20 ARSTHACTS OF CEEMICAL PAPERS. Organic Chemistry. Tetrabromides of Diallyl. By G. CIAMICIAR and F. ANDERLINI (Bey. 22 2497-!2500).-A small quantity of an oily bromide C6H1,,Br1 is formed in preparing diallyl tetrabromide (m. p. 63") by treating the hydrocarbon with bromine ; when the crude product is crystallised from alcohol the liquid bromide remains in solution. It boils at 135-140" (about 8 mm.) with slight decomposition and its molecular weight determined by Raoult's method in benzene solu- tion was found to be 325 as the average of two experiments. ?-Pen tyleneglycol and its An'hydride (Tetrahydromethyl- furfuran). By A. LIPP (Bey. 22 2567-2573).-y-PentylenegIycol (Freer and Perkin Trans. 1887 836) mixes in all proportions with water alcohol and chloroibrm is rather sparingly soluble in ether in presence of moisture and is insoluble in light petroleum.At -18" it is quite viscid. It boils at 219-220" (under 713mm. pressure) and does not decompose at 236". Sp. gr. = 1.0003 a t 0" (water at 0" = 1). When heated with 35-40 per cent. hydrobromic acid for one hour at loo" the anhydride is formed ; this boils at 77-7.9" ; sp. gr. = 0.8748 a t 0" (water a t 0" = 1). It !is not changed when heated with water a t 200-210". y-Penty Zene dihrornide CHBrMe.CH2*CH2*CHzBr is obtained by heating the glycol or the anhydride with 3 to 4 parts of fuming hydro- bromic acid for three hours at 100". I t boils at 200-202'with partial decomposition is insoluble in water readily soluble in alcohol ether chloroform and carbon bisulphide. Action of Lead Peroxide on Organic Substances in Alkaline Solution.By M. GLASER and T. MORAWSKI (Jfonatsh. 10 57%- 584).-When a mixture of glycerol (2 grams) sodium or potassium hydroxide (5-10 grams) and lead peroxide ('25 grams) contained in water (100 c.c.) is gently heated a vigorous evolution of hydrogen occurs sodium or potassium formato being simultaneously formed according to the equation C3Hs03 + 3 0 = H2 + SH*COOH. About 97 per cent. of the theoret cal quantity of formic acid is produced. Under somewhat similar circumstances ethylene glycol also yieIds hydrogen and formic acid (yield about 60 per cent.) G2H6Oz + 2 0 = F. S. K. Ammonia is also withaut action on it at 200". N. 3. &I.ORQANIC CHEMISTRY. 22 H + 2CH,O2. peroxide with polyhydric alcohols in alkaline solution. The,authors intend to study the behaviour of lend G.T. 31. Action of Ammoniacal Cupric Oxide on Carbon Compounds. By C. VINCEPT and DELACHAXAL (Conzpt. rend. 109 615 -616).- Pure sorbite is completely precipitated by ammoniacal cupric oxide and hence cannot be separated from mmnilol by means of this reagent (compare Guignet Abstr. 1889 1133). Action of Cuprammonium Sulphate on Sorbite. By C. E. GUIGNET (Coiiipt. rend. 109,645).-Cupr,zmmonium sulphate un- doubtedly precipitates sorbite (preceding abstract) but it precipi- tates mannitol more rapidly and by fractional precipit,ation the author has been able repeatedly to separate pure mannitol from liquids which also contained sorbite. C. H. l3. C. H. B. Sorbite. By C. VINCEXT and DELACHANAL (Conipt.rend. 109 676-679).-Sorbtte exists in the fruit of all the wsaceSe and espe- cially in pears cherries arid plnms which contain 0.7 to 0 8 per cent. When heated with concentrated hydriodic acid it yields /3-hexyl iodide which boils at 16'7" undera pressure of 753 min. ; when heated with alcoholic potash i t yields /3-hexylene boiling a t 68.5 under a pressure of 735 mm. and acetic and butyric acids when oxidised. 90 C.C. of water and 35 grams of red phosphorus were gradually mixcd with 150 grams of iodine in a capacious retort 60 grams of crystallised sorbite was added and the mixture gently heated. An energetic reaction took place and /3- hexyl iodide was obtained in almost theoretical quantity no resinous products being formed. Mannitol yields the same /3- hexyl iodide when treated wit,h hydriodic acid.When heated with acetic anhydride and a small quantity of zinc chloride sorbite yields a hexacetate C6H,(OAc) which is obtained as a very thick colourless syrup on washing the crude product with water dissolving in ether and evaporating the filtered ethereal solu- tions. It follows from these results that the constitution of anhydrous sorbite is c6&( OH),. C. H. B Transformation of Cane Sugar .*into Dextrose. By J. BOCK (Che:;i. Cedr. 1889 ii 30 from Oster-ungar. xeit. Zucker. h i d . L w d w . 18 194) .