abstr., 1887, 853) are essentially the same as those previously arrived at by the author (Abstr., 1886, 269). w. P. w. PecuIiar Modification of UrobiIin. By E. SALKOWSKY (Chpm. Centr., 18, 1089) -On examination of a sample of urine peculiarly rich in urobilin, itl was observed that on keeping this colouring matter disappeared without any marked change of the colour of the urine. This conversion of the urobilin seems not to be conditioned by the ammoniacal fermentation of the urine or by the presence of micro-organisms, Urobilin is a substance readily decomposed, and passes into a modification which, although still coloured, shows no absorption-bands, nor fluorescence with zinc clrloride in ammoniacal solution, and is not taken up by chloroform.It is probable that in most normal urines, urobilin, as well as its decomposition-products, is present. V. H. V. Chemical Formation of Albumin. By C. P. W. KKUKEKBEKG (Chem. Centr., 1887, lOSS).-W hen keratin, previously purified by the action of pepsin and trypsin, is heated with water in a sealed tube, it dissolves to form an alkaline liquid, possessing a strong odour of hydrogen sulphide, This liquid contains a non-dialysable substance, keratinose, precipitated by ammonium sulphate, which agrees with hemialburnose as regards these reactions, although it does not give the hydrochloric acid test,.Kemtinose is converted by pepsin and hydrochloric acid a t a blood-heat into keratinpeptone, which is not precipitated by ammonium sulphate. Under the same conditions spongin yields spongiorzose, ft soluble, indiff usible substance ; this is also converted into spoupiopeptone. By the dccomposition of spongin, carbamitle seems to be formed. The author considers that the albu- minoids and skeletins are related to albumin as methyl to methyl ether. V. H. V. Coagulation of Albumin. By V. MIcHAn,oFF (Chem. Centr., 1887, 1088).-According to the author the coagulation of albumin is due to one of two phenomena, namely, t'he true coagulation induced by the action of ferments or heat, a process analogous to etherification OK the formation of polyhydro-silicates or glycols, and a pseudo-coagula- tion caused by a loss of " gelatinose-water," which corresponds w i t h the loss of water of crystallisation of salts.The coagulating power of salts on solutions of albumin is dependent on the nature of the aoid and base therein contained; the maximum effect is produced by ammonium, the mean by sodium, and the minimum by potassium salts. Again, in the case of ammonium salts, the sulphate is more74 ABSTRACTS OF CHEXICAL PAPERS. ---- 0 ,. .. .. ,. H.. .. .. .. N.. .. .. .. S .. .. .. .. 0 .. .. .. . . efficient than the nitrate, and of potassium salts the snlphate than the chloride. V. H. V. Egg Albumin and Albumoses. By R. H.’CHITTENDEN and P. R. BOLTON (Studies from Lab. Physiol. Chem., Yale Uuiv., 2, 126-155). --These experiments were designed to contrast the products of diges- tion of egg albumin with those obtained by Kuhne and Chittenden from fibrin.Four samples of albumin were prepared ; i n some cases it was separated from globulin by saturation wi tjh magnesium sul- phate, in others by dilution and the subsequent addition of acetic acid. An elementary analysis of these four samples gave the following average percentages :-C, 52.18 ; H, 6.93 ; N, 15.81 ; S, 1.87 ; 0, 23.21. Further, coagulated products did not differ in composition from non-coagulated albumin. These results do not agree with any of the formula ascribed to albumin by previous observers. Peptic digestion of fhe albumin resulted in the formation of albu- minoses of which the percentage composition and reactions were determined.In composition they were found t o differ from each other somewhat more than the albumoses from fibrin ; collectively, however, there is less difference in composition between the albu- Moses and the egg albumin from which they were formed than in the case of the albumoses from fibrin. The following table gives the final results :- Proto- Deutero- Proto- Deutero- Egg. albumose. albumose. Fibrin’ albumose. albumose. albumin. -- ------- - 50’7’: 50.65 52.68 51-07 51.62 52.33 6-78 6.83 6 *83 6 -98 6.97 6 *98 17.14 17.17 16-91 16’00 15-82 15.85 1.08 0 -97 1 .lo 1 -95 1 *96 1 -82 24?23 24.38 22.48 24.00 23.63 23-02 Fibrili products. Egg albumin products. I I n their yeactions the different albumoses (proto-, deutero-, hetero-, and dys-albumose) obtained from egg albumin do not differ essentially from those obtained from fibrin.W. I). H. Metallic Compounds of Albumin and Myosin. By R. H. CHITTENDEN and H. H. WHITEHOUSE (Studies from Lab. Physiol. Chem., Yale Univ., 95--125).--Many researches on the subject of the metallic compounds of albumin have been carried out since Lieber- kuhn attempted to establish the molecular weight of albumin by the analysis OE copper albuminate. The more recent work of Harnack (Abstr., 1882, 747) showed that two compounds of albumin (from white of egg) with copper occur, one containing 1.35 per cent., and the otlier 2-64 per cent. of copper. I n the present research, albumin was freed from globulin by the use of dilute acetic acid, and both theORGANIC CHEMISTRY. 75 acetate and snlphate of copper were used in the preparation of the albuminate.The precipitate was well washed with water, powdered, and dried. The percentage of copper was first determined as cupric oxide by ignition and weighing : the oxide was then dissoived in dilute nitric acid, treated with hydrogen sulphide, and the amount of cuprous sulphide obtained weighed. By the former method, in 15 prepam- tions the average result was 1.17 per cent. of copper; and by the latter method 0.94 per cent. ; the preparations, therefore, contain 0.23 per cerit. of ash. I n order to obtain less ash, Harnack dissolved tthe albuminate in sodium carbonate and reprecipitated it by the careful addition of acid; this process was repeated several times. This treatment certainly increases t,he percentage of copper, but is a source of error, as the sodium carbonate withdraws a portion of the a1 bumin.Long-continued washing with water also causes partial dissociation of the compound. The results obtained correspond with the formula (C72H11,N18S022)~ + Cu - H,. A normal lead salt causes a small precipitate when added to albu- min, whilst with basic lead acetate the albumin is completely precipi- tated. This confirms the previous statement of Berzelius (Lehrbuch der Chemie, 9, 29). The preparations were well washed from both lead and albumin, dried, and the lead was determined, first by simple ignition, and then obta,ined as sulphate, which was ignited. The results indicate that more than one compound of lead is formed, that made by the addition of a large excess of the basic acetate, containing about five times as much lead as the ordinary basic lead compounds.An iron compound Tvbich was found to be more stable than the copper albuminate, and corresponded fairly well with the formula ( C72H:llzN18s02,)4 + Fe -H3, and a zinc compound, (C7,H,,,N18S02,)a + Zn - H2 ; acid compounds with uranium, (~,2Hl12N18s022)3 + U - H2 ; with mercury, (C7,Hl,,N,8S0,)4 + Hg - H,; and with silver, (C7,Hll,N,8SO,2), + Ag. - Ha, were also prepared and analysed. Much stress is not laid on such forrnu1Be;as it seems possible to form a large variety of compounds by simply modifying the conditions of precipitations. This, with the undoubted tendency of the compounds to dissociation, may account for the lack of agreement in the results of different workers.Similar compounds prepared from myosin obtained by extracting ox flesh with 15 per cent. ammonium chloride were prepared, and the percentage results show that these two forms of prote'id matter do not form corresponding compounds with the metallic salts used. This is illustrated by the following table :-76 ABSTRACTS OF CHEMICAL PAPERS. --. ......... .......... .......... .......... .......... ......... .......... .......... .......... Copper compound Iron 9 , Zinc 9 7 Ura,nyl ,, Mercury ,, Lead ?, Silver ,, Nickel ,, Cobalt ,, Egg albumin. 0 *94 per cent. Cu 0.95 ,, Fe 0.91 ,, Zn 4.60 ,, U 2.89 ,, 2.56 ,? 4.09 ,, Ag Ff - Myosia. 1-17 per cent. Cu 2.29 ,, Pe 0.72 ,, Zn 2.43 ,, Hg 4-70 ,, Ni 6-03 ,, Co 7-49 ), u - - W. D. H. Casein and Caseoses.By R. H. CHITTENDEN and H. M. PAINTER (Studies from Lab. Physiol. C'hern., Yale Univ., 2, 156-199),- Danilewsky ( Z e i t . physiol. Chem., 7, 433) has asserted that casejin is a mixture of two protejids, caseoprotalbin, partially soluble, and caseoalbumin, insoluble in hot 50 per cent. alcohol. Hammarsten (ibid., 7, 227) has shown that the peculiar behaviour of Danilewsky's case'in is due to its containing calcium phosphate, the presence of which impurit'y depends on the use of hydrochloric acid in the pre- cipitatioii of the case'in, as this acid does not favour the removal of the salt as well as acetic acid. He also considers that casein is a single prote'id. I n the present research, seTen distinct preparations of casejin were made. Elementary analyses show a close agreement throughout, and the results mcreover accord closely with those of Hainmars ten, I n the digestion of casein with hydrochloric acid, peptones are ultimately formed, and the name caseose is given to the intermediate products.These were separated by the methods of Kiihne and Chit- tenden into proto-, hetero-, and deutero-caseose, which correspond with the albunioses with similar names. The quantity of heterocaseose obtained was usually very small. The reactions characteristic of albumoses apply generally to the caseoses. Unlike proto-albumose however, protocnseose is precipihated from aqueous solutions by acetic acid. The average of the analyses of 10 preparations of proto- caseose gives the following percentage results :- I-_I-- --I---!--- Protocaseose ........1 52.89 1 7.10 I 15-94 1 0.95 1 23.12 Case'in.. ........... 53.30 7.07 15.91 0.82 22.03 Deuterocaseose contains ZL smaller percentage of carbon than proto- caseose, and heterocaseose contains fully as much carbon as case'in itself. An insoluble, semi-gelatinous substance which separates in the first stage digestion has not yet been inveshigated. Weyl's com- mercial " case'in-peptone " contains large quantities of caseoses. W. D. H."P PHYSIOLOGICAL CHEMISTRY. 1 4 Animal Tannin. By M. VILLON (Cham. News, 56, 175).-corn weevils CCaZandra graneria) were killed, ground in a mortar, and digested for one hour in boiling 90 per cent. alcohol. The residue from the evaporat,ion of the extract is taken up with ethyl acetate at SO", .and precipitated by means of ammoiiiacal zinc a,cetate.The preci- pitate is decomposed with oxalic acid, and the solution evaporated in R vacuum. In this way 3 per cent. of a substance having all the general properties of tannin is obtained from the weevils. This animal tannin, fracticomitanrzin, forms small reddis h-ye!Iow scales. D. A, L.ORG ANIU CHEMISTRY. 35Organic Chemistry.Arrangement in Space of the Atoms in the Molecules ofCarbon-compounds. By J . WISLICENJS (Chem. Centr., 188’7, 1005-1009).--Van’t Hoff and Le Be1 were the first to explain the opticaldiflerence of certain carbon-compounds by a difference in the relativearrangement of the atoms in space within the mo.lecde ; since theirwork, however, no serious attempt has been made t o apply theirtheory t o explain the isomerism of certain compounds, whose com-position, according to present views, is identical.a 36 ABSTRACTS OF CHEMICAL PAPERS.Such peculiar cases as those established by the researches of Fittigon the isomerism of male’ic and fumaric acids, however, and the dis-covery of a third and fourth monobromocinnamic acid, have beenclassified under the generic term of alloisomerism. Chemists hithertoseem to have contented themselves with a name.Adopting the hypothesis of van’t HoiYand Le Be1 that t.he atomsoccupy the solid angles of a tetrahedron, being arranged around acentral carbon-atom it is evident that two carbon-atoms, associatedtogether in the parafflno‘id form of combination, would revolve aroundone common axis, passing through the point of union of the atomsand the direction of attractiou of two associated atoms, such as thoseof hydrogeu.When two carbon-atoms are combined together, as inthe olefines, they can only revolve round an axis which is the straightline connecting the two common carbon-atoms.Supposing all four of the affinities of the saturating atoms areunequal, then six isomerides are possible, in the case of two pairsthree isomerides, and three also if two affinities are equal and twounequal. For male‘ic acid, van’t Hoff has proposed the formulaCH*COOHIICH-COOH, so that for fumaric acid the formula will beCOO*HCHIICH-COOHIn order to explain the conversion of malei’c into fumaric acid throughthe intervention of halogen-derivatives of succinic acid, it is sup-posed that the atoms combined with neighbouring carbon-atomsmutually react on one another according to their chemical affinity.Hence, it follows that two carbon-atoms combined together by oneaffinity, and being in a poRition by revolution around their axis to giveway to this attraction, will so arrange themselves that the associatedradicles interchange positions in the syshem.Such a relative arrange-ment will be stable in the cold, but at a higher temperature, as theinteroscillation of tbe elements will be more frequent, there is aloosening of the affinities, and a different configuration ensues. Whenan unsaturated compound passes into one that is saturated, it is in-different to which of the two carbon-atoms each particular radicleattaches itself ; the compounds formed are identical.But if an atom iscombined with two different radicles, then by addition an asymmetri-cal carbon-atom results according as the added atoms attach them-selves to one or other position of affinity. This explains the forma-tion of optically inactive compounds under these conditions, sinceboth modifications are produced in equal quantities.As regards the nomenclature of these dieerent geometricallyisomeric configurations, it is proposed to call the arrangementaCb aCb11 the centrally or axially symmetrical, and the arrangement 11bCa aCbthe plane symmetrical.The following examples are given in illustration of the abovOROANIC GHEMISTRT. 37views :-Tolane dichloride exists in two modifications ; according tothe author's hypothesis, the modification of higher me1 ting point,obtained by the direct chlorination of tolane, is the plane symmetricalPh*C*Cl Ph*C-Cl11 , whilst the other is the axially symmetrical 11 Asfumaric acid is principally formed by heating malic acid, in which,doubtless, the carboxyl-group has more inclination towards thehydrogen-atom than to the hydroxyl- or other carboxyl-group, itsPh.C*Cl C1.C.PhC 0OH.C H-OHconstitution may be represented by a configuration I HHOC o OH'from which by the abstraction of a molecule of water the formulaCOOHGHII results.The conversion of ethyl maleate into ethylfnmarate by iodine is explained by the intermediate formation ofdiiodosuccinnic acid, an interchange of position of the iodine- andhydrogen-atoms ; the removal of a, molecule of hydrogen iodide givesethyl iodofumarate, which in its turn is reduced by the hydrogen iodideto ethyl fumarate.The reverse process of conversion of fumaric into male'ic acidthrough the intervention of dibromosuccinic acid can be explained inlike manner.The isomerism of crotonic and isocrotonic acid is alsoof a similar order, the constitution of the one being expressible by aformula 11 , of the other as 11 . Cinnamic acidshould also exist in two geometrically isomeric forms, of which, asyet, only one has been obtained.HC-COOHH*C*Me Me43.HHOCOOH H*C*COOH/it-Coumaric acid has the plane symmetrical arrangementHC CeH,. 0 Has it is easily converted into its lactone, conmarin ; i n its isomeride, theatoms are arranged in the axially symmetrical configuration ; this, byfuming hydrobromic acid, is converted into coumarin, by temporaryaddition of a, molecule of the acid, and by an inclination towardsformation of the lactone.By this theory, the removal of the elements of a halogen acid andsimultaneously of carbonic anhydride from the sodium salt' of ap-halogen substituted acid is expiained, as also the foi-mation ofanhydrides and lactones when two carbDxyl- or a hydroxyl- andcarboxyl-group are in the y-position.The author is engaged on experimental evidence in favour of thistheory.V. H. V.Nitrosates, Nitrosites, and their Derivatives. By 0. WALLACH(dnnalen, 241, 288--315).-The crystalline compound which Guthri38 ABSTRACTS OF CHEMICAL PAPXRS.(Annulen, 116, 248 ; 119, 84) obtained by the direct union of amylenewith nitrogen peroxide, is most conveniently prepared by passing thenitrous fumes evolved by the action of strong nitric acid on arseniousoxide into a well-cooled mixture of amylene (1 vol.) and glacial aceticacid (2 vols.).The operation is interrupted when the colour of theliquid changes from blue to green. The crystals are washed withacetic acid, afterwards with water. As commercial amylene is amixture, the product is not homogeneous. On recrystallisation fromchloroform or benzene, two substances having the compositionC5H,,N20a are deposited, namely, cubes melting at 96-97', and needlesmelting a t 89". This compound is not a dinitrite but 8 nitroso-nitrateor nitrosate.On boiling with alcohol and aniline, it yields anilinenitrate and nmyZenenitrolaniZine, NHPh*C5Hg : NOH. The basemelts a t 140-141". It dissolves freely in ether, chloroform, warmalcohol, and in dilute acids, and crystallises well. The hydrochloride,CIIHl,N20,HC1, is deposited from a hot aqueous solution in anhydrouscrystals. It is best prepared by passing hydrogen chloride into anethereal solution of the base, when the hydrochloride is precipi-tated in the form of a crystalline powder. The w'troso-compound,NO*NPh*C,H,:NOH, is deposited as a crystalline powder when asolution of sodium nitrite is poured into ail acid solution of tLe base.It melts at 327-128", and is soluble in alcohol and in alkalis.Thenitroso-compound is reprecipitated on adding an acid to t,he alkalinesolution. The hydrochloride is decomposed by boiling with water,or better with hydrochloric acid, yielding hydroxylamine and a ketondbase, NHPh*C,H,: 0. The new base melts a t 61", and is soluble inalcohol, ether, and in hot, 6ater.AmyleiLenitro123ctratolzl.idine, CI2HlsN20, and its hydrochloride andnitrate form well-developed crystals. The base melts a t 111-112",and the nitroso-derivative a t 147-148". The hydrochloride is decom-posed on boiling it with hydrochloric acid, yielding hydroxylamineand the base C,,H,,N20 melting a t 98".The nitroso-derivativemelts with decomposition a t 149-150". The hydrochloride is moresoluble in water than the corresponding para-salt.Amylenenitrolorthoanisidine melts a t 138-139".The hydrochlorideis deposited from its aqueous solution in prisms. Amylene nitrosateand piperidine act on each other very energetically, forming a crystal-line base, C,,H,,N,O. It melts at 95-96", and is insoluble in waterand in alkalis. The hydro-chloride is art oily liquid, but the platinochloride (c,,H,oN,0)2,HB,PtC:16,forms beautiful prisms. Arnylenerzitroldiethyla~t~ine crystallises i4plates and melts a t 71-72". ArnylenenitroEalLylamine is soluble inwater. The hydrochloride, C8H16N20,HCl, is crystalline. This base isisomeric with nitrosoconiine.Amylene nitrosate acts on sodium ethoxide, forming a crystallinecompound which melts a t loo", and also on ethyl acetoacetate, yieldinga crjstalline compound of the compositionAmylenenitrolorthotoluidine melts a t 115".The Yalts dissolve freely in water.C,H,,NO*CH(C OMe) *COOEt.Guthrie (bc.cit.) observed that amyl nitrosate acts on potassiuORQANIC CHENISTRY. 39cjanide, but the author finds that a crystalline compound and potas-sium nitrate, not a liquid and a m i t r i t e , are formed in the reaction.A blue crystalline compound is formed by passing nitrous fumesinto brornamylene dissolved in acetic acid, and pouring the crudeproduct into water. This compound acts on piperidine at the ordinarytemperature, yielding a colonrlesg, crystalline substance which exhibitsneither acid nor basic properties. It is soluble in alcohol, is rich inbromine, and has an odour resembling that of camphor.Synthetical Experiments in the Sugar-group.w.c. w.By E. FISCHEBand J. TAFEL (Ber., 20, 8566-2575).-1t was previously shown(Abstr., 1887, 651) that acraldehyde bromide is converted by barytainto what is probably a glucose. With phenylhydraaine, the productof the reaction yields a- and P-phenlylacrosazones, melting a t 205'and 148" respectively.When isoglucosamine oxalate (Fischer, Abstr., 1886, 934) is dis-solved in ice-water (10 parts) and treated with sodium nitrite, anevolution of nitrogen takes place ; after three hours, the temperatureis aliowed to rise to 20". The product is exactly neutralised withaqueous soda, evaporated in a vacuum, and the residue extracted n-ithabsolute alcohol. On evaporating the solution, levulose is obtained asa yellowish syrup ; the spec.rotatory power a t 80"=25". It producesstrong fermentation with yeast in 10 minutes, gives a precipitateof pheny lglucosazone wit'h phenylhydrazine, and yields Kiliani's levu-lose hydrocyanide when treated with hydrocyanic acid. The consti-t ution of isoglucosamine is probably NH2.C &,*GO. [ CH( OH) I3.CH2.OH.Ledderhose's isomeric glucosamine has possibly the constitutionC: 11 0. C H ( N H,) [ C H ( 0 H ) ] BG H i 0 H .a-Phenylncrosazone is obtained in the following manner : A solu-tion of 75 grams of pure, crystallised barium hydroxide in 1-25 litreOF water is cooled with ice-water; 50 grams of freshly-distilledacraldehyde bromide is then added by drops, the baryta solutionbeing kept violently shaken.Eight preparations are united, madeslightly acid with sulphuric acid, and treated with a strong solutionof sodium sulphate until the barium is completely precipitated. After12 hours, it is filtered, neutralieed with aqueous soda, and evapo-rated in it vacuum to 18 litre. When cold, a solution of phenyl-hy drazine hydrochloride (50 grams) and sodium acetate (50 grams)in 100 C.C. of water is added, and the whole left for 12 hours; itis then filtered and warmed on it water-bath wikh 150 grams more ofphenylhydrazine hydrochloride and 150 grams of sodium acetatre. Inthe course of foul. hours, a half crystalline and half resinous preci-pitate separates; this is washed with water and extracted withether, when the greater part of the resin and the /I-phenylacrosazonedissolves, leaving the a-phenylacrosazone.After filtration, the a-com-pound is repeatedly extracted with boiling alcohol, and treated withhot water, after which it is almost pure. The yield from $00 gi*ams ofbromide is 18 grams. It melts a t 205" (uncorr.), and is very sparinglysoluble. On addiug water to the hot alcoholic solution, it sepwntssin long, slender needles.a-Acrosaniine, Cs&N05, is prepared similarly to isoglucosamin40 ABSTHACTS OF CHEMICAL PAPERS.(Zoc. cit.) by reducing the acrosazone with zinc-dust and acetic acid,and is purified by means of the oxnlate. It shows all the reactions ofthe glucosamines. When the oxnlate is dissolved in ice-water andtreated with sodium nitrite, a-acrose, C6H120,, is formed; this isobtained as a light-brown syrup, having a sweet taste.It reducesFehling's solution.p-Pheiiy Lncrosazolte, C,aH22N404, is obtained by evaporating itsethereal extract' (obtained in the purification of the a-compound), dis-solving in alcohol, and precipitatiag with water. The dried productis exhausted with cold benzene several times. The yellow crystalline~esidue is boiled with acetone (2 parts), filtered, and precipitatedwith ether and light petroleum. It crystallises in slender, yellownsedles melting at 148", dissolves in alcohol and acetone much morereadily than the a-compound, but is almost insoluble in ether whenpure. The yield is small.The resemblance of a-phenylacrosazone to phenylglucosazone makesi t probable t.hat a-acrose has the constitution expressed by the formulaOH.CH,*[CH(OH)]4*CIEE0 ; the constitution of p-acrose would thenbe OH*CH,*CEI(OH)*CH(OH)*C(OH) (CH2*OH)GH0 orOH.CH,.CH(OH).CH( OX).CO-CH(OH)*CH2*OH.The lower melting point and more ready solubiIity of the p-osazonepoint to its being a derivative of a sugar with an abnormal carbon-chain.Isodulcitolphett yllydrazine, CsHl,04 N2H Ph, mystallises from alcoholin colourless plates melting at 159'.It is insoluble in ether, readilysoluble in water and in alcohol. The aqueous solution is dextro-rotatory.Lactosephen?/Zhyarazine, C16HPBOION2, is prepared by adding phenyl-hydrazine (1 part) to a solution of milk-sugar (2 parts), in hot water(2 parts). After two days, twice the volume of absolute alcohol isadded, and the whole treated with much ether.The syrupy preci-pitate after being repeatedly dissolved in alcohol and precipitated withether, is obtained as a solid mass. I t is filtered, quickly washedwith ether, and dried in a vacuum over sulphuric acid. It dissolvesreadily in water and in alcohol, and is insoluble in ether. It islaevorotatory. N. H. M.Isonitrosogalactose. By P. RISCHBIETH (Bw., 20, 2673-2674).-When galactose (1 gram) and hydroxylamine hydrochloride(0.4 gram) are dissolved in a sniall quantity of water, treated withsodium carbonate (0.65 gram), and allowed to remain for 24 hours,isolzitrosogaZwttose, C6H1,0, : NOH, is obtained as a colourless, crys-talline substance which melts at 175-176", and is readily soluble inhot water, soluble in hot dilute alcohol, and practically insoluble inether and absolute alcohol.Under similar conditions, no separationcould be obtained from dextrose, levulose, or arabinose. w. P. w.By C. WEHMER(Ber., 20, 2614--2618).-Plants which readily produce starch fromdextror;le, cane-sugar, mannitol, and glycerd, do not produce starchin any determinable amount from formose.The Carbohydrate Character of FormoeeORGANIC CHERIISTRY. 41When 28 grams of formose syrup is boiled with 100 C.C. of wuterand 5 grams of hydrochloric acid (sp. gr. 1.2) for 11 hours, a sepa-ration of humic suhstance (3.5 grams) takes place. The filtrate showsthe iodoform reaction distinctly and reduces Fehling's solution. Nolevulinic acid is formed.13 per cent. phosphoric acid produced thesame decornposition, also without formation of levulinic acid.The author concludes t h a t formose is not a carbohydrate.Saccharification in Vegetable Tissues. By BONDONNEAU andFORET (Compt. rend., 105, 61 7--618).-The amylaceous plant isheated at 90-100" with acid of 1 t o 2 per cent., and the starch isgradually and completely converted into dextrin, glucose, saccharose,&c., and the soluble products thus formed diffuse through the cell-walls into the surrounding liquid. When the proportion of sugar inthe liquid ceases to increase, the process is finished. This method isreadily applied on a large scale. The exhausted pulp is free fromstarch, but constitutes a valuable nitrogenous food-stuff for cattle.The pulp from maize has the composition,-Water, i9.15 ; ash, 1.22 ;nitrogenous matter, 8-38 (containing nitrogen, 1.31) ; oil, 5.48 ; cellu-lose and loss, 5-77 = 100.It will be observed that water has beensubstituted for the starch.N. H. M.C. H. B.Amines of the Paraan and Benzene Series. By MALBOT(Compt. rend., 105, 574-576) .-In the reactions described, unlessotherwise stated, the substances were mixed in equal molecular pro-portions.Ethylamine and aqueous ammonia at 100" yield triethylamine, butst 130" tetrethylammoniurn chloride is obtained in considerablequantity. Propyl iodide under the same conditions yields tripropyl-ltmine at loo", snd tetrapropylammonium iodide at 150". Althoughpure tripropylamine combines but slowly with propyl iodide in thecold, combination becomes complete at 150".Tripropylamine has noaction on propyl chloride in the cold, and the reaction takes placeslowly at 150", but becomes very rapid at 190", the products beingtripropylamine and dipropylamine hydrochlorides and propylene.Rutyl iodide and aqueous ammonia at 160" yield only tributylamine,and the action of tributylamine on butyl iodide is strictly analogoust o that which takes place with the corresponding propyl-derivatives,Tributylamine acts slowly on -butyl chloride at 80°, but at 170" piiredibutylamine hydrochloride and butylcne are obtained. Dibutyl-amine and butyl iodide in the cold yield dihutylamine hydriodideand free tributylamine; at a higher temperature, the reaction isanalogous to that obthined with the chloride.Isoamsl iodide and aqueous ammonia at 150" yield tetramyl-ammonium iodide.T'riamylamine acts slowly on amyl iodide in thecold, but at 150" triamylamine hydriodide and amylene are formed.At ZOO", the reaction is very rapid, and the products are diamylaminehydriodide and amylene. With amyl chloride, a salt of trinmylamineis formed at 17O", and undergoes no further alteration even at '210".Dinmy lamine and amyl iodide yield diarnylamine hpdriodide, freetrismglamine, and te tramylarnmonium iodide42 ABSTRACTS OF CHEMICAL PAPERS.Capryl chloride with aqueous ammonia in equal molecular propor-tions at 170" yields monocaprylamine together with a small quantityof the dinmine and caprylene. With twice the proportion of ammonia,the diamine is the chief product,, and no caprylene is formed.Capryliodide with an equivalent quautity of ammonia a t 160" yields onlymonocaprylamine, either free or tocether with caprylene, the latteroccupying a t 120" a volume equal to half the volume of capryl iodideused.Benzyl and metatolyl chlorides yield the tertiary amines almostexclusively, whilst cinnarnyl chloride yields the secondary amine, Thebases are obtained in the form of salts by the action of the correspond-ing alcoholic chlorides. The formation of a bivalent hydrocarbon isespecially marked with styrolylamines, cinnamene being obtained inlarge quantity. It is identical w i t h the synthetical cinnamene ofBerthelot, and part of it is obtained in the form of metacinnamene.Whether the products of these reactions are in the free stmate or inthe form of salts is determined by the conditions of equilibriumbetween the rival attractions of the ammonia and the amines for theethereal salt which is present, and the acid contained in this salt.The increasing complexity of the amines is the result of a series ofsuccessive tlransformations, a bivalent hydrocarbon being producedsimultaneously.This last fact is i u favour of the ethylene theory ofthe constitution of amines. C. H. B.Allyl-diguan idine and its Derivatives. By A. SMOLEA (Monatsh.;8,3i9--390) .-Allyldiguanidine copper silkhate, ( C,H,,N,),Cu,H,S04,is obtained by dissolving dicyandiamide in aqueous copper sulphatoand adding allylamine; the mixture is then heated for some hoursat 100".This salt is more soluble in alkaline solutions than in purewater ; it separates from boiling solutions in carmine-red, anhy-drous crystals, from cold solutions in pale rose-coloured, microscopicneedles with 1 mol. H,O. The other salts were made from the fore-going by double decomposition. The chloride, (C5H,0N,),C~i,2HC,1 +2H,O, yields groups of rose-red crystals easily soluble in water to anamet hyst-coloured solution. The nitrate, ( C5H1,N5) Jh,2HN 03, formsdark-red crystals easily soluble in water. Other salts were prepared.Copper-allyldiguanidine, ( C6H10N6)2C~, was obtained by precipitatinga boiling solution of the sulphate with soda. It crystallises in darkrose-red needles, sparingly soluble in cold, more soluble in boilingwater. A solution of this base precipitates metallic hydroxides fromsolutions of metallic chlorides, the chloride described above remainingi n solution.Allyldiguanidine sulphute, ( C3H,lN5)2,H2SO* + QH20, was obtainedby the action of hydrogen sulphide on the copper salt suspended inwater.It crystallises in prisms, and is soluble in water, insoluble inalcohol. The acid sukhate, C5Hl,N5,H2SO~ + $H,O, crystallises inscales. The chloride, C5H,lN5,HCI, yields transparent prisms easilysoluble in water and alcohol. It yields no precipitate with PtCl,,nor with potassium tartrate. The acid chloride, C5HllN6,2HCl, formssmall, transparent prisms easily soluble in water and alcohol. AIZyl-diguanidine, CZH6N5*CBH5, was prepared by treating a solution of theWhen heated above 130°, the base decomposesORGANIC CHEMISTRY.43raulphate with the calculated quantity of barium hydroxide and alsoby the action of hydrogen sulphide on copper all yldiguanidine sus-pended in water. It forms a dightly crystalline, very hygroscopicmass, is strongly alkaline in character, displacing ammonia from itssalts and absorbing carbonic anhydride from the air. When heatedwith potash and chloroform, it yields allylcarbamine (C,H,*NC).In chemical characteristics, the above copper compound somewhatresembles the alkalilie earthy metals, the allyldiguanidine, the alkalimetals and especially sodium.Isonitroso-compounds. By E. BECKMANN (Ber., 20,2580-2585 ;compare Abstr., 1887, 826) .-The intramolecular change which takesplace when diphenylketoxime is treated with phosphorus pentaclilorideor with sulphuric acid, is also produced by hydrochloric acid, acet,icchloride, acetic anhydride, and acetic acid.When a cooled soluti.on of diphenylketoxime in 10 parts of glacialacetic acid containing acetic anhydride is saturated with hydrogenchloride, and then heated at TOO", the oxime is completely convertedinto benzanilide; this is precipitated by sodium carbonate, and re-crystallised from alcohol.~~ethy~phenylk~toxime when similarlytreated yields acetanilide, which separates as hydrochloride on coo 1-iiig the solution; the reacfion takes place in the cold, but requiressome days.Methylpropylketoxime is converted by hydrochloric acid into thecompound NHPr*CMeO,HCl, and not into the compound NHMe-CPrO.When diphenylketoxime is heated with acetic anhydride in presenceof hydroxylamine hydrochloride a t 150", acetanilide and benzoic acidare formed.Methylphenjlketoxime when heated with 10 parts ofacetic anhydride for six hours a t loo", yields the compoundCMePh : N*OAc (Rattner, Rer., 20, 506). This crystallises fromlight petroleum in forked needles mel6ing a t 55".Glacial acetic acid at 180" acts on diphenylketoxinie with forma-tion of benzanilide, acetanilide, and benzoic acid. Methylphenyl-ketoxime is converted by hot glacial acetic acid into oily products ;acetanilide is not formed. I?. H. M.L. T. T.Oxidation by Means of Hydrogen Peroxide. By C.WURSTER( B e y . , 20, 2631--263S).-The author showed previously (Centr. fiirYhysiol., 1887, 33) that organic acids are quickly oxidised by hydro-gen peroxide to carbonic anhydride ; the higher fatty acids and oils,cane- and grape-sugar, are rather stable towards hydrogen peroxide,whilst boiled starch is converted first into crythrodextrin and theninto sugar.Hydrogen peroxide (6 mols.) reacts with hydroxylamine sulphate a t40" with formation of sulphnric acid, nitric acid (2 mols.), and water(12 mols.) . Hydroxylamine hydrochloride is similarly converted intohydrochloric and nitric acids and water.When an aqueous solution of phenol is treated with a hydroxyl-amine salt aud hydrogen peroxide, nitrosophenol is formed.Phenylhydrazine is converted by hydrogen peroxide into benzeneand diazobeuzeneiinide.The production of benzene makes it pro-The yield is quantitative44 ABSTRACTS OF CHEhlICAL PAPERS.bable that free diazobenzene is first formed in the oxidation of theh y drazi ne.By P.RISCHBIETH (Ber., 20, 2669-2673).-Isonitrosovaleric mid (Abstr.,1883, 1129) can readily be obtained by dissolving hydroxylaminehydrochloride (50 grams) and levulinic acid (83 grams) in a smallquantity of water and adding a concentrated aqueous solution ofsodium carbonate (38 grams) ; a separation of the acid immediatelyoccurs, and this is pi-rrified by recrystallisation froni water. Theyield amounts to 90 per cent. of that theoretically possible. Whentreated with hydrogen chloride, the acid melts and absorbs the gas,and on warming the product, a sudden reaction occurs with the evolu-tion of nitrogen, and production of a black residue.On oxidationwith dilute nitric acid, a large volume of gas is evolved, and aceticand succiriic acids are formed; the residue is, moreover, found to befree from nitrogen. If the acid (6 grams) is heated with sulphuricacid( 10 grams) in a vacuum at 150", succinic acid sublimes, and nitrogenis evolved ; when, however, a much larger proportion of sulphuric acid(36 grams) is employed, and the heating is continued jor 6 to 12hours at 100" at the ordinary pressure, the elements of a molecule ofwater are withdrawn from the molecule of isonitrosovaleric acid, andthe " inner anhydride," npvaleroximidolactone, together with succinicacid, resu1t.s.N.H. M.Isonitrosovaleric Acid and v-Valeroximidolactone.r- Valeroximidolactone, CM&EH<g2>C0, cryskllises from etherand water in long, white prisms; it melts at 69-70" when slowlyheated, and at a somewhat higher temperature when the heat'ing ia rapid,and boils at 232" without decomposition. When heated with aqueousalkalis, it yields the corresponding salts of isonitrosovaleric acid, butdilute sulphuric acid, hydrogen chloride, fuming hydrochloric acid,and ammonia are without action on it at 100". O n distillation withnitric acid (sp. gr. = 1*4), a distillate is obtained which contains inaddition to unaltered lactone at least two distinct crystalline com-pounds ; these have not yet been further examined.New Source of Capric Acid.By A. BUISINE and P. BUTSINE:( C o n y t . rend., 105, 61&617).--Capric acid does not exist as such insuint, but au aqueous solution of suiiit undergoes fermentation underthe influence of microbes, and the quantity of fatty acids and especi-ally of capric acid is greatly increased, the proportion of the latterrising to 5 per cent.The capric acid ir;; separated by distillation, saponification, andsubsequent fractionation, and is finally crystallised from boiling water.It forms a crystalline, buttery mass, with an odour of rancid butter,melts at 31", is soluble in alcohol and ether, and is slightly soluble inboiling water, from which it crptallisea in white needles. Thebarium salt is soinble in alcohol.C. H. B.W. P. W.Linoleic Acid. By L. M. NORTOX and H. A. RICHARDSON (Ber., 20,2735--2736).-When endeavouring to dry linoleic acid at 100" in ORQANIC CHEM ISTRT. 45current of hydrogen, the authors found that a. continued loss of weightoccurred even after 28 hours, although no change in composition tookplace. Linoleic acid can be distilled without any appearance of de-composition at 290" under 89 mm. pressure, and a colourless productis obtained amounting to about three-fourths of the mid taken. Thisconsists of an acid, CmH%O2, which cannot again be distilled in avacuum without decomposition; its sp. gr. is 0.9108 a t 15", and itsvapour-density = 153.Under similar conditions, ricinoleic acid yields an acid agreeing inButanedicarboxylic Acid.By R. OTTO and A. R~SSING (Ber., 20,2736-2747).-By the reduction of dimethylmale'ic acids, two batane-dicarboxylic acids are obtained, the one, melting at 193-194', whichhas been shown to be symmetrical dimethylsuccinic acid, the other,ethylmethylmalonic acid, melting at 118-120". I n this paper, theanhydrides of these acids are more particularly studied. The formeron dry distillation yields an anhydride melting at 87", previouslydescribed by Bischoff and Rach ; but thiR substance on rehydrationand crystallisation from the aqueous solution yields not only theoriginal or symmetrical dimethylsuccinic acid, but also the above-mentioned isomeric ethylmethylmalonic acid. On the other hand,the symmetrical dimet hylsuccinic acid, when treated with excess ofacetic chloride, yields an anhydride isomeric with the above, whichcrystallises in rhombic tables melting at 38"; this on rehydrationyields the original acid only.Again the butanedicarboxylic or ethylmethylmalonic acid, meltingat 121", remains unaltered on dry distillation, but when treated withacetic chloride i t yields a n anhydride of the same melting point,86-87", and crystalline form as the former of the anhydrides mentionedabove, but which, however, differs from it in yielding on rehydrationthe original acid only.Distillation of Citric Acid with Glycerol.By P. DE CLERMONTand P. CHAUTARD (Compt. rend., 105, 520-523).-500 grams ofcrystallised citric acid mixed with 750 grams of ordinary glycerol of28" are distilled in a glass retort of 3 litres capacity, and the productredistilled. The first fraction consists of about 250 grams of watercontbining a small quantity of acraldehyde, &c.; some crystalsalso separate in the colder part of the apparatus. The mass thenswells up, and the teriiperature musk be reduced, but it is afterwardsgradually raised until the distillation is complete. The distillateduring this second stage consists of 650 to 700 grams of liquid. Thetotal products of the decomposition are 950 grams of liquid, 30 gramsof a bulky, carbonaceous residue, carbonic oxide and carbonicanhydride, and vapours of acetone and acraldehyde. I n addition towater containing small quantities of acraldehyde, the only products inthe distillate are unaltered glycerol and pyruvine or the pyruvic ether ofglycide, MeCO*COO-CH,.CH<-O->, which is also obtained by thedistillation of glycerol with tartaric acid or glyceric acid.Probablycomposition with that just described. w. P. w.V. H. V.CH46 ABSTRACTS OF CHEMICAL PAPERS.the pyruvine is a product of the reaction between glycerol and glycericacid, the latter being formed as an intermediate product.The pyrnvine thus obtained crystallises in large, prismatic needles,or tables, which melt a t 82" and boil a t 241" under a pressure of764 mm. C. H. B.Double Lactone of Metasaccharic Acid. By H. KILIANI (Bw.,20,2710-2716) .-The oxidation product of the lactorie of arabinose-carboxylic acid (Abstr., 1887, 465) dissolves readily in aqueousammonia, and from the solution the diumide of metasaccharic acid,C,H,,O,N,, separates as a white powder, consisting of microscopic,tabular, monoclinic crystals, which become yellow a t 170" and melt a t189-190" with complete decomposition.The compound has aneutral reaction, and when heated at 100" with potassium hydroxideFields the potassium salt of metasaccharic acid as a colourless syrup ;this becomes crystalline on stirring, and in aqueous solution doesnot reduce Pehling's solution.On treatment with a cold solution of phenylhydrazine hydrochloride(1 part) and sodium acetate (1.5 pwt), in water (10 parts), the oxida-tion product yields the monophenylh ydrazide of the lactone of meta-snccharic acid, Cl2HI40,N2 ; this crystallises in colourless, microscopicmales with 8 mol.H,O, dissolves readily in hot water and alcohol, andwhen rapidly heated becomes yellow at 185", and melts a t 130-192"with decomposition. If the mixture w i t h phenylhydrazine (which,to obtain the preceding compound is allowed to remain for 20 minutesfor the crysta,llisxtion to take place) is a t once poured into boilingwater, the diphenylhydj-azide of metasaccharic acid, CleH2206N,, separate8after 10 to 15 minutes in yellowish-white, microscopic scales, whichbecome yellow a t 210°, melt at 21 2-213" with decomposition, and arevery sparingly soluble in boiling water aiid alcohol. The solution inconcentrated sulphuric acid is coloured red or bluish-violet by ferricchloride.When the oxidation product (12 grams) is dissolved in water(300 grams), treated with 3 per cent.sodium amalgam (200 grams),and dilute sulphuric acid added gradually so that the solution neverbecomes alkaline, allowed to remain fire days with a farther 200 gramsof sodium amalgam, then treated with sulphuric acid and alcohol tofree the product from sodium sulpliate, and the mother-liquorevaporated, a syrup is obtained which still reduces alkaline coppersolution, and from which mannite (2 grams) crystallises on standingover sulphuric acid. The strongly acid mother-liquor seems to consistof the lactone of a bibasic acid (? metasaccharic acid), a strongly acidsyrup having similar properties being also obtained by continuedheating of the oxidation product with water, or by repeated evapora-tion of its aqueous solution.The oxidation product of the lactone of nrabinose-carboxylic aciddissolves in 18, not, 8, parts of cold water (compare loc.cit.), andreadily reduces alkaline copper solution. The aqueous solutions of itspotassium and sodium salts, even in the absence of free alkali, becomecolonred intensely red on heating, or when allowed to evaporatespontaneously (Ber., 20, 343). The author, however, concludes, froORGASIC CHEhlISTRP, 47the preceding experiments, that the oxidation product is not thelactone of a ketonaldehydic acid, but is a double lactone of meta-CH(OH)*CH*O.CO -saccharic acid, I ), orwhich, on account of its peculiar constitution is very labile, and ontreatment with alkalis even at the ordinary temperature undergoesmolecular change, or perhaps reduction to an aldehyde -compoundjielding mannite by the action of nascent hydrogen.Thiohydantoin.By R. ANDREASCH (Monatsh., 8, 407-424).-Loven has recently shown (Abstr., 1885, 241) that a methylene-groupsituated between a carbonyl-group and a sulphur-atom possessessimilar properties to the methylene-group in ethyl malonate andacetoacetate. With the object of ascertaining whether this is thecase in hydanto'in, the author has prepared the disilver-derivative, andfrom that the dimethyl-compound,Disilz~e~-tJ~iohydan.to'i?z, Ag2C3N,H2S0, was obtained by adding a warmaqueous solution of thiohydantoTn to ammoniacal silver nitrate. Itforms a white, granular substance, sparingly soluble in nitric acid,insoluble in ammonia.I t blackens when exposed to light. Whentreated with methyl iodide, the silver compound yields P-dimethyithio-hydantozn, XH C<,,.,,>. This substance is easily soluble inwater, sparingly in cold alcohol, crrstallises in hexagonal scales, meltsat 114", and decomposes at a slightly higher temperature. Whenoxidised in hydrochloric solution by barium chlorate, carbonic anhy-dride and mei-captan are evolved, and the residue is found tocontain carbamide, and a mixture of barium salts which cannot beseparated, but one of which seems to be barium methylsulphonate.When heated wit,h barium hydroxide, the hydantoi'n yields cyanamideand some sulphur compounds which could not be isolated.Witlh the aim of determining the constitution of tlhe above com-pound, the author atternpted to prepare the two isomeric dimethyl-hydanto'ins in other ways.a-Dimethylthiohydan.tozn,W. P. W.S*CMe2may be prepared by heating together dimethylthiocarbamide and chlor-acetic acid in aqueous solutioi~. It is easily soluble in water, alcohol,ether, and carbon bisulphide, crystallises in long, thin, colourlessprisms, melts at 71", and boils a t a rather higher temperature. Itvolatilises slowly a t ordiuary temperatures. It bas an odour some-what resembling that of nicotine. When heated with aqueous alkalis,it yields thioglycollic acid. The isonitl.oso-derivative, C,H,N,SO,,yields yellowish scales melting at 220". Imidocarbnminethioisobzl,tyri,:anhydride, C5N2H8S0, was prepared by heating together thiocarb-amide and x-bromisobutyric acid.It crystallises in plates, is easil48 ABSTRACTS OF CHEMEIIICAL PAPERS.soluble in alcohol and boiling water, sparingly in cold water, andmelts at 242". When oxidised with nitric acid, this substance yieldscarbamide and sdphoisohufyric mid, SO,EI*C,H,~COOH, which formsa barium salt, BaC,H,SO, + 4H,O, crystallising in needles, easilyRoluble in water, insoluble in alcohol. The sodium salt, Na,C,H,SO, +&H20, forms glistening needles eiisily soluble in water, insoluble inalcohol. The same sulpho-acid is obtained by the action of chloro-sulphonic acid on isobutyric acid. The action of ammonium sulphiteon a-bromisobutyric acid produces, however, an isomeric sulpho-acid,yielding an easily soIuble barium salt, BaC4H,S05 + 2H20, cryeta1-lising in needles.It is thus clear that this imido-anhydride is not, identical with the/3dimethglthiohydantoYn, as the author had anticipated. As it waspossible that in the formation of the imido-anhydride a transformationfrom the iso- to the normal butvric series had occurred, the authorS*CHEt prepared imidocarbaminethiobu~~,yric anhydride, NH : C<NH.co >,by the action of a-bromobutyric acid on thiocarbamide.This crystal-liRes in short, thick needles, easily soluhle in boiling water, and meltsat 200". It is not identical with the compound obtained from iso-butyric acid. The constitution of the latter is therefore still doubtful,but its formation may perhaps be due to the action of thiocarbamideon the methacrylic acid formed by the elimination of hydrogen bromidefrom the bromisobutyric acid,CH,: CMe*COOH + CS(NH2)2 = CHMe<Co.2GH>C 1 NH + H20.The consitution of the ,&compound would then be correctly expressedby the formula given above.Thiohydantok when treated with benzaldehpde yields amidinethio-cinnanzic ( b e n z ~ l i d e n e t h i o h y d n ~ ~ o ~ c ) acid, NH C(NH,)(COOH) CHPh ;this forms white, microscopic needles, insoluble in water, soluble inalcohol.Several salts of thioliydantoin are described.The subphate,(C3H,N,S0)2,H2S04, forms plates soluble in water ; the nitrate, flatneedles or prisms ; the ozalate, C,H4N2S0,C2H,04 + H20, prisms ;the pzcrate yellow, microscopic needles.Thiohydantoin is best prepared as follows : 50 grams of thiocarb-amide is dissolved in + litre water, and 62 grams of chloracetic aciddissolved in 50 C.C.of water added. The whole is heated a t 80-90"until reaction has ceased, and when cold it is gradually neutralisedwith soda, care being taken never to let the solution become alkaline.Orthothioxen and Orthothiophendicarboxylic Acid. By W.GR~NEWALD (Ber., 20, 8585-2587).-0rthothioxen (Paal, Abstr.,1887, 1101) is prepared by distilling an intimate mixture of 10 gramsof p-methyllerulinic acid and 17 grams of phosphorus trisulphide ina, capacious retort. 250 gi*ams of methyllevulinic acid yielded 150grams of pure product. It is a colourless, strongly refractive oil,h%ving an odour of petroleum ; it boils a t 136-137" (corr.).Sp. gr. at21" = 0.9938. When treated with 1 per cent. solution of potassiizm per-manganate, a monocarboxylic acid only is formed ; this melts a t 134.5".CH SSimilar a,cids seem to be produced with other aldehydes.L. T. TORGANIC CHEMISTRY. 49Ort7~othiophendicarboxylic acid, C4SH,(COOH)2, is obtained by theaction of 1 per cent. permanganate solution on the monocarboxylicacid ; the product is steam-distilled to remove unchanged mono-carboxylic acid. It crystallises in long needles which do not melt a t860", but decompose at a higher temperature. When heated withrcsorcinol at 200", a product is obtained which dissolves in strongaqueous alkali with dark-red coloration ; the colour changes to yellowon diluting with water; the solution then shows a yellowish-greenfluorescence.The silver salt forms white flakes irisoluble in water ;the barium saZt separates in colourless crystals, readily soluble in hotwater. The dimethyl salt crptallises from alcohol in colourless platesmelting at 595". N. H. M.Action of Carbonic Anhydride on Aromatic Amines. ByA. DITTE (Compt. rend., 105, 612--614).-When an aniline salt ismixed with an aqueous solution of a normal or hydrogen carbonate,carbonic anhydride is given off, and aniline separates in the free state,no aniline carbonate being formed. Carbonic anhydride is not solublein aniline, and does not combine with i t under ordinary pressure evenat -8', the temperature at which aniline solidifies.I€, however, dry carbonic anhydride and aniline are compressed ina Cailletet's apparatus, the auiline dissolves the carbonic anhydride,jncreasiug to about twice its original volume, and a limpid layer ofthe liquefied gas swims on the surface of the solution and volatilisesat 15" under a pressure of 40 atmos.If the compressed liquid iscooled to 8-10", it crystallises in transparent, white needles, andwhen the aniline and carbonic anhydride are in equal molecular pro-portions, solidification is complete. When the carbonic anhydride isin excess, it forms a, layer above the crystals. When aniline is inexcess, it does not at once dissolve the carbonic anhydride, and thefwo liquids form distinct layers, but on gentle agitation the carbonicanhydride is dissolved, and crystallisation takes place a t 8".It isevident that carbonic anhydride and aniline combine in equal molecu-lar proportions to form a compound which crystallises a t 8", andis liquid or remains in superfusion at loo, and decomposes when thepressure is released. The tension of dissociation a t different tempe-ratures is as follows :-Temperature . . . . . . . . . . 0" 2" 5" 7"Pressure in atmos. . . . . 6 9 17 28Orthotoluidiiie behaves in a precisely similar manner, and the com-pound crystallises in brilliant, white needles. The behaviour of meta-xylidene is similar in that the two liquids mix, but no crjstals formeven a t -12".Pyridine and its homoIogues show no tendency to combine withcarbonic anhydride ; the two liquids do not mix. C. H. B.Benzylidene Compounds. By L.ROHLER (,4nrzaZen, 241, 358-362) .-An alcoholic solution of berizylidenepara toluidine is convertedinto benzylparatoluidine by the action of sodium amalgain. TheVOL. LIV. 50 ABSTRACTS OF CHEMICAL PAPEM.base distils at 33.2-313", and solidifies in the course of several weeks.it is freely soluble in alcohol and ether. The hydrochloride is solublein alcohol and in hot benzene, and the sulphate is soluble in water.The nitroso-compound melts a t 53".Benxyl-~-na~~hthylamime cr;gstallises in prisms, and melts a t 68". Thenitroso-derivative forms yellow needles, soluble in alcohol, ether,benzene, and light petroleum.Benzy Zarnidodimethy Zaniline, prepared from the condensation-productof benzaldehyde and smidodimethylaniline, melts st 48", and distilswithout decomposition.The nitrosnnzins is deposited from alcohol inyellow needles.It melts a t 111-112°.It melts a t 127-128" with decomposition. w. c. w.Reduction Products of Bensylidene Compounds. By 0.FISCHER (AnnaZen, 241, 328-331).-The author has previouslypointed out (Abstr., 1886, 546) that 3 per cent. sodium amalgamreduces a solution of hydrobenzamide in absolute alcohol to dibenzyl-amine and monobenzylamine ; ammonia and toluene are alwaysliberated during the reaction. Under similar treatment, benzylidene-aniline is converted into benzylsniline.The salt which is deposited when nit,rosobenzyIa,niline is treatedwith a,lcoholic hydrogen chloride is a mixture of benzylaniline hydro-chloride and benzylidene aniline.w. c. w.Hydroxybenzyliden 8 Compounds. By 0. EM MERICH (AnmaZen,241, 343-358) .-Orthohydroxy benzy Zandine, HO*C,H,*CH,-NHPh,is obtained by the action of sodium amalgam on a solution of hydroxy-benzylideneaniline in absolute alcohol. It melts at 106", and issoluble in alcohol and ether. The sulphate and hydrochloride arefreely soluble in water. The platinochloride forms reddish-yellowneedles, melting a t 184" with decomposition. A tetranitro-derivative,C,H9NO(X02),, is formed when the base is treated with a mixture ofsulphuric and nitric acids. It melts a t 66" with decomposition, and issoluble in alcohol, acetic acid, and light petroleum.Orthohydroxz~ber~zyl~aratoZuid~ne, HO.C,H,.CH,.NH.CsH,Me, ob-tained by the reduction of the hydroxybenzylideneparatoluidine,crystallises in white plates and needles, and melts at 116".It issoluble in alcohol and ether. The sulphate and hydrochloride dissolvefreely in water. The platinochloride crystallises in needles. Thetetranitro-derivative formR yellow needles, soluble in alcohol, benzene,and acetic acid. By the action of methyl iodide,the base is converted into ortl~omethoellben~uy~aratoluidine,It melts a t 168".OMe.CsH4*CH,-NH*C6H4Me,a crystalline compound melting at 110", and soluble in alcohol, ether,hnd benzene.Orthodih ydroxydibenzylarnine is prepared by the action of sodiumamalgam on an alcoholic solution of hydrosalicylamide. It crystal-]ifies in needles, melts a t 170°, and dissolves freely in ether, alcohol,benzene, and light petroleum.The sulphate, nitrate, and hydroORGANIC CHEMISTRY. 51chloride are soluble in water.needles, and is soluble in water.yields on reduction orthoh2/dro;eybe.1~zyl-p-n~ph~h~lam~t~e,The platinochloride crystallises inThe condensation compound of salicylaldehgde and p-naphthyleminen crystalline substance melting at 147". It is soluble in alcohol, ether,benzene, and light petroleum. The alcoholic solution exhi bits areddish-violet fluorescence. The sulphate is liquid, and the platino-chloride crystallises with difficulty.Orthohydrozy benayl-p-n,a~hlhylnitrosamin,e melts at 165" with decom-position. On exposure to the air, the compound decomposes spon-taneously at the ordinary temperature. It is soluble in alcohol andether.Orthomethoxybenzyl-~-naphthylain,ine crystallises in needles,melts at 92", and dissolves freely in alcohol and ether.Parahydroaybenxy laniline, prepared from parahydroxybenzylidene-aniline, is soluble in alcohol and ether. It melts a t 208", and forms acrystalline platinochloride.Pal.ahydroxybenzyZtol1~idine melts at 186". Parahydroxybenzyl-P-nnphthylamine melts: at 117". The sulphate is soluble in alcohol, butalmost insoluble in water. The nitrosamine melts at 142", and dis-solves in alcohol and ether. It is unstable. w. c. w.Anisylamines. By 0. J. STEINHART (AnubaZen, 241, 332-343).-A solution of anishydramide in absolute alcohol is converted into amixture of mono- and di-anisylamine by the action of sodium amalgama t the ordinary temperature.Dianis?ylanaine, NH(CH2.C6H,*OMe)2,forms white, needle-shapsd crystals soluble in alcohol and ether, Itmelts a t 34", and decomposes on distillation. The hydrochloride issoluble i n alcohol, and crystallises in fiat prisms. It melts at 243".The platinochloride is crystalline but unstable. The nitroso-derivative,(OMe-C,H,-CH,),N*NO, crystallises in needles, and melts at 80". Anisykamine is a colourless liquid boiling at 220-223". It, is miscible withalcohol, ether, and water, and it absorbs carbonic anhydride from theair. It can be separated from dianisylamine by its volatility in acurrent of st,eam. The hydrochloride forms white plates which arefreely soluble in water, and melt at 230". The platinochloride crystal-lises in pale-yellow, glistening needles.An i s y 1 nnil ine, MeO*C6H4*C H,*NH P h , prepared from a nish ydrani lid e,crystallises in prisms, and dissolves freely in the usual solvents.Itmelts at 64*5", and forms a crystalline hydrochloride, sulphate, andplatinochloride. The nitroso-derivative melts a t 104". It crystallisesin prisms, and is soluble in alcohol.Anish ydroparatoluide, OM&C6H4-CH NC6RbMe, forms whiLe needles,and melts a t 92". Anisyl~aratoluidilze, OMe.C6H4*CH2*NH2*CsH4Me,forms white prisms, melting a t 68". It is soluble in all the usualsolvents with the exception of water. The hydrochloride and platino-chloride are crystalline, but the salts have a tendency to decom-pose when their solutions are evaporated. The rdrosamine melts at108".Anisaldehyde and orthotoluidine condense, forming anishydrortho-It melts at 210".e 52 ABSTRACTS OF CHEMICAL PAPERS.toluide, which yields orthotoluylanisylamine on reduction.The basemelts a t 55".Anis y Zid enenap hi! h y lam ine ( /3) , OMe C6H4* C H N C 1oH7, crys t alli ses inplates, and melts at 98". Anisyl-P-naphthyZa??/,ine is soluble inalcohol, benzene, and in light petroleum. It melts at 101". The saltsare sparingly soluble in water, and are rather unstable. The nitros-amine melts at 133", and crystallises in plates. AnisylidenedimethyZ-paraphenylenediamhze forms greenish-yellow needles. It melts at148", and yields on rednction anisyldimethylpcrr~pheny lenediamine,OMc*CsH4.CH,*NH.CsH4.~Me~. This base crystallises in plates, andmelts a t 104".The alcoholic solution decomposes on exposure to theThe nitrosamine is an oily liquid.air, and the nitroso-compound is unstable. w. c. w.Salts of Picramic Acid. By A. SMOLKA (Monatsh., 8, 391-398).-The salts of this acid having heen but little studied, the nut,hor hasprepared and examined a number of them. Tn some cases they wereobtained by the direct action of picramie acid on the metallic carbon-ate, in others by double decomposition. The following table showsthe results obtained :--Formula of salt. Description.Dark red crystalsDark reddish-brown walesYellow, microsco-pic needlesGreenish - yellowneedlesScarlet, microaco-pic crystalsDull yellow, mi-croscopic needleSmall, reddiuh-brown needlesDark &eel-greenneedlesGreenish- yellow,amorphouspowderamorphouspowderDark olive-green,Ratio of solubility inwater.I.Boiling.1 :4Q% at 15 -5'1 : 19.9 ,, 17 '01 : 5890 ,, 23 '01 : 1215 ,, 23 *O1:21010 ,, 17.51?3172 ,, 18.01 :2632 ,, 20.51 : 97 *5 ,, 19 -0insolubleinsoluble11. Cold--freelyfreely1 : 1842I : 3181: 124811 : 11511 : 1494freelyI : 3292I : 3538Tempera-ture ofdecompo-sition.--abont150'140140-150°140°120140-145O140-150Moo1401 a-1 45'If the salt is heated slowly, the decomposition takes place quietly,but if rapidly, explosions occur, especially with the sodium and leadsalts. The aqueous solutions vary in colonr from pale orange to darkblood-red. L.T. TORGANIC CHEMISTRY. 53Chlorine and Bromine-derivatives of Citraconanil. By T.MORAWSICI and J. KLAUDY (Monatsh., 8, 399-406) .-Citraconpara-chloranil, C5H402 : N-C6H,C1, is formed (together with chloranilines)when a stream of chlorine is passed into water in which finely-dividedcitraconanil is suspended. It crystallises in white, glistening needles,soluble in alcohol and melting a t 114,5". With care i t may be sub-limed in long, glass-like needles. When heated with ammonia, ityields parachloraniline and citraconic acid, showing the correctness ofthe above formula.When bromine acts on citraconil, bronzocitraconprLrabrornani1,C,H,BrO, : N*CsHpBr, is formed. This crystallises in white, shiningneedles, soluble in alcohol and melting at 178".It can be sublimed,b u t decomposes if heated rapidly. When heated with ammonia,parabromaniline is formed, together with hydrogen bromide, muchresinous matter, and an acid of the formiila C7H,BrOa. This acidyields a silver salt, AgzC7€3,B.rO4, crystallising in prisms, and a leadsalt, PbC7H7Br04, forming microscopic crystals. It appears, therefore,that the original bromo-derivative contained one bromine-atom in thecitraconic nucleus, and that when heated with ammonia this nucleusis converted into a higher brominated homologue of the citraconicseries, together with other bye-products.When only enough bromine is employed for the formation ofeitraconparabromanil, white, crystalline needles melting at about 11 8"were obtained, but this compound has not yet been obtained in a purestate.L. T. T.Action of Phenylhydrazine on E thy1 Chloracetoacetate. ByG. RENDER (Ber., 20, 2747--2752).--Ethyl chloracetoacetate reactswith phenylhydrazine in ethereal solution to form a compound,C12H14N202 ; it is probable that a hydrazine-derivative,NHPh*N CMeCHCl-COOEt,is at first formed, which is subsequently converted into a compound,NPli : N*CHMe*CHCl*COOEt, and finally by abstraction of theelements of hydrogen chloride into NPh : N-CMe : CH-COOEt, orethy lic P-phenylazocrotonate. This substance crys tallises in long, redneedles, meltling at 50*5", very soluble in alcohol ; on saponification, ityields a potassium salt, NPh N*CMe: CH-COOK, which formsreddish-yellow scales, very soluble in water, insoluble in alcohol.The salt on acidification yields the corresponding anhydride as abrownish-yellow powder, whose purification presents considerabledifficulty.Ethylic /3-phenylazocrotonate when reduced yields phenyl.rnethylpyrazolone and its first oxidation product or its bis-derivn-tive, together with a substance not further examined. The bis-deri-vative yields with bromine a compound, C2,€€,,NaO,Br, which crystal-lises in colourless needles, melting a t 217" with decomposition.a-Naphthylamine with ethylic chloracetoacetate yields a compound,C,,J316N02C1 ; this crystallises in colourless prisms, meltiiig at 75" ; itsformation is due to a change analogous to the first of the reactionsgiven above in the case of phenylhydrazine. V. H.V54 ABSTRACTS OF CHEMICAL PAPERS.Isomeric Phthalophenylhydrasfnes. By G. PELLIZARI (Gaxnetta,17, 278--285).-The author has previously described two isomericphthalyl-derivatives of phenylhydraxine obtained by the action ofthis base on phthalimide and phthalic anhydride respectively (Abstr.,1886, 125). To the former, melting at 179", the constitutionNHPh*N <Co>C6HH", to the latter, melting a t 210°, the constitution GONPh-CO <NH-CO>CGHa was assigned. If these formule are correct, amethyl-derivative of the former, or anilophthalimide, on separationof the phthalyl grouping, should yield a symmetrical methylphenyl-hydrazine, NPhMe*NH2, that of the latter, or phthalophenylhydrazine,the symmetrical derivative, NHPh-NHMe. Phthalophenylhydrazine,heated with methyl iodide and alcohol, yields a methyl-derivative,crystallising in long, yellowish-white prisms, which melt at 125"without decomposition ; this is decomposed by concentrated hydro-chloric acid, yielding methylphen ylhydraeine, NHPh-NHMe.Theconstitution of the isomeride has previously been proved by Eotte,but in answer to his criticisms (Abstr., 1887, 770) it is shown thatphthalic anhydride and phenylhydrazine, reacting in molecular pro-portions, give either anilophthalimide or phthalophenylhydraxine,according to the temperature ; at ordinary t'emperatures, phenyl-hydrazine-phthalic acid is at first formed, which on subsequent heat.-ing yields ariilophthalimide ; if, however, the reaction proceeds at 163",the melting point of the acid, a t which temperature it is unstable,phthalophenylhydrazine is formed in the greater proportion.Dyes from Aniline Chromates.By S . GRAWITZ (Compt. rend.,Azophenine. By 0. N. WITT (Bey., 20, 2659-2660).-A yplyto Fischer and Hepp (Abstr., 1887, 1105), in which the author poiiitsout that the constitutional formula proposed by them is inadmissible,since azoplienine does not form an acetyl-derivative when heated withacetic anhydride, and yields a considerable quantity of aniline ontreatment with tin and hydrochloric acid. On these grounds, theauthor adheres to his published views on the constitution of azo-By P. BARBIER and L. VIGNON (Compt.rend., 105, 670-672) .-Paranitrosodimethylaniline has no action onaniline at the ordinary temperature in presence of water, glacialacetic acid, or an excess of aniline, but a t 80" there is an extremelyviolent reaction.If equal molecular proportions of aniline and paranitrosodimethyl-aniline are dissolved in eight times their weight of ethyl alcohol of 92",and heated on a water-bath, a reaction takes place a t 80", with con-siderable development of heat, and is complete in about three hours.When the liquid is cooled, a solid separates, which is washed withdilute hydrochloric acid, and then crystallised from boiling toluene.I'etranaethyZlliumido-azobe.nzene is thus obtained in brilliant, brown,V.H. V.105, 576--577).-A question of priority and patent right.phenine (Abstr., 1887, 821). w. P. w.Substituted SafraninesOHBAKIC CHEMISTRY.35crystalline plates, which melt imperfectly a t 218-220" without vola-tilisation, and when reduced with zinc and salphuric acid, yielddimethylparaphenylenediamine in almost theoretical quantity. It. isalmost insoluble in water, and only slightly soluble in dilute acids, butdissolves in concentrated acids forming deep red solutions.The alcoholic liquid separated from the tetramethpldiamido-azo-hneene has a deep, violet-red colour, and when evaporated leaves aviscid residue, which dissolves almost completely in water. Whenthis solution is mixed with sodium carbonate, a precipitate is formed,and if the filtrate is mixed with sodium chloride, dimethylphenosafra-nine Beparates, and is purified by repeating the treatment with sodiumcarbonate and chloride.The equation representing the reaction is-ZNHzPh + ~C~EIANO*NM~~,HC~ = ClsHZON, + CWHIgNdCl +3H20 + 2HC1.C. H. B.Action of Acid Amides on Bromacetophenones. By M. LEWY(Ber., 20, 2576-2580) .-When bromacetophenone is heated withacetamide (2 parts) a t l't0-130", for one hour, a base, C,,H,NO, is ob-tained. This forms long, colourless needles, readily soluble in alcoholand ether; it melts a t 45", and boils a t 241-242'; it has slightlybasic properties. The hydrochloride, CloH9N0,HCl, crystallises insmall needles ; when treated with an excess of hydrogen chloride, ityields a heavy, fuming oil, possibly an acid salt. The platino-k&m&, (CloN,NO),,H,PtC16 + 2Hz0, separates in dense, yellowflakes, consisting of' orange-coloured needles, which melt a t 130-140with decomposition.The subhate forms white, lustrous plates, whichdecompose in contact with water. The picrate crystallises in lemon-coloured needles, melting at 133-134'.The formamide base, CgH,NO, prepared by heating bromaceto-phenone with formamide, is a thick, colourless oil, which becomesyellow when exposed to air ; it solidifies when cooled with a freezingmixture, melts at 6", and boils at 220-222'. The hydrochZoride meltsat 80". The pZutinochZoride (with 2 mols. HzO) crystallises in slender,yellow needles. The hermawtide base, CIBHIINO, is prepared by heatingbromacetophenone and benzamide a t 140-150" ; the product isextracted several times with boiling water, and the residue fractionallydistilled. It crystallises from alcohol in large, colourless plates,readily soluble in the usual solvents, melts a t 102-103", and boils a t338-340". The hydrochloride crystallises in slender, matted needles ;it is slowly decomposed by boiling water.N. H. hLIsonitroso-compounds : Isobenzaldoxime. By E. BECKMANN(Ber., 20, 2766-2768) .-When benzaldoxime is mixed with sulphuricacid in presence of ice, a solid, white substance separates out undercertain conditions ; sometimes an oil is obtained. The former, pro-bably a poly rneride of benzaldoxime, crystallises in glistening needles,melting at 128-1.30"; it is distinguishable from benzamide by itscrystalline form. The oil is benzaldehyde, produced by the re-forma56 ABSTRACTS OF CHEMICAL PAPERS.tion of the oxime and its subsequent decomposition by the acidpresent.V. H. V.Condensation of Cinnamic Acid with Gallic Acid. By E.JACOBSEN and P. JULIUS (Bey., 20, 2,588-25,89).--St?lrogaZZo7,CI6Hl0O5, is prepared by heating cinnamic acid (10 parts), gallic acid(12 parts), and sulphuric acid (150 parts) at 45-55', for two to threehours. The product is poured into water, filtered, and the precipitatewashed with slightly acidified boiling water. It crystallises in bright-yellow, microscopic needles, which do not melt a t 350"; it is verysparingly soluble, except in boiling alcohol, aniline, and glacial aceticacid, and sublimes when carefully heated in large, yellow, lustrousneedles. Alkalis dissolve it with green colour, which changes to blue,and then red, when the solution is heated.The solution in sulphuricacid is yellowish-red. When oxidised with dilute nitric acid, it yieldsa large amount of phthalic acid. The triacetyl-cleri~nfive, C22H1606,crystallises in pale-yellow needles. With mordants, styrogallol yieldsshades similar to those obtained with nitroalizarin. N. H. M.Paradiphenoldicarboxylic: Acid. By R,. SCHMITT and C.KRETZSCHMAR (Bey., 2 0, 2 703-2 704) .-Pu~*adiphenoZdicarboayl~c acid,COOH-C6H,( OH).C6H,( OH)*COOH, is obtained when sodium para-diphenol is heated in an autoclave with liquid carbonic anhydride at200" for nine hours, and the resulting product is treated with an acid.It crystallises in small, microscopic needles, melts at 131" with theevolution of carbonic anhydride, is not volatile with steam, has aslightly bitter taste, and is readily soluble in ethyl and methyl alcoholand in ether, sparingly soluble in water (100 C.C.of water at 15" dis-solving 0*0052 gram of the acid), and insoluble in benzene and chloro-form. Suspended in water, it is coloured bluish-violet with ferricchloride, the colour changing to a dull brown on heating, whilst thesodium salt when similarly treated yields a deep blue solution, fromwhich indigo-blue flocks separate. w. P. nT.Orthamidotriphenylmethane. By 0. FISCHER and A. FRANKE L(Annalen, 241, 362-368) .--The preparation of diphenylquinolyl-methane has been previously described by the authors (Abstr., 1886,561). The sulphate and picrate are precipitated on the addition ofsulphuric or picric acid to alcoholic solutions of the base.The nitro-derivative melts a t 213" with decomposition, and the amido-compoundon oxidation forms a riolet-coloured solution.Triphenylmethaneorthocarboxy lic acid is prepared by slowly addinga solution of the hydrochloride of the diazo-compound of amidotri-phenvlmethane to a solution of potassium cyanide and copper sulphatea t 9d". The crude product is sa,ponified with alcoholic potash, andthe acid precipitated from the aqueous solution of the potassium saltby hydrocliloric acid. Alcohol, ether, acetic acid, and benzene dis-solve the acid freely. It melts a t 162" and volatilises without decom-position ; i t is identical with the acid Baeyer (Abstr., 1880, 650)obtained f r o n phthalophenone.Orthoh ydrozytri~he?zylmet}~ane is formed by passing air through ORGANIC CHENISTRY. 57solution of dia zoamidotrip henylmet hane sulp hate, and boiling theproduct in a current of carbonic anhydride.It is soluble in alcoholand ether, and melts a t 118".The acetic derivative of amidotriphenylmethane melts a t 168-169",and is freely soluble in alcohol, benzene, and acetic acid. The thio-carbamide melts a t 12fjo, and dissolves readily in ether, carbon bisul-phide, and hot alcohol. w. c. w.Two Dihydroxynaphthalenes. By A. EMMERT (Anna.len, 241,368-373) .-$-Naphthol yields t w o sdplionic acids on treatment withsulphuric acid, and each acid is converted into a dihydroxynaphtha-lene by fusion with potmh.~-~-DihydroxynapJ~tl~alene melts a t 615-216", and dissolves freelyin alcohol and et,her.Ferric chloride produces a yellowish-whiteprecipitate. A t 120" alcoholic potash and ethyl iodide coiivert thedihydroxynaphthalene into an ethyl ether, Cl0H6( OEt,). It formssilky plates and melts at 162". The diacetate, C,oHt-I,(OAc)2, melts a t175".P-a- Dihydroxynaphthalene is soluble in alcohol, ether, benzene, andwater. It melfs a t 1 7 8 O , and gives a blue precipitate with ferricchloride. The dietliyl ether crystallises in prisms, melting at, 67", andthe diacetate forms rhombic plates and melts at 108". W. C. W.Derivatives of Di-p-naphthylamine. By C. RIS (Ber., 20,261 8-2628). -Crude di-/3-nap hthylamine is purified by distillationand crystallisation from benzene ; it melts at about 471".Met7&yldi-P-naphlh?/Inmine, NMe( C1,H7)2, is prepared by heating di-naphthylamine and methyl iodide (equal molecular weights) for fivehours at 150", and ci-ystallises from alcohol in nearly colourless needlesmelting a t 139-140".It dissolves rather readily in warm alcohol,glacial acetic acid, benzene, and ether, and is almost insoluble in lightpetroleum. The alcoholic solution shows a bluish-violet fluorescence.It is insoluble in dilute mineral acids; the hydrochZoride forms slender,lustrous crystals, which decompose quickly in presence of water. Thesolution in strong sulphuric acid is yellow, and acquires an intensebrown colour on addition of a trace of a nitrite or nitrate.Ethyldi-/3-naphthyZamine, NEt(C&€,),, crystallises in almost colour-less prisms melting a t 231"; it resembles the methyl compound insolubility ; the hydi-och Zoride is a white, crystalline powder.H e t h y l di-~-)taphth!iZcarba;lriate, N( CloH,),.COOMe, is obtained byheating di-/3-naphthylamine and methyl chloroformate (equal weights)at 150-160" for two and a half hours.It crystallises from alcoholin slender, white needles, melting at 113-114", dissolves readily inalcohol, ether, and benzene. It crystallises from benzene with $ mol.CcH6.Tetrabromodi-p-naph tJyEamine, C20H,,Br,N, is prepared by the actionof bromine (4 mols.) on a well-cooled solution of di-p-naphthylaminein glacial acetic acid. It crystallises in long, white, matted needles,which melt a t 245-2246".It dissolves rather readily in hot benzeneand cumene, very sparingly in ether, light petroleum, and alcohol.It distils almost without decomposition58 ABSTRACTS OF CHEMICAL PAPERS.It is not attacked by boiling concentrated aqueous potash ; brominedoes not act on it.Octobromodi-P-?taphthyZanzine, CzoH,Br,N, is formed when /3-dinaph-thylamine, as dust, is added to an excess of bromine in presence ofalnminium bromide. The product is stirred well, and the yellow pre-cipit'ate, after being treated with alkali and with boiling hydrochloricacid to remove adhering bromine and aluminium, is crystallised fromcumene. It forms slender, white needles, which melt at about 300",and dissolve readily in boiling nitrobenzene, less in boiling cumene ;in other solvents it is sparingly or not at all soluble.is prepared by adding thecalculated amount of sodium nitrite dissolved in a little water to itmixture of alcohol and sulphuric acid containing di-P-naphthylaminein the form of dust.It crystallises from benzene in groups of whiteneedles, melting at 139-lPO", sparingly soluble in alcohol, readily inbenzene.Dinit.l.odi-P-naphthy~amin.e, Cz0H,3N(N0z)2, is formed when strongnitric: acid is slowly added to a cooled solution of the amine in glacialacetic acid; it separates after some time as a yellow powder. Itcrystallises in yellowish-red needles, melting at 224-225", readilysoluble in boiling cumene, less soluble in benzene, and almost in-soluble in alcohol and ether.T~tran.itrorZi-p-na~hthz/Z~zmine, CzOHllN(N02)P, is obtained by gradu-ally adding nitric acid (3 pn.rts) mixed with glacial acetic acid to asolution of dinaphthylamine (1 part), in glacial acetic acid.Itcrystallises from nitrobenzene in grains, which melt at 285-286",and detonate when more strongly heated. It is sparingly or not atall soluble in the ordinal-y solvents, readily soluble in boiling nitro-benzene.Hexanitrodi-P-naphthylamine, CzoH9N( NOz),, prepared by heatingthe finely-powdered amine with fuming nitric acid, could not be ob-tained in crystals. It dissolves readily in alcohol, less in glacialacetic acid, and is almost insoluble in ether, benzene, cumene, andnitrobenzene. Alkaline carbouahes dissolve it readily. When mixedwith excess of copper oxide, it decomposes with explosive violence,and was therefore not analysed.The potassium and ba&m salts wereaualysed ; they are both amorphous.Benzoylortko?iitrodi-P-n~phthylscmine, C2THlsNO*N02, is prepared byadding a mixture of fuming nitric and sulphuric acids to a solution ofbenzoyldi-p-naphthylamine in cold glacial acetic acid, and subse-quently heating the whole at 50-60". It crystallises from benzenein well-formed, yellow, transparent crystals (with 1 mol. C6H6), melt-ing at 95". Crystallised from alcohol it melts at 168". It dissolvesreadily in warm benzene, less in alcohol.Benzenylriap?~thyle7Leanzidine, N< CPh >NGlaH,, is obtained by re- GoH,ducing benzoylnitrodinaphthylamine dissolved in glacial acetic acidwith excess of tin and hydrochloric acid.It crystallises from benzenein transparent, slender needles (with 1 mol. c,H6) melting at 113-114" ; when crystallised from other solvents it melts at 163". It sub-limes when carefully heated in small, colourless plates, and distilsNitrosodi-P-naphthyZn?nine, M0.N ( C1ORGANIC CHEMISTRY. 59with slight decomposition. I t is readily soluble. The hydrochlorideforms slender, matted needles which decompose in contact with water.Naphthaphenaaine. By P. BRUNNER and 0. N. WITT (Ber., 20,2660-2663). - Naphthaphenasinesulplzowic acid is obtained whennaphthaphenazine is heated with 10 times its weight of 35 per cent.fuming sulphuric acid at 100" for 12 hours. It crystallises in orange-red needles, melts above 290°, and is soluble in water and alcohol.Inconcentrated sulphuric acid it dissolvss with a deep orange-browncolour, which becomes orange-yellow on dilution. The sodium salt,,C16H,N2*SOsNa + 2H,O, was prepared. On fusion with potassiumhydroxide, a ewrhodol is obtained which differs from that previouslydescribed (Abstr., 1887, 153), since it dissolves in hydrochloric acidwith a red colour, and in concentrated sulphuric acid with A dark-green colour changing to red on dilution. A similar compound hasbeen prepared by diasotising the eurhodine formed by the reductionof nitronap h t haphenazin e.Cy artowph thaph enazine, C16H9N2* CN, is obtained when sodiumnaphthaphenazinesulphonate is distilled with potassium cyanide ordry potassium ferricyanide. Crystallised from cumene, it melts at236-5237', and dissolves in concentrated snlphuric acid with a cherrj-red colour, which changes through orange to yellow on dilution.Ifheated with hydrochloric acid under pressure, it is decomposed intonaphthaphenazine and formic acid, but when heated with alcoholicpotash at 220-250" it is partially converted into naphthaphenaxine-carboxylic acid. This is sparingly soluble in the ordinary solvents,melts above 360", and dissolves in concentrated sulphuric acid with adeep-red colour, changing to yellow on dilution. The potassium saltcrystallises in white needles and is sparingly soluble in water.N. H. M.w. P. w.Naphtholcarboxylic Acids. By R. SCHMITT and E. BURKARD(Ber., 20, 2699-2704) .-a-NnpIit?~olcarbo~l~c acid (m.p. 187") canbe prepared by heating sodium a-naphthol with liquid carbonic anhy-dride in an autoclave at 130°, and is a comparatively stable compound(compare Abstr., 1887, 732), since it is only partially decomposed byprolonged boiling with water, in which it is very sparingly soluble.The aqueous solution is coloured greenish-blue by ferric chloride.The sodiurn salt, with 3 mols. HzO, crystallises in large, thin, nacreousscales; the ammoniurri salt forms long needles; the calcium and bariumsalts crystalhe in long needles. The methyl salt, OH*CloH6*COOMe,melts at 78", the ethyl salt at 49', and the phenyl salt at 96". Theacetgl-derivative, OAc.Cl~~6*COOH, melts at 158" ; the bromo-deriva-tive, OH*CloH&r*COOH, melts at 238" ; the nitro-derivative,melts at 202", and yields P-nitro-a-naphthol when 'heated with lime ;the amido-derivative melts above 200", and its acetyl-compound at183".paraxobenzenesulphonic acid-a-naphtholcarboxylic acid,OH.C1&L,( NO,) .C 0 OH,Metadiazonaphtholcarboxylic acid, OH*CloH5<, CO@ N>, andS03H*C6H4*N2* C~oH~(OE€) *C 0 OH60 ABSTRACTS OF CHEMICAL PAPERS.were also obtained, and the latter on reduction with zinc andhydrochloric acid yields an amido-a-naphtholcarboxylic acid whichcrystallises in colourless, prismatic needles, is very sparinglysoluble in water, and melts above 200", but differs from theamido-derivative just described since its acet y I-compound meltsat 195O.When sodium P-naphthol is similarly heated with liquid carbonicanhydride in an autoclave at 130", /I-naphtholcarboxylic acid is ob-tained, and is sepnrahed by treating the product with ammoniumcarbonate and precipitating with hydrochloric acid.This acid readilydecomposes on heating, and shows all the properties of Kauffmann'sacid (Abstr., 7 882, lOtj8). Ferric chloride colours its aqueous solu-tion a pure blue. The ammoniim salt crystallises in yellow needles,whilst the barium, calcium, and silver salts. resemble the correspondingsalts of the a-acid. The methyl salt melts at 76", and the ethyl salta t 5 5 O .When sodium P-napht,hol is heated a t 280-290" in a current ofcarbonic anhydride, absorption of the gas rapidly takes place, and aproduct is obtained consisting of &naphthol, undecomposed sodium&naphthol, and ~-?LaphthoZcarboxylic acid. This acid is extremelystable, and crystallises from water in lustrous, rhombic, Tellow scales,which melt a t 216" without decomposition, and are readily soluble inalcohol and ether, soluble in tolnene, benzene, and chloroform, andsparinrrlv soluble in hot water.Ferric chloride colours the aqueoussolution blue. w. P. w.Terpenes. Part VI. By 0. WALLACH (Annulen,, 241,315-328).-The compound which the author (Abstr., 1887, 967) recently de-scribed as terpene nitrite is terpinene nitrosite. It forms monocliniccrystals ; a : b : c = 1.0103 : 1 : 0.66978 ; /3 = 80" 31'.Terpinene nitroZeth,yZarnine, NHEt2*CIoHl, : NOR, is obtained byboiling for a short time an alcoholic solution of the nitrosite with astrong aqueous solution of ethylamine.The crude product is pouredinto water, the precipitate dissolved in hydrochloric acid, and the basereprecipitated by ammonia, The base melts a t 130-131", and dis-solves in boiling alcohol, ether, chloroform, and in warm dilutesolutions of alkalis. The hydrochloride, C12H,N,0,HC1, is crystalline,and dissolves freely in water and alcohol. The nitroso-compoundmelts a t 133-133". It is decomposed by boiling with an excess ofhydrochloric acid, yielding hydroxylamine.Terpinene nitroldiethylamine, NEt2*CloHl, : NOH, melts at 11 7-1 18".Terpinene gzitrohethylarnirze, NHMe.CloH15 : NOH, crystallises inprisms and melts at 141". The dimethylamine, NiNe,*CloHl, NOH,melts a t 160-161". It dissolves in chloroform.The amylamine-compound is less soluble in alcohol and ether thanthe preceding substances.It melts a t 118-119". The piperidiwe,CloHlsNO,NCsHlo, melts a t 153-154'. It is insoluble in alkalis, butits salts are freely soluble in water. The hydrochloride is obtained asan oil on passing dry hydrogen chloride into an ethereal solution ofthe base.Terpinene rritrolamine is formed by adding ammonia to a hoORGANIC CKEiWSTRT. G1alcoholic solution of terpinene nitrosite. After recrystallisation fromhot water it melts at 116-118".By adding a mixture of nitric acid and amyl nitrite to carvene orcitronene saturated with dry hydrogen chloride, Maissen (Gazzettu,13, 99) obtained a crystalline compound melting with decompositiona t 1 1 ~ 1 1 5 " .The author has obtained the same or similar deriva-tives from cinnamene and dipentene. They melt at 109" and 110-111" respectively, and act oh organic am"ines, yielding crystallinebases. vv. c. w.Constitution of some Pyrroline-derivatives. Ry G. CIAMICIANand P. SILBER (Ber., 20, 2594-2607 ; compare Abstr., 1887, 597).-Uibromodiacetyl~~rrol~ne, C4NHAc,Pr2, is prepared by the action ofbromine vaponr on a warm solution of 2 grams of pyrrylenedimethyl-diketone in 700 C.C. of water. It crystallises from alcohol in whiteneedles melting a t 1'71-1 72", insolrible in waber, soluble in alcohol,ether, and in alkaline carbonates. Nitric acid oxidises it readily a tthe ordinary temperature t o dibromomale'irnide ; the constitution ofthe base is therefore [Br, : Ac, = 3 : 4 : 2 : 51.C4NHBr2Ac*NOZ [Br2 : Ac : NO, =3 : 4 : 2 : 51, is formed when dibromodiacetylpyri-oline (8 grams) isdissolved in fuming nitric acid (80 grams), and crystallises fromalcohol in long, white needles melting at 206".It is soluble inalcohol, ether, ethyl acetate, hot glacial acetic acid, and benzene, verysparingly soluble i n water, insoluble in light petroleum. Alkaliliecarbonates dissolve it readiiy with intense yellow colour.Dinitrodibromopyrroline, C4NHBr,(N02)2 [= 3 : 4 : 2 : 51, is ob-tained by the action of a well-cooled mixture of sulphuric and fumingnitric acids on the mononitro-compound. It crystallises from waterin large, yellow plates (with 1 mol. €LO), which melt at about169" with decomposition ; it is readily soluble in ether, alcohol, hot.water, and hot benzene, and dissolves in alkaline carbonates withevolution of carbonic anhydride, If the mixed acids are allowed toact on the mononitro-compound at the ordinary temperature, dibromo-maleamide, melting at 227", is formed.The latter is also formedwhen dinitrodibromopyrroline is heated at 165" ; nitric oxide isevolved.When dinitrodibromopyrroline is heated with sulphuric acid(20 parts) it is converted quantitatively into dibroniomaleic acid. It isprobable that the imide of dibromomale'ic acid, and. therefore, maleic~-itr~dibromacetyI'PYrO'o liire,Lcid also, are symmetrically rather than unsymmetrically constituted :CBr*CO CBr *CO <Csr.Co>NH, rather tha,n <C.c&NH>.(Compare Anschutz,Abstr., 1887, 916).Dibromopyrrolinedicarboxylic acid behaves towards fuming nitricacid in a manner similar to dibromodiacetylpyrroline ; dinitro-dibromopyrroline is formedidentical with that obtained from dibromodiacetylpyrroline. Thereaction shows that the two carboxyl-groups in pyrrolinedicarboxylicacid have the positions 2 : 5.Methyl dibromopyrrolinedicarbox2/late, CJYHBr,(COOMe)?, is ob-[NO, : NO, : B r : Br = 2 : 5 : 3 : 4G2 ABSTRACTS OF CHEMICAL PAPERS.tained by dissolving methyl pyrrolinedicarboxylate (3 grams) in water(1 litre), and saturating the lukewarm solution with bromine vapour.The yield is 4.5 grams of pure product. It crystallises from alcoholin long, white needles, melting a t 222", soluble in ether, almostinsoluble in water.When 2 grams of the salt is a,dded to 40 gramsof fuming nitric acid a t -Is", and the whole poured into 400 C.C. ofice-wa,ter, and treated with potash (30 grams), the compoundC4H,BrNOa is obtained. It is a crystalline compound, melting a t168-171" with deconiposition, soluble i n ether, alcohol, and hotbenzene, rather sparingly soluble i n water, and insoluble in lightpetroleum. It dissolves in alkaline carbonates with evolution of car-bonic anhydride. The constitutional formula CBrO*C(NOH)*COOMeis suggested for it.Methyl dibromacetylcnrbopyrrolate, C*NHBr,Ac*COOMe, is pre-pared in a manner similar to the methyl salt of the bromodicarboxylicacid, which it completely resembles in its behaviour towards fumingnitric acid.Dibromacety lmeth y lpyrroline, C7H7Br,N0, is prepared by treatinga solution of 2 grams of acetylmethylpyrroline, melting a t 85-86'(Abstr., 1886, 719), with an excess of bromine.It crystallises fromdilute alcohol in long, white needles, of a silky lustre, melts at 161-162", dissolves in ether, carbon bisulphide, and chloroform, and issparingly soluble in boiling water. When the finely-powderedcompound is warmed with fuming nitric acid, dibromomalejimid e(m. p. 227") is formed. The constitution of acetylmethylpyrroline istherefore [Ac : Me = 2 : 51.In order to obtain further evidence as to the constitution of pyrnvylmethyl ketone and Schwanert's carbopyrrolic acid, tribromacetyl-pyrroline and methyl tribromocarbopyrrolate were converted intodibromomaleimide by the action of nitric acid.C4NHBr2Ac..N0, [Br : Br : Ac : NO,= 2 : 3 : 5 : 41, is prepared by the action of bromine on nitracetyl-pyrroline, melting at 197" (Abstr., 1885,810 and 992).It crystal-lises from alcohol in needles melting a t 1 7 5 O , soluble in ether, warmdcohol, and glacial acetic acid, sparingly soluble in warm water,insoluble in light petroleum. The non-identity of this compoundwith the dibromo-derivative described above, and the probabili t ythat in the nitracetyl-compound (m. p. 197") the acetyl-group has thea-position, make it probable that the nitracetyl-compound has theconstitution [NO2 : Ac = 3 or 4 : 2 or 51.A table of all pyrroline-derivatives (halogen-derivatives and ethersexcepted) of known constitution is given.Synthesis of Pyridine and Piperidine-derivatives.By C. PAALand C. STRASSER (Ber., 20, 2756--2766).-Diphenacylacetic acid(Abstr,, 1887, 261) when treated with alcoholic ammonia yields theammonium salt of ad-dip heny ldi~y~ropyridine-cy-carboa y l i c acid,C,NH,Ph,*COONH*. This salt is soluble in water and concentratedhydrochloric acid ; on acidification with sulphuric acid, the corre-sponding acid separates, but is quickly decomposed. On dry distilla-tion, ammonia is given off, and aa'-di~heny~yridir~ecnrboxyl,ic acid,liibrornon;tracefy.?pyrroline,N. H. MORGANIC CHEMISTRY. 63C5NH,Ph,.COOH, is produced, which after purification crystallises indelicate, white needles or prisms, melting at 275', soluble i n alcohol,sparingly soluble in chloroform.The acid is not altered by nitrousacid, acetic chloride, or oxidising agents. Its ammonium salt doesnot exist in the free state ; the silver salt is a heavy, white precipitate ;the chromate a dark-red, amorphous precipitate ; the aurochloride iscrystalline.Dip heny Zppiperidine- y-carboz y Zic acid, C5NH8P h,CO 0 H, obtainedtogether with the above mid, and separated from i t by its greatersolubility, forms crystalline crusts; it melts at 339', and sublimeswithout decomposition, its alkaline salts are very soluble, the bariumand silver salts are white precipitates. Its nitroso-derirative crystal-lises in pale-yellow, glistening needles melting at l59", and is solublein ether and alcohol.aa-Diphenylpyridine, C5NH3Ph, obtained by the distillation of thecalcium salt of the carboxylic acid with lime, crystallises in long,glistening needles melting at 81-82" ; its platinochloride forms yellowneedles, and the auroclzloride a crystalline precipitate ; the rnethiodidecrystallises in needles melting at 203".aa-Diphen.ti~iperinine, C5NH9Ph,, obtained by the hydrogenation ofthe above base, is a thick, pale-yellow oil ; its ?ydrochZoride crystallisesi n white needles; the platimchloride and the aurochloride and thenitroso - deriunt ive cry stallise with difficulty .V. H. V.3-Methylpyridine and 3-Methylpiperidine. By C. STOEHR(Ber., 20, 2727--2733).--The picoline obtained by distilling strych-nine with lime (Abstr., 1887, 604) proves on further examination tobe p-picoline, since nicotinic acid is found to be the sole pr-d uct onoxidation with 2 per cent.permanganate solution. Some quantity ofthe base was prepared to enable an examination of its properties to bemade, and the results are compared with those of previous observers.P-Picoline thus obtained boils at 14.5-150" after two fractionations ;by conversion of this product into the mercurochloride and regenera-tion of the base, i t gives a product which mostly passes over between148' a n d 149" (compare Hesekiel, Abstr., 1885, 812). The platino-chloride, (C6H,N)2,H,PtC16 + H,O, has the properties of' the saltdescribed by Baeyer (AnnaZen, 155, 285), melts when dry at 195(:loses 1 mol. H,O when allowed to remain i n a desiccator, and whenheated at 120" loses in addition I mol.HCI, the compound thusobtained, (G',H7N),,HCl,PtC14, melting at 211-212". The aiirochloridemelts at 182-1 83". The mercuroch loride, C6H7N, H C1,2HgCl, (com-pare Hesekiel, Abstr., 1886, 256), crystallises from hot water inslender, ramifying needles, from dilute hydrochloric acid in indentedscales, or long, compact needles, and from concentrated hydrochloyicacid, in which it is very soluble, in small, well-formed prismaticcrystals melting at 139-140". The picrate crystallises in six-sidedscales melting at 142-143".3-Methylpiperidine, obtained by reduction of the P-picoline in alco-holic solution with sodium, is readily soluble in water, and yields ahydrochloride, crptallising in dazzling, white needles.w. P. w64 ABSTRACTS OF CHEMICAL PAPERS.2 : 6 Methylethylpyridine and 2 : 4 Methylethylpyridine.By M. SCHULTZ ( R e r . , 20, 2729-2727) .--Picoline ethiodide, whenheated at 280-300" for 1 to 1 i hours, yields a mixture of bases.To separate these, the product is treated with water, acidified, dis-tilled to remove a small quantity of an arornhtic oil, then renderedalkaline and again distilled. The mixture of bases so obtained, whichboils between 100" and 200", is fractionated, and the fractions boilingat 1 56-16(j0, 166-172", and 172-182" repeatedly refractionated ;in this way fractions boiling at 138-163" and 169-174'are obtained,and these consist chiefly of 2 : 6 methylethylpyridine and 2 : 4 methyl-e thy1 pyridine respectively.2 : 6 ~feth?/lethyZpyridi.lze, C8HIIN, is a colourless, hygroscopic, oilyliquid, having a sweet, aromatic! odour recalling that of picoline, andwhen moist, an alkaline reaction.It is sparingly soluble in water,readily volatile with steam, and yields salts which readily deliquescein air: The platinochboride, (C8H1,N),,H,PtCl,, crptallises in tabular,triclinic crystals, melts at 173-174" (after drying a t 110"), and isreadily soluble in hot water, insoluble in alcohol and ether ; the auro-clzloride, CsHllN,HAuC14, crystnllises in yellow needles, melts at 1 lo",and is sparingly soluble in water, readily soluble in ether alcohol.On reduction with sodium in hot alcoholic solution, copellidine,C,H,,N [Me : Et = 2 : 61, is obtained; this is a colourless, oilyliquid, which boils a t 147-151", fumes slightly in the air, has thecharacteristic odour of piperidine bases, and a strongly alkaline reac-tion.The nitroso-derivative is a brown oil 5 the hydrochloride,C,H,N,HCl, crystallises in white needles, and though readily solublein water and alcohol is only slightly hygroscopic. When oxidised with2 per cent. permanganate solution, 2 : 6 methplethylpyridine is con-verted into a dicarboxylic acid melting a t 226", and identical withLadenburg and Roth's dipicolinic acid (Abdtr., 1885, 557).2 : 4 Nethybethylpyridine, [Me : Et = 2 : 41, is a hygroscopic,colourless, oily liquid, which in its properties closely resembles the2 : &derivative. The pZntinochZoride, (C8Hl1N),,H2PtCI,, forms red-dish-yellow, tabular crystnla, which after drying a t 110" melt a t 190" ;the aurochloride, C8HI1N7HAuC14, crystallises in yellow needles,begins to fuse a t 83", melts a t 90", and is soluble in hot water,readily soluble in alcohol and ether.When the base is reduced withsodium in hot alcoholic solution, i t is converted into copeblidine,[Me : E t = 2 : 41 C,Hl,N; this is a colourless, oily liquid, whichboils a t 155-160", has a strongly alkaline reaction, and an odoursimilar to that of the 2 : 6 base. The hydrochloride, C8HITN,HCI,crystallises in white needles, is readily soluble in water and alcohol,and is slightly hygroscopic. 011 oxidation with 2 per cent. perman-ganate aolution in the cold or on heating, 2 : 4 methylethylpyridineyields a dicarboxylic acid whose melting point rose from 204" to 211"after three crystallisations.This author regards this acid as beingidentical with Ladenburg and Roth's lutidinic acid (Abstr., 1885,815), and ascribes its lower melting point to the presence of a smallqnarltity of pioolinic acid. w. I?. wORGANIC CHEMISTRY. 65Phenylated Piperidine and Pyridine Bases. By 0. BALLY(Ber., 20, .2590-2594).--r-Phenylpi~eridil~e. C,NH,,Ph, is preparedfrom r-phenylpyridine and purified by distillation. It melts at57*5-58", and boils a t 255-2S7" under 727 mm. pressure; it is astrong base, almost insoluble in water. The salts are readily soluble.The hydrochloride crystallises in needles ; the platitrochloride formsorange-coloured plates, melting a t 204-207".It gives no precipitatewith picric acid ; the original base gives a precipitate even i n vcrydilute s o h tion.C,NH,Me2Ph [Me : P h : Me = 2 : 4 : 61, is ob-tained by distilling potassium plienyllutidinegarboxylate (preparedfrom benzaldehyde, ethyl acetoacetate, and ammonia) with lime, a t thelowest possible temperature. It is purified by means of the hjdro-chloride, and crystallises from ether in prisms melting a t 54.5-55".I t boils a t 287" under 731 mm. pressure. The salts are generallysparingly soluble ; the hydrochloride (with 3 mols. H20) crj stallises inslender, matted needles which do not melt at 300" ; tlie platino-chloride, (C,,H,,N),,H2PtCl, + 4H20, forms orange-coloured needles ;the rzitmte and chromate melt at 177" and 228" respectively, bothcrystallise in needles.yPhenyZlupefidine, C,NH,PhMe,, is prepared by the action ofsodium (2.5 parts) on phenyllutidine (1 part) dissolved in absolutealcohol ; it is separated from unchanged phenyllutidine by distilla-tion.It is a colourless oil of a peculiar odour, boiling a t 274"under 73L mm. pressure. The hydrocltloride and iritrate cryhtallise inprisms ; the dinitrate melts at 210" ; the platinochloride crystallises ingold-coloured plates melting a t 237". Besides pheriyliupetidine, acompound, probably hepty Zbenzene, CHPh( CH,*CH,Me),, is producedin the reduction of phenyllutidine.When .I-phenyllu~idylilcna nzethiodide (prepared by digesting the basewith methyl iodide in a reflux apparatus) is treated with stroiig aqueouspotash, a base is obtained which jields a hydrochloride id;Jnticalwith that formed by the action of silver chloride on methylpheuyl-In tidylium iodide.Methyl-yphenyllutidylium iodide is a crystalline substance s p r inglysoluble in hot water.Phenyllutidine,N. H.M.&innamylpyridine. By H. BAURATH (Ber., 20,2719-2720).-When a-piuoline and benzaldehyde in equimolecular proportions areheated with zinc chloride at 220-225" for six hours, a-cinnamylpyri-&be, C5NH,*CH : CHPh, is obtained, and after removal of unalteledbenzaldehyde by steam distillation can be separated by rendering theproduct alkaline and distilling with superheated steam. Tlie base,already prepared but not described bF Jacobsen and Reimer (Alnstr.,1884, 335), is crystalline, melts at 90.5-91", boils at 313-314O(uncorr., under 733 mm.pressure), and is readily soluble i n carbonbisulphide and ether, soluble in alcohol, benzene, and light petro-leum, and practically insoluble in water. The salts generttlly crystal-lise in needles : the platinochloride, (C13H3,~N)z,HzPtCI, + d H 2 0 ,decomposes when heated to expel the water of crptallisation. Ontreatment with bromine in carbon bisulphide solution, the base yieldsVOL. LlV. 66 ABSTRACTS OF CHEMICAL PAPERS.an additive compound, C,,H,,NBr,, which crystallises from alcohol incompact needles melting at 166-167" ; this derivative yields a. newbase when heated with alcoholic potash. Derivatives of a-cinna,myl-pyridine have also been obtained by the action of hydriodic acid andby redilction of sodium and alcohol, and will be described in a latercommunication.w. P. w.Ethylquinoline. By L. REHER (Ber., 2 0 , 2734-2735).-Doehnerhaving found the boiling point of n-ethylquinoline to be 24,5-246"(Abstr., 1887, 504), the author has redetermined the boiling points ofa- and y-ethylquinoline (ihid., 279) by converting the bases into theplatinochlorides, recrystallising these repeatedly from concentratedhydrochloric acid, and regenerating the bases from the pure salts bymeans of hydrogen sulphide. a-Ethylquinoline boils a t 256-6-258.6"(corr.) and y-ethylquinoline boils a t 271-274" (corr.), and the pureplatinochlorides melt a t 189" and 203" respectively. From the purebases, c3Lromates were prepared crystallising in red needles, and crys-talline zincochlorides were also obtained, that of the y-base formingwhite, concentrically-grouped needles melting a t 195".DiethyZquirLoZinP, obtained by the decomposition of the mercuro-chloride (Zoc.c i t . ) , is a colourless liquid having it quinoline-likeodour, and boiling a t 282.8-284%0 (corr.). The plutinochloyide,(CqH,NEt,),,H,PtC1,, crystallises in orange-red needles, and melts a t217" after previous blackening. On oxidation with chromic acid, thebase yields a fimall quantity of an acid which crystallises in asbestos-By R. SCHMTTT andF. ENGELMANN (Ber., 20,2690-2695).--Further examination of ortho-hydroxyqainolinecarhoxylic acid (Abstr., 1887, 738) shows that itbegins to fuse at 137", that carbonic anhydride and orthohydroxy-qninoline are formed a t 144-145", and that the decomposition iscomplete a t 150".The ammonium salt, OH*CgNH5*CO@NH, + H2Q,crystall ises in glistening, pnle-yellow needles, and is soluble in water ;the bal-iwn salt, (OH*C,NH,*COO),Ba + 2H20, crystallises in long,silky needles, and is sparingly soluble in water ; the caZciunz salt cry+tnllises in stellate groups of prisms ; a basic barium salt, C10NH50aBa,and a basic calcium salt were also prepared; the former is verysparingly soluble in water. The phew$ salt, OH*CgNH5*COOPh,obtained by heating equimolecular proportions of the acid and phenolat 170", forms colourless, short prisms and melts a t 225-226". Thehydrochloride of the acid, OH-C9NH,-COOH,HC1, crystallises in largeprisms, and the mitrute in yellow needles ; both salts are decomposedby water.On treatment with strong nitric acid, a dinitrohydroxy-quinoline is obtained which is probably identical with that describedby Bedall and Fischer (Abstr., 1881, 613 ; Ber., 14, 1368) ; it crystal-lises in golden-yellow scales, melts a t 276" with blackening and theevolution of gas, is sparingly soluble in most solvents, and readilydecomposes alkaline carbonates, forming the corresponding salts.2\il.trohydroxyquinoZinecurboxZllic ncid, N02*C,NHa(OH).COOH, isprepared by heating the nitrate of orthohydroxyquinolinecarboxyliccoloured needles melting a t 190". w. P. w.Orthohydroxyquinolinecarboxylic AcidORGANIC CHEMISTRY. 67acid with rtcetic acid at 100" ; the resulting brown mass is extractedwith acetic acid until it becomes yellow, and is then purified bysoliition in hydrochloric acid and subsequent precipitation with water.It crystallises from water in yellow needles showing a vitreous lustre,decomposes at 200" with the evolution of carbonic anhydride, and dis-solves readily in concentrated hydrochloric acid, in alkalis and in alka-line carbonates, but is sparingly soluble in acetic acid.When heatedabove 200°, nitrohydroxyquinoline, NO,*C,NH,*OH, is formed ; thiscrystallises in yellow needles, melts at 173", is readily soluble in aceticacid and hot, hydrochloric acid,less so inalcohol and ether. On treatmentwith bromine (2 mols.) a t loo", a dibromohydroxyquinoline identicalwith that prepared by Bedall and Fischer (Zoc.cit.) is obtained togetherwith bromohydroxyquiiiolinecnrboxy1l:c acid, OH*C9NHdBr*COOH ; thiscrystallises in matted, citron-yellow needles, melts at 233-235"with the evolution of carbonic anhydride, a,nd yields a hydrochloridewhich crystallises in well-formed tables, and decomposes when boiledwith water. BromohydroxlJqwinoline, CgNHBByOH, formed quanti-tatively when the bromo-acid is heated a t 200°, crystralIises in whiteneedles, melts at 119-120", and is readily soluble in the ordinarysolvents except water. w. P. w.Parahydroxyquinolinecarboxylic Acid. By R. SCHMITT and J.ALTSCHUL (Ber., 20, 2695-2698).- When potassium parahyd coxv -quinoline is heated with liquid carbonic anhydride in an autoclave at170" for six to seven hours, a quantitative yield of potassium para-hydroxyquinolinecarboxylate is obtained ; the sodium-compoundcannot be substituted for the potassium-derivati.ce in this reaction.Parahydroxy~uin,r,linecarbozylic acid, OH*C9NT3,.COOH, crystallisesfrom water in yellowish-white flocks consisting of microscopic prisms,melts at 203-204" with the evolution of carbonic anhydride andformation of parahydroxyquinoline, and is sparingly soluble in alcohol,ether, benzene, and hot water.Ferric chloride colours the aqueoussolution red. The hydrochloride, OH*CgNH,~COOH,HCl, crystal-h e s in long, colourless needles, G r from concentrated hydrochloricacid in short, thick prisms, is decomposed by water, and yields awell-crystallised platinochloride ; the mitrote, formed by digesting theacid with nitric acid (sp.gr. = 1*35), crystallises in large, whiteneedles, and is decomposed by water. The ammonium salt, with 4 mol. HzO, crystallises in long, colourless needles, and is soluble inwater, the solution evolving ammonia when boiled ; the barium salt,with 2 mols. HzO, crystallises in colourless tufts of needles, and doesnot form a basic salt when treated with barium hydroxide.If the nitrate of parahydroxyquinolinecarboxylic acid is heated withnitric acid, yellowish-red prisms separate on cooling, which whentreated with water decompose into nitric acid and nitrohydroxyquino-line ; this crystallises in yellow needles, melts a t 136", and is probablyidentical with Skraup's nitrohydroxyquinoline (Abstr., 1882, 92).w. P. w.Constitution of Glutazine. Ry R. V. PECHMANN (Rer., 20, 2655-2658 ; compare Abstr., 1887, 155).--Nitroglutazina, C5H N 0 *NO*, f i 68 ABSTRACTS OF CHEMICAL PAPERS.is obtained together with dinitroglutazine when nitrous oxide ispassed into a cold aqueous solution of glutazine. It crystallises fromwater in orange-yellow plates which decompose a t 170 -180" withon tmelting. Dinitroglutazine, C5H4N,02(N0,),, crystallises from waterin yellow plates. Both compounds give colourless solutions withacetic acid and zinc-dust which become red when exposed to air.When heated with alkali, they are converted, with evolution oE am-monia, into sparingly soluble salts whicb crystallise in sulphur-colonred,matted needles and explode when heated.These results make itimprobable that glutazine contains an amido-group.The nitronitrosamine, N02.C5H4Wz02.N0, is obtained when glutnzine(1 part) dissolved in the smallest amount of dilute aqueous soda istreated with sodium nitrite (1 part); water is added (so that thewhole amounts to 30 parts), and the whole is poured into a mixture ofglacial acetic acid (5 parts) and water (30 parts). I n a short; time itsolidifies to an orange-coloured magma. The sodium saZt, C5H3NaN405,so obtained ci-ystallises in yellow needles with water of crystallisation.Acids precipitate greenish-yellow needles from the solution. Whenthe sodium salt dissolved i n glacial aeetic acid is warmed withexcess of sodium nitrite, the sodium salt of the dinitronitrosamine,C5H2NaN5O7, separates as a, cinnabar-coloured, crystalline powder.This dissolves sparingly in water, readily in alkalis.When warmedwith dilute acids nitrous acid is given off.Dibes7xoylgZutazine, C5H4N202Bz2, is obtained by heating glutaziriewith benzoic chloride on a water-bath f o r two to three hours, andcryst,allises from glacial acetic acid in lustrous, brownish plates meltingat 215-5216'. It is insoluble in water and in alkalis, sparingly solublein alcohol.The above results show that there are only two hydrogen-atoms inglutazine displaceable by acid radicles, and that these are present asiniidoliydrogen as shown by the formula NH< c0'cH2>C NH.CO-CH,N. H. M.Reactions of Caffe'ine and Caffe'idine.By &I. WERNECKE(Chem. Cenfr., 1887, 1082--1084j .-Hydriodic acid, like hydrochloricacid, decomposes caffeine into carbonic oxide and anhydride, formicacid, sarcosirie, ammonia, and methy lamine ; if phosphorus is added,glycocine is formed instead of sarcosine, whilst hydrogen phosphideand pliosphoninm iodide are evoliied. Although methyl iodide readilycombines with cafleine to form, the methiodide, the formation of the cor-respoiiding ethyl-compound presents considerable difhulty. Phenyl-hydrazine will not combine with caffeine; from this it would seemthat in this casa, as an an;~loqiie of carbamide, the carbonyl-group isdirectly combined with the nitrogen-atom.Ca-ft h e ch lo?-iodide, CsHI,N4O2,CI1, is produced when sodium nitriteand potassium iodide are added to a, hydrochloric acid solution of thisbase ; it forms golden needles melting a t 182--183", and is decom-posed into it.: const,itnents by ammonia or by boiling with water.Themethod proposed by Mdy and Andreasch for the preparation of caffei-dine presents no advantage over that of Strecker. Caffeine sulphatORQANIC CHEMISTRY. 69differs from the hydroiodide in that the farmer, when heated, turnspurple-red, whilst the latter yields a green mass ; the anrochlorideof caffeine cannot be isolated. The base is best separated from thesulphate by means of basic lead carbonate. Methy leafezdine hydr-iodide is not a well-defined substance, but the free base is crystallineand melts at 86-88' ; dimethy Zccrflei'dine forms leaflets melting at123".The author ascribes the following constitution to cdeidine,"<NMe*C(NH) NM+CHy.~~~e.V. H. V.Hydroquinine. By 0. HESSE (Annalen, 241, 255-287) .-Hydro-quinine, C2OH26N~02, exists ready. formed in cinchona bark, and ispresent in varying quantities in commercial quinine. It is COII-veniently prepared from the mother-liquor obtained in the manu-facture of the acid sulphate of quinine. The mother-liquor isneutralised and the neutral salt dissolved in sulphuric acid, quininexionosulphate crystallises, and the mother-liquor containing the hydro-quinine is again neutralised. By repeating these operations a salt isobtained containing 30 per cent. of hydroquinine sulphate. The quinineis removed by oxidising the solution in sulphuric acid with potassiumpermanganate, the mixture is filtered and the hydroquinine liberatedby the addition of an alkali and extracted with ether.The base isdeposited from its solution in chloroform in needles and from hotacetone in long plates. Many of the properties of the compound havebeen previously described by the author (Abstr., 1882, 1113). It islaevogyrate [a]= = -1142.2" for a 2.4 per cent. solution in 95 perper cent. alcohol at 20", and [a]= = -227.1" for an aqueous solutionof the same strength under similar conditions. (40 C.C. normal hydro-chloric acid were contained i n each 100 C.C. of water used for the solu-tion.) When ammonia is added to a solution of equal molecular propor-tions of cupre'ine and hydroquinine in water containing sulphuric acid,and the acid mixture extracted with ether, a crystalline compound ofcupre'ine and hydroquinine is obtained, C,oH2,N20,,C,~H2~N,02 + 2H20.Hydroquinine forms similar compounds with conchinine and hydro-conchinine. It also unites with two and with three molecules ofcinchonidine, forming crystalline compounds which do not contain anywater of crystallisation. Analogous compounds are formed withhydrocinchonidine and with homocinchonidine.Anethoillztldroq~inine, (CJI&zO2)2, C&,,O + 2H20, is depositedin quadratic prisms from a solution of 5 parts of hydroquinine and1 part of anethoil in warm dcohol.Hydroquinine forms three series of salts, which are as a rule moresoluble than the corresponding salts of quinine.The normal sulpl~at~e,( Cz~H~6N20z)2,H2S04 + 6Hz0, has been previously described (Zoc. cit.).It forms a crystalline compound with phenol, ( CzoH26~zOZ),S03, C6H60 + 2H20, which is spayingly soluble in cold water. The acid sulphate,C20H26N202,S0& + 3Hz0, is freely soluble in water and alcohol.At 140°, the anhydrous salt is converted into hydroquinine sulphate.The disulphate is amorphous. Dichroic crystals resembling hydro70 ABSTRACTS OF CHEPolICAL PAPERS.quinine herepathite are obtained by adding potassiiim iodide (2 mols.)to an alcoholic solution of the acid sulphate (4 mols.), and acting onthe product with an alcoholic solution of iodine.Hydroquinine hyposulphite, ( CzOH26NzOz)a,H2Sz0, -f- 2H20, formswhite prisms sparingly soluble in water.The hydrochloride,CmH26Nz02HC1 + 2Hz0,crystallises in prisms, andis freely soluble in alcohol and water. Theplntinochlorides, ( C20H26Nz02)z,H2PtC16 + 3H20 and C20Hz6Nz02,~zPtCI,-t- 2Hz0, are amorphous and are sparingly soluble in water; themercurochloride, ( CzoHz6Nz~zH~1)zH~CI,, crystallises in needles. Thehydrobromides, CzoHzaN20z,HBr + 2Hz0 and C20Hz6N20R,2HBr + 3H20,also form needles. The neutral hydriodide is a colourless oily liqnidwhich solidifies to an amorphous mass. Potassium iodide producesin acid solutions of hydroquinine salts a yellow, crystalline precipi-tate of the acid hydriodide, CzoHz6NzO2,2HI + 4H20. On theaddition of iodine to the alcoholic solution of this salt, dichroic,ueedle-shaped crystals of the composition C2,,H2,N20,2(IH,IZ) aredeposited.The acetate, CmH26N202,C2H402 + 5Hz0, crystallises inneedles and is freely soluble in alcohol and water. The benzoateand sdicylate dissolve freely in alcohol. The benzoate is anhydrous.The piperonate, CzoHz6NzOz,C8~604, is soluble in water and in chloro-form. Thc oxalate is deposited from hot alcohol in prisms containing6 mols. H20. The tartrate also crystallises in prisms containing2 mols. H,O. It is soluble in alcohol, water, and in a mixtureof alcohol and chloroform. The citrate and arssnate crystallise with10 rnols. HzO, the phosphate with 7 mols. H,O. The chromate,( Cz0H26NzOz)zHzCr04 + 6Hz0, forms golden needles. The dichromateis an oily liquid.Hydroquinicine dissolves freely in ether, alcohol, chloroform, and indilute acids. The solution in dilute sulphuric acid is yellow; thecolour changes to green on the addition of chlorine water and ammonia,b u t the mixture is not fluorescent. An ethereal solution of oxalicacid produces in an ethereal solution of hydroquinicine an amorphousprecipitate soluble in chloroform.The normal sulphate cryst,allisesin needles and dissolves freely in alcohol and in water.Hydroquinine platinockloride, C20Hz6N202, HzPtCI, + HzO, formsorange-coloured crystals. Hydroquinine unites with methyl iodide,forming the compound CzoH26Nz0z,MeI + CzH60. It crystallises inprisms of a yellow colour and dissolves in hot alcohol. It meltsat 218". On treatment with silver chloride, it is converted intothe chloride CzoHz6Nz0z,MeCl + 2Hz0.The acid platinochlol"ide,C,Hz6N,0z,Me*HPt Cl6 + 2H20, forms orange-coloured crystals, andthe normal salt, (C~OEIZ~N,O,M~),,P~CI,, pale-yellow needles. Hydro-quinine methylhydroxide is amorphous. It is soluble in alcoholand water. The solutions are caustic and absorb carbonic anhy-dride.AcetyEhy droquinhe, Cz0R25N202Ac, is amorphous. It melts at 40"and dissolves freely in alcohol, ether, benzene, and in acids. Thesolution is laevogyrate, and the solution in sulphuric acid is fluorescent.The platinockloride contains 2 mols. H20, and the normal sulphateORGANIC CHEMISTRY. 71which is soluble in hot water and alcohol, crystallises with 9 mols.Hydroquinine is converted into hydrocupreyne dihydrochloride bythe action of hydrochloric acid, sp.gr. 1.125, a t 150". Hydrocuprezize,C,9H,,N,0, + 2H20, exists as a crystalline powder freely soluble inether, alcohol, and chloroform. It melts at 168-170°, and exhibitsa strong basic reaction and forms crystalline salts. Solutions of thenormal salts have a greenish-yellow colour, the acid salts are colour-less. The sulphate, ( ClgH,,N,O,),,H2SO4, is sparingly soluble in waterand in alcohol. The tartrate is sparingly soluble in water, but thedihydrochloride, CleH2iNz02,2HCl + HzO, is freely soluble i n water.The acid platinochloride, C19HzrNz0z,H~PtC16, is crystalline and in-soluble in water.~ydroquininesulpponic acid, C,oH,N,O,*SO,H + H,O, is prepared bydissolving hydroquinine in sulphuric acid a t the ordinary tempera-ture.The solution is poured into water and mixed with excess ofammonia. The acid crystallises in cubes and is soluble in boilingwater, alcohol, and hot solutions of alkalis. It dissolves freely inacids, with which it forms crystalline compounds. The anhydrousacid inelts a t 239".The presence of hydroquinine in cinchona bark vitiates the resultsobtained in the estimation of quinine by the ordinary polariscopicmet hod. w. (3. w.H,O.Apocinchine and Apochinine. By W. J. COMSTOCK and W.KOENIGS (Ber., 20, 2674-8689).-Analyses of salts and bromo-derivatives of apocinchine show that the formula, previously assignedto the base (Abstr., 1882, 224) must be altered to C19H19NO; theformula ascribed to ethylapocinchinic acid (Abstr., 1885, 1248) ig,huwever, retained.The authors now attribute the formation of thecombustible, gaseous halogen compound (? methyl chloride) in thepreparation of apocinchine to some secondary change in the reaction.Apocinc hine hydro bromid e, C19Hlg N 0, HBr, crystal lises from alcoholichydrogen bromide in small, yellow needles, and melts at about 256';the hydriodide, C1gH1gNO,HI, is a yellow, cryst'alline salt ; the PZutinG-chloride, (C,gHlgNO),,H2PtC16, forms orange-yellow crystals and meltsat about 235". The acetyl-derivat,ive, ClyHI8NOAc, forms practicallycolourless crystals, and melts a t 118-119" ; the double phosphates ofapocinchine and ammonium, barium, acd potassium, were also pro-pared, and crystallise well.Bronaapoci?i,chine, CI9H,,NOBr, is prepared by gradually addingbromine to apocinchine hydrobromide dissolved in equal parts ofchloroform and acetic acid until the yellow perbromide begins t3separate; sodiiim hydrogen sulphite is then added and the baseobtained from the chloroform and aqueous layers by evaporation andprecipitation. It is crystalline, melts at 186-188", and is readilysoluble in aqueons soda, benzene, chloroform, and ethyl acetate, lessso in alcohol, carbon bisulphide, ether, and light petroleum.Brom-apocinchine is not altered by prolonged boiling with alcoholic soda,and yields bromoform and cinchonic acid on oxidation with 4 per cent.chromic acid solution72 ABSTRACTS OF CHEMICAL PAPERS.Dibroniethylapocinchine, ClgH,,NBr2*OEt, is prepared by adding ethyl-apocinchine (10 grams) to well-cooled bromine (15 c.c.), digesting theproduct after 12 hours with sodium hydrogen sulphite.and extractingwith alcoholic ammonia; the deposit from the alcoholic solution isthen boiled with dilute sutphnric acid, the resulting solution treatedwith ether and aqueous soda, and the base obtained from the ethereallayer by evaporation. It melts at 116-118". The alkaline solution,after separation from the ether, is found to contain dibromapocin-chine.Ethylapocinchinic acid forms a crystalline hydrochloride and hydro-bromide. The silver salt, C,,H,,NO?Ag, is a white, crystalline saltunaffected by light ; the platinochlorzde, (C,,H,gN0,),,H,PtC16, is pre-cipitated in volumiiious, slender, straw-yellow needles, which are con-verted into small, compact, orange-yellow crystals, when the salt isheated on a water-bath for a short time.Homupocinchina, C,H,,NO, the compound formed together withcarbonic anhydride and ethyl chloride when ethylapocinchinic acid isheated a t 130" with hydrochloric acid (Zoc.cit.), crystallises fromdilate alcohol in colourless crystals which contain water of crystallisa-tion and melt a t 184-185'. It is sparingly soluble in water, ether,benzene, and chloroform, readily soluble in hot alcohol, and differsfrom apocinchine, to which it shows much similarity, in its readysolubility in dilu te aqueous soda. The kydrob romide, CI,H,,NO,HBr + H20, crystallises in glistening, transparent, yellow needles orprisms, melts at 221-222", and is sparingly soluble in water and inexcess of dilute hydrobromic acid.The ethyl-derivative yields acrystalline, yellow sulphate. On fusion with potassium hydroxide,homapocinchine is converted into a compound which probably corre-sponds to oxyapocinchine. When oxidised in very dilute solution withpermangmate, ethylapocinchine yields a mixture of solid acids whichdissolve in dilute sulphuric acid and alkalis. Ethylapocinchinic acidis one constituent of the mixture. To effect a separation, the productis boiled with hydrobromic acid (sp. gr. 1-49>, and the solution treatedwith aqueous soda which precipitates homapocinchine ; careful ncidifi-cation of the filtrate then precipitates a mixture of a t least two acids,of which the one of lower melting point is the more soluble in alcohol.The more soluble acid, C,,H,,NO, or ClgHJVO,, dissolves in dilutemineral acids, melts at 230" with the evolution of gas, and at 240" yieldscarbonic anhydride and a compound, CliH,,NO,.This crystallisesfrom dilute alcohol in colourless, silky needles, melts a t 0,23", is notvolatile without decomposition, and is soluble in dilute araids andalkalis. The hydrobromide, sulphate, and nit rate are crystalline, andsparingly soluble.AcetyZoxya23ocinchilzcl, CI9Hl,NO2Ac, melts at 201--203", and issoluble in alcohol, benzene, and light petroleum.From considerations based on analyses of its salts, the authors haveadopted the formula Cl9H,,NO, for chinine, instead of that previouslyproposed (Abstr., 1885, 910). Chinine h!/ldrobrowide, C19H19N02,HBr,crys tallises in long, sulphur-yellow needles, and is decomposed bywater.The remainder of the paper is devoted to a discussion of the conORQ AKIC CHEMISTRE'.73stitution of these alkalo'ids, in which the authors adhere t o the viewsalready put forward wit>h regard to apocinchine (Abstr., 1885, 1248 ;1887, 600), and suggest that cinchine niay possibly be a dialkyl-amidophenylquinoline, and t,hat the second benzene nucleus is presentin a partially hydrogenated form. w. P. w.Strychninesulphonic Acids. Bp C. STOEHR (Ber., 20, 2i33-2734).-A note calling attention to the fact that the results obtainedby Guareschi (Abstr., 1887, 853) are essentially the same as thosepreviously arrived at by the author (Abstr., 1886, 269).w. P. w.PecuIiar Modification of UrobiIin. By E. SALKOWSKY (Chpm.Centr., 18, 1089) -On examination of a sample of urine peculiarlyrich in urobilin, itl was observed that on keeping this colouringmatter disappeared without any marked change of the colour of theurine. This conversion of the urobilin seems not to be conditionedby the ammoniacal fermentation of the urine or by the presence ofmicro-organisms, Urobilin is a substance readily decomposed, andpasses into a modification which, although still coloured, shows noabsorption-bands, nor fluorescence with zinc clrloride in ammoniacalsolution, and is not taken up by chloroform. It is probable that inmost normal urines, urobilin, as well as its decomposition-products, ispresent.V. H. V.Chemical Formation of Albumin. By C. P. W. KKUKEKBEKG(Chem. Centr., 1887, lOSS).-W hen keratin, previously purified by theaction of pepsin and trypsin, is heated with water in a sealed tube, itdissolves to form an alkaline liquid, possessing a strong odour ofhydrogen sulphide, This liquid contains a non-dialysable substance,keratinose, precipitated by ammonium sulphate, which agrees withhemialburnose as regards these reactions, although it does not givethe hydrochloric acid test,. Kemtinose is converted by pepsin andhydrochloric acid a t a blood-heat into keratinpeptone, which is notprecipitated by ammonium sulphate. Under the same conditionsspongin yields spongiorzose, ft soluble, indiff usible substance ; this isalso converted into spoupiopeptone. By the dccomposition of spongin,carbamitle seems to be formed. The author considers that the albu-minoids and skeletins are related to albumin as methyl to methylether. V. H. V.Coagulation of Albumin. By V. MIcHAn,oFF (Chem. Centr.,1887, 1088).-According to the author the coagulation of albumin isdue to one of two phenomena, namely, t'he true coagulation induced bythe action of ferments or heat, a process analogous to etherification OKthe formation of polyhydro-silicates or glycols, and a pseudo-coagula-tion caused by a loss of " gelatinose-water," which corresponds w i t hthe loss of water of crystallisation of salts. The coagulating power ofsalts on solutions of albumin is dependent on the nature of the aoidand base therein contained; the maximum effect is produced byammonium, the mean by sodium, and the minimum by potassiumsalts. Again, in the case of ammonium salts, the sulphate is mor74 ABSTRACTS OF CHEXICAL PAPERS.----0 ,. .. .. ,.H.. .. .. ..N.. .. .. ..S .. .. .. ..0 .. .. .. . .efficient than the nitrate, and of potassium salts the snlphate than thechloride. V. H. V.Egg Albumin and Albumoses. By R. H.’CHITTENDEN and P. R.BOLTON (Studies from Lab. Physiol. Chem., Yale Uuiv., 2, 126-155).--These experiments were designed to contrast the products of diges-tion of egg albumin with those obtained by Kuhne and Chittendenfrom fibrin. Four samples of albumin were prepared ; i n some casesit was separated from globulin by saturation wi tjh magnesium sul-phate, in others by dilution and the subsequent addition of aceticacid. An elementary analysis of these four samples gave the followingaverage percentages :-C, 52.18 ; H, 6.93 ; N, 15.81 ; S, 1.87 ; 0,23.21. Further, coagulated products did not differ in compositionfrom non-coagulated albumin. These results do not agree with anyof the formula ascribed to albumin by previous observers.Peptic digestion of fhe albumin resulted in the formation of albu-minoses of which the percentage composition and reactions weredetermined. In composition they were found t o differ from eachother somewhat more than the albumoses from fibrin ; collectively,however, there is less difference in composition between the albu-Moses and the egg albumin from which they were formed than inthe case of the albumoses from fibrin. The following table givesthe final results :-Proto- Deutero- Proto- Deutero- Egg.albumose. albumose. Fibrin’ albumose. albumose. albumin.-- ------- -50’7’: 50.65 52.68 51-07 51.62 52.336-78 6.83 6 *83 6 -98 6.97 6 *9817.14 17.17 16-91 16’00 15-82 15.851.08 0 -97 1 .lo 1 -95 1 *96 1 -8224?23 24.38 22.48 24.00 23.63 23-02Fibrili products. Egg albumin products. II n their yeactions the different albumoses (proto-, deutero-, hetero-,and dys-albumose) obtained from egg albumin do not differ essentiallyfrom those obtained from fibrin. W. I). H.Metallic Compounds of Albumin and Myosin. By R. H.CHITTENDEN and H. H. WHITEHOUSE (Studies from Lab. Physiol.Chem., Yale Univ., 95--125).--Many researches on the subject of themetallic compounds of albumin have been carried out since Lieber-kuhn attempted to establish the molecular weight of albumin by theanalysis OE copper albuminate. The more recent work of Harnack(Abstr., 1882, 747) showed that two compounds of albumin (fromwhite of egg) with copper occur, one containing 1.35 per cent., andthe otlier 2-64 per cent. of copper. I n the present research, albuminwas freed from globulin by the use of dilute acetic acid, and both thORGANIC CHEMISTRY. 75acetate and snlphate of copper were used in the preparation of thealbuminate. The precipitate was well washed with water, powdered,and dried. The percentage of copper was first determined as cupricoxide by ignition and weighing : the oxide was then dissoived in dilutenitric acid, treated with hydrogen sulphide, and the amount of cuproussulphide obtained weighed. By the former method, in 15 prepam-tions the average result was 1.17 per cent. of copper; and by thelatter method 0.94 per cent. ; the preparations, therefore, contain 0.23per cerit. of ash. I n order to obtain less ash, Harnack dissolved tthealbuminate in sodium carbonate and reprecipitated it by the carefuladdition of acid; this process was repeated several times. Thistreatment certainly increases t,he percentage of copper, but is asource of error, as the sodium carbonate withdraws a portion of thea1 bumin. Long-continued washing with water also causes partialdissociation of the compound. The results obtained correspond withthe formula (C72H11,N18S022)~ + Cu - H,.A normal lead salt causes a small precipitate when added to albu-min, whilst with basic lead acetate the albumin is completely precipi-tated. This confirms the previous statement of Berzelius (Lehrbuchder Chemie, 9, 29). The preparations were well washed from bothlead and albumin, dried, and the lead was determined, first by simpleignition, and then obta,ined as sulphate, which was ignited. Theresults indicate that more than one compound of lead is formed, thatmade by the addition of a large excess of the basic acetate, containingabout five times as much lead as the ordinary basic lead compounds.An iron compound Tvbich was found to be more stable than thecopper albuminate, and corresponded fairly well with the formula( C72H:llzN18s02,)4 + Fe -H3, and a zinc compound, (C7,H,,,N18S02,)a +Zn - H2 ; acid compounds with uranium, (~,2Hl12N18s022)3 + U - H2 ;with mercury, (C7,Hl,,N,8S0,)4 + Hg - H,; and with silver,(C7,Hll,N,8SO,2), + Ag. - Ha, were also prepared and analysed.Much stress is not laid on such forrnu1Be;as it seems possible to forma large variety of compounds by simply modifying the conditions ofprecipitations. This, with the undoubted tendency of the compoundsto dissociation, may account for the lack of agreement in the resultsof different workers. Similar compounds prepared from myosinobtained by extracting ox flesh with 15 per cent. ammonium chloridewere prepared, and the percentage results show that these two formsof prote'id matter do not form corresponding compounds with themetallic salts used. This is illustrated by the following table :76 ABSTRACTS OF CHEMICAL PAPERS.--.......... .......... ........................................................... ..........Copper compoundIron 9 ,Zinc 9 7Ura,nyl ,,Mercury ,,Lead ?,Silver ,,Nickel ,,Cobalt ,,Egg albumin.0 *94 per cent. Cu0.95 ,, Fe0.91 ,, Zn4.60 ,, U2.89 ,,2.56 ,?4.09 ,, AgFf-Myosia.1-17 per cent. Cu2.29 ,, Pe0.72 ,, Zn2.43 ,, Hg4-70 ,, Ni6-03 ,, Co7-49 ), u--W. D. H.Casein and Caseoses. By R. H. CHITTENDEN and H. M. PAINTER(Studies from Lab. Physiol. C'hern., Yale Univ., 2, 156-199),-Danilewsky ( Z e i t . physiol. Chem., 7, 433) has asserted that casejin isa mixture of two protejids, caseoprotalbin, partially soluble, andcaseoalbumin, insoluble in hot 50 per cent. alcohol. Hammarsten(ibid., 7, 227) has shown that the peculiar behaviour of Danilewsky'scase'in is due to its containing calcium phosphate, the presence ofwhich impurit'y depends on the use of hydrochloric acid in the pre-cipitatioii of the case'in, as this acid does not favour the removal ofthe salt as well as acetic acid. He also considers that casein is asingle prote'id. I n the present research, seTen distinct preparationsof casejin were made. Elementary analyses show a close agreementthroughout, and the results mcreover accord closely with those ofHainmars ten,I n the digestion of casein with hydrochloric acid, peptones areultimately formed, and the name caseose is given to the intermediateproducts. These were separated by the methods of Kiihne and Chit-tenden into proto-, hetero-, and deutero-caseose, which correspond withthe albunioses with similar names. The quantity of heterocaseoseobtained was usually very small. The reactions characteristic ofalbumoses apply generally to the caseoses. Unlike proto-albumosehowever, protocnseose is precipihated from aqueous solutions by aceticacid. The average of the analyses of 10 preparations of proto-caseose gives the following percentage results :-I-_I-- --I---!---Protocaseose ........ 1 52.89 1 7.10 I 15-94 1 0.95 1 23.12Case'in.. ........... 53.30 7.07 15.91 0.82 22.03Deuterocaseose contains ZL smaller percentage of carbon than proto-caseose, and heterocaseose contains fully as much carbon as case'initself.An insoluble, semi-gelatinous substance which separates in thefirst stage digestion has not yet been inveshigated. Weyl's com-mercial " case'in-peptone " contains large quantities of caseoses.W. D. H"P PHYSIOLOGICAL CHEMISTRY. 1 4Animal Tannin. By M. VILLON (Cham. News, 56, 175).-cornweevils CCaZandra graneria) were killed, ground in a mortar, anddigested for one hour in boiling 90 per cent. alcohol. The residuefrom the evaporat,ion of the extract is taken up with ethyl acetate atSO", .and precipitated by means of ammoiiiacal zinc a,cetate. The preci-pitate is decomposed with oxalic acid, and the solution evaporated inR vacuum. In this way 3 per cent. of a substance having all thegeneral properties of tannin is obtained from the weevils. This animaltannin, fracticomitanrzin, forms small reddis h-ye!Iow scales.D. A, L