-Cherries which had been preserved by heating with a hot concentrated solution of cane-sugar and which had kept perfectly sound during the winter were allowed to remain for four or five days in a loosely covered dish when it was found that they were coatedwith a white crystalline mass which after separation and recrystallisation proved to be dextrose.Levulose was not found. The exact circums tames under which this change took place could not be determined. J. W. L. Raffinose. By BERTHELOT (Conzpt. r e d . 109 548-550).-The ordinary crystals of raflinose are generally regarde.1 as having the28 ABSTRACTS OF UHEMXCAL PAPERS. composition C,,H,,016 + 5H20 but rafliriose from cotton seed sepa- rates from dilute alcohol in the form of a syrup which gradually solidifies to lamellar crystals which contain 6 mols. H,O and are different from the ordinary crystals. The rotatory power of their solution is however the same as that of a solution of the ordinar;)- crystals. The aut,hor confirms Tollens' observat'ion that good beer yeast fer- nients raffinose completely but that weak yeast ferments only about one-third even after 48 hours zlthough during the same time it will completely ferment eaccharose and glucose.I t seems most probable tlint uiider these conditions raffinose splits up into glucose which ferments and either a saccharose which has a sinall reducing power like lactose or a mixture of two glucoses only one of which has reducing power. C. H. B. By D. LOISEAU (C'ompt. 1-e7atZ. 109 614-615).-111 a sealed paper dated March 5th' 1888 the author described the following results Raffinose is com- pletely fermented by low bcer yeast but with high beer yeast only about one-third of the total possible alcohol is formed whilst the solution has a reducing power equivalent to that of a quantity of glucose equivalent t o the amount of raEnose which has been fey- mented.It is probable that 2 mols. of raffinose are converted into 1 mol. of laevogyrnte glucose which always ferments and twice the quaiitity of a dextrogyrate compoiind which is not fermented by high yeast. Prolonged contact with acids converts this compound into glucose which is completely fermented by both forms of yeast. This difference in behaviour wit,h raflinose may be used as a means of distinguishing between high and low yeast (compare Berthelot preceding abstract). C. H. B. Lactose. By E. W. T. JOKES (Analyst 14 81-83).-Having obtained some very pure crystallised lactose the author has redeter- mined the specific rotatory power and cupric reduction.For a solu- tion of 5 grams of the crystals C,,H2,0 + H,O in 100 c.c. pi.('- pared hot and of sp. gr. 1018.6 at 15*5" the values obtained are :- Fermentation of Rafhose by Beer Yeast. For C,2H,,01,. 60.5" 54.6 CUO x 0.5723 = C1ZHZZO1I. CuO x 0.6024 = ClzH2z0,1 + H20. The determinations were made by O'Sullivan's method the cuprous oxide being converted iuto cupric oxide by careful ignition and weighed. Lactose is not affected optically or in reducing power by heating with citric acid whilst cane sugar is completely inverted. The cryst,als do not lose their water by 24 11oui*s' heating in a water-oven bnt if dissolved in water and re-dried the anhydrous sugar is obtained in a few hours. 31. J. S.ORGANIC CHEMISTRY. 23 Methylhydrazine.By G. v. BR~~NING (Annalen 253 5-14).- I n order to prepare methylhydrazine nitrosomethylcarbamide NO-NMe-CONH is first obtained by adding the theoretical quantity of solid sodium nitrite to a solution of methylcarbamide nitrate mixed wif h powdered ice. Not more tban 50 grams of methylcarbamide nitrate should be used in each operation. The nitroso-compound forms small yellow crystalline plates and melts at 123-124" with decomposition. It is soluble in hot water alcohol and ether. The aqueous solution is decomposed by prolonged boiling. Methylhydrazine is prepared by adding zinc-dust (4 parts) in small quantities to the nitroso-compound suspended in water (6 parts) and acetic acid ( 2 i parts) ; the tempe- rature of the mixture must be kept between 5" and 15" and the operation lasts two to three hours.The product is filtered; the filtrate acidified with hydrochloric acid concentrated and the thick liquid boiled with 3 pwts of strong hydrochloric acid for 12 hours in a flask provided with a reflux condenser in order to decompose the carbamide; the well-cooled liquid is then mixed with an excess of sodium hydroxide and distilled in a current of steam the distilla- tion being stopped as soon as the distillate ceases to reduce l-'ehling's solution. The distillate consists of an aqueous solution of methyl- hydraziiie ammonia and methylamine. The latter compounds are removed by boiling the solution briskly for eight hours in a flask with a reflux condenser. The methylhydrazine is converted into the acid sulphate which is deposited on the addition of absolute alcohol to the concentrated solution. The free base is obtained by decomposing a concentrated solution of the sulphate with sodium hydroxide.The last traces of water are removed by treating the base with barium oxide in sealed tubes at 100". Methylhydrazine NHMe*NH2 is a colourless mobile liquid fuming in damp air. It boils a t 87" (745 mm.) and is miscible in all. proportions with water alcohol and ether. It strongly red iices Fehling's solution at the ordinary temperature and attacks cork caoutchouc and the skin. The acid s d p h u t e N,HJfe,H2SO4 forms long white needles. It melts a t 139.5" and decomposes a t 182". Unlike the normal sulphate it is insoluble in alcohol. The hydrochloride is precipitated from its alcoholic solution by ether.The picrate is deposited from alcohol in yellow needle-shaped crystals and melts a t 162" with decomposition. Methylseinicarbazide NH,*CO*N2H,Me prepared by the action of potassium cyannte on methylhydrazine sulphate. crystallises in prismatic plates and melts at 113". It is freely soluble in water and alcohol. 1Clethylphenylthiosemicarbazide NHPh.CS*N,H2Me is formed by the action of phenylthiocarbimide on an aqueous solution of methylhydrazine. This compound is soluble in water and alcohol and melts at 143"; the aqueous solution is decomposed by mineral acids. Dibenzoy Zmethylhydrazine N,HMeBz is freely soluble in alcohol and in dilute alkalis ; it melts at 143" and crystallises in colourless needles. Metlylpicraxide N,H,Me*C,H,(NO,) is formed when an alcoholic solution of picryl chloride is added to a solution of the base.It crystallises in yellow plates melts a t 171" with decomposit]ion and is freelv soluble in alcohol and ether. OxnZyZd inaethyZhydraci?ze N,H,Me*C,O,*N,H,Me melts at 221" but The oxalate is soluble in warm alcohol.2 4 Al3STHACTS OF CHEMICAL PAPERY. it begins to sublime about 160". It is soluble in alcohol and reduces Fehling's solution when gently warmed. The nitroso-derivative crystallises in plates and melts at 147" with decomposition. Action of Methylhydrazine on Dialdehydes and Diketones. By K. KOHLRAUSCH (A.nii.aZen 253 15-24).-Methylphenylhydr- azine yeacts with berizile a t loo" yielding b e n z i Z e m e t h y l ~ h e ~ ~ ~ ~ Z h ~ d ~ r a x o ~ ~ e COPh.CPIi:K*NMel,h a crystalline substance freely soluble in alcohol ether and light petroleum.It melts a t 5.5-56" and is completely decomposed a t 200" ; it is also decomposed by strong hydrochloric acid a t the ordinary temperature. Benzilemethylphenyiosuzone C,Ph,(N*NMePh) is formed when a mixture of benzile (1 mol.) and methylphenylhydrazine ('2; niols.) is heated a t 120" ; the crude product is treated with hot dilute sulphuric acid to remove the excess of base and the red crystalline mass which is deposited when the mixture cools is purified by recrystallisation from alcohol. The pure substance forlns yellow needles soluble in ether arid acetone melts a t 1 7 ~ - 1 8 ~ " and is decomposed a t 220' ; it is not readily attacked by strong hydiw hloric acid. Olyoxulrtteti~ylp;pherLyl.,scizolze C,H2(N*NMePh) is deposited as a yellow pi-ecipttat,e when an aqueous solution of glyoxal is added to nil acetic acid solution of niethylpheiiylhydrazine.It melts a t 217-218" and is completely decomposed a t 250". This osazone does uot give a characteristic coloration with ferric chloride. i s freely soluble in ether.. It melts a t 103-104" and begins to decom- pose a t 2 10'. 1'.2'.3'-MethylplienylacetylilLclole is formed when methylpheiiylhydrazone is fused with zinc chloride. The indole melts a t 136" arid dissolves freelyin glacial acetic acid. It is decom- posed by strong hydrochloric acid a t loo" yielding Degen's 1'.2-methylplie1rylindole (Abstr. 1887 149). Acet!jlu,:etonem~t~~~ZplisiLylh~drazirL~ CHi?Ac.CMe:N*NePh is a yeliow oil which can be distilled in a vacuum without decomposition.The compound formed by the action of niethylphenylhydrazine on an excess of acetonylacetone could not be isolated as it undergoes spon tsrieous decomposition losing a molecule of water and changing into the methylphenylamidodimethylpyrroline described by Knorr (Abstr. 1887 276). a c e t o n y l i c e t o . r L e m ~ t ~ ~ y l ~ ~ ~ e n ~ I l ~ ~ ~ i y d r a % o n e C2H4( CMe:NMePh) is deposited in the form of an oil which slowly crystallises when an aqueous solution of acet,onylacetone is added to excess of metliyl- phenyl hydrazine dissolved in acetic acid. The crystals melt at 143-144!" and dissolve in alcohol ether benzene and light petroleum. The diliydrazone dissolves also in hydrochloric acid ; when this solu- tioii is heated the preceding pyrroline-compound appears to be formed.w. c. w. w. c. w. Be 7 b zoy 1 ace t o ? A e rn e 1 IL y lp h my 1 hg d r az 011 e C H A c * C P h N * N Me P h Derivatives of Dichloromaleimide. By G. CIAMICIAN and p. SICBEE (Ber. 22 fL490-2497).-Chlorar1ilidomaleimide (m. p. 195-196") is decomposed when heated a.bore its melting- point; it is soluble in ether and hot alcohol but only sparingly in boiling water.ORGANIC CEEMISTRP. 25 It dissolves in hot dilute sulphuric acid,.yielding a colourless solution and in alcoholic solutions dimethylanilme produces a reddish-brown coloration. Chloramidomaleinzide C,C102(NH,) :NH is obtained in sinall quantity when dichloromaleirnide is he8 ted under pressure with excess of alcoholic ammonia.It ci~ystallises from water in golden needles melts a t 280" and is soluble in alcohol and ether but insoluble in benzene. It dissolves in alkalis with a yellow coloration but the solution becomes colourless on heating. Dich ZoromuZewnic acid COOH-C,Cl,-CO-NH + H20 prepared by heating dichloromaleiniide (8 grams) with ammonia (80 c.c.) in sealed tubes separates from water in crystalline aggregates melts a t 175" with decomposition and is soluble in ether alcohol and warm water but insoluble in benzene. The silver salt CaHC1,N0,Ag2 crystallises in colourless needles and explodes when heated. An orange-red compound CuH,,N,O or C,,H,,N,O2 separates in crystals when dichloromaleimide is heated with phenylhydrazine in alcoholic solution. This substance crystallises from boiling acetone or glacial acetic acid in orange-red needles melts at 269-271" with decomposition and is only sparingly soluble i n most ordinary solvents.It dissolves in concentrated sulphuric acid with an intense red coloration and on adding water an orange-red flocculent substance is precipitated. P. S. K. BJ- E. BAUMANN and E. F n o m ( B e y . 22,2600- 26~9).-P-Trithioaldel~yde (Klinper Abstr. 1879 780) is formed when hydrogen sulphide is passed through a mixture of aldehyde (1 part) with alcohol previously saturated with hydrogen chloride (3 parts) ; crystals soon separate and the whole becomes solid. The product is washed with water and crystallised from alcohol from which it separates in Iong needles melting a t 125-126". A small amount of a-trithioaldehyde melting a t 101-102" is also formed as well as a few crystals of a substance melting a t 76" possibly Marck- wald's y-derivative (Abstr.1886 865). a-Trithioaldehyde is obtained as the chief product when eqiral parts of aldehyde water and strong hydrochloric acid are used. It crlstal- lises from acetone ill splendid prisms an inch long. The /%compound is also formed. p-'l'hiobenzaldehyde and ythiobenzaldehyde are formed when hydro- gen sulphide is passed through a mixture of benzaldeb yde and alcoholic hydrogen chloride. The product is boiled with benzene until almost all is dissolved; on cooling the @compound separates in crystals having the ComposiLion sc7H6s + c6H6 (not C7H,S 4- CsHc Klinger) ; this gives up all the benzene a t ItjO" and a portion when kept a t the ordinary temperature for a long time.y-T~~iobenzuZdehy~e C7H6S crystallises from Senzene in small pointed needles melting a t 166-167". The crystals contain no benzene of crystallisation. When the solution in benzene is treated with iodine the whole solidifies after some time being converted into the p-derivative. When a - or P-trithioaldehyds is oxidised with potassium perman- Thioaldehydes.26 ABSTRACTS OF CHEXICAL PAPERS. ganate they both give as end-product a trisdphone C6Rl2S3O6 together with products containing less oxygen (compare Guareschi Abstr. 1884 294). This forms slender needles softens at 340" becoming yellow and sublimes a t a higher temperature without melt- ing. It is almost insoluble in water very sparingly soluble in alcohol ether chloroform and benzene more soluble in hot acetic acid; it also dissolves readily in strong nitric or sulphuric acid but is pre- cipitated by water.Alkalis dissolve it readily and it can be crystal- lised from ammonia and alkaline carbonates. The constitution of trithioaldehyde sulphone is S02<CHMe.SO:>CHMe. CHMe* S 0 When an alcoholic alkaline solution of the substance is treated with methyl iodide the compound CgH18S3O6 melting at 302" is formed. I n a similar manner ethyl- allyl- and benzyl-groups may be added. N. H. M. Thio-derivatives of Ketones. By E. BAUMANN and E. FROMX ( B e r . 22 2.592-2599 ; compare Abstr. 1889 852).-Thioacetone CSMe is formed as a readily volatile oil in the preparation of tri- thioacetone and tetrathioacetone (Zoc. cit.) but was not isolated owing to it's instability and the difficulty of separating it from trithioacetone.It is also produced together with ethyl sulpliide and other sulphur- derivatives when acetone-ethylmercaptole CMe,(SEt) is heated above 160". Owing to the very unpleasant odour of the compound which is stronger tIhan that of any other known substance the smallest traces of it being sufficient to infect whole districts the study of the compound was not continued. Trithioacetone is decomposed by strong nitric acid with explosive violence. A further examination of the sulphone obtained by oxidising tri- thioacetone with potassium permanganate (loo. cit.) showed that this could be separated by crystallisation from alcohol inho two substances. The more sparingly soluble compound triacetnnetrisulphone C9H,,S306 crystallises from glacial acetic acid in slender needles which melt at.302" (uncorr.) and sublime readily. The more readily soluble com- pound CsHl8SsO4 is probably tritlzioacetonedisu~lio~e ; it melts at 208". Acetonetrisulphone is not changed by acids and alkalis; it dis- solves in strong acids and is precipitated by water unchanged. Boiling fuming nitric acid has no action on it. Its constitution is probably CMe2<S02,.CMe:>S02. The compound CgHl,S304 dissolves in bromine pielding an unstable bromine-derivative which readily decomposes with evolution of hy- drogen bromide. When gently heated with fuming nitric acid the compound is oxidised with formation of much sulphuric acid. Probably the substance has the constitution S<C&e:,so:>CMe2.SO *CMe CMe -SO N. H. M. The Introduction of Acid Radicles into Ketone Molecules. By L. CLAISEN (BUZZ. Xoc. Chin&. [S] 1 496-510 ; compare Abstr.,ORGANIC CHEMISTRY. 27 1888 666 671 676 and 1889 5S4 619 850).-B re'sume' of the author's already published work on this subject concluding with a discussion as to the theory of the reactions. Substituted Acrylic and Propiolic Acids. By C. F. MARERY and A. W. S w r H (Ber. 22 2659-2660) .-When a,!%dichloracrylic acid is dissolved in carbon bisulphidc and chlorine passed through the solution whilst it is exposed to sunlight tetrachloroproyiolzic acid C,HCl,-COOH gradually crystallisea out. It forms large rhombic prisms is soluble in carbon bisulphide chloroform and water and melts a t 76". Its barium salt crystallises in prisms ; its ca1ciu.m salt in needles; its potassium salt in plates.Its silver salt is very un- stable When ap-dichloracrylic acid is heated with hydrobromic acid in closed tubes a t 110-120" bromodichloI.opro~ionic acid is formed. It is soluble in water and boiling carbon bisulpliide ci-ystallises in prisms and melts at 75-76'. When an aqueous solution of bromopropiolic acid is mixed with hypochlorous acid and left. in the dark chlorobro.ulzhydroxyacrzJlic acid C,(OH)ClBr.COOH is formed. It is easily soluble in boiling wa.ter is crystalline and melts a t 104-105". I t s silaer salt is soluble in nitric acid and is very unstable in aqueous solution. T. G. N. L. T. T. Action of Phosphorus Pentachloride on Chloralide.Tetra- chlorethylidene Trichlorolactate. By R. ANSCH~TZ and A. R. HASLAM (Annalen 253 121-131).-The compound of the composi- tion C,HC1,O3 which the authors obtained by the action of phos- phorus pentachloride on chloralide (Abstr. 1887 9151 proves to be the tetrachlorethylidene trichlorolactate. It boils a t 276" without decomposition. Nethyl and ethyl alcohol act on this compound at the ordinary temperature yielding hydrogen chloride and the ethyl or methyl salts of trichloracetic and trichlorolactic acids. Normal propyl and isobutyl alcohols act less energetically than ethyl alcohol. Normalpropyl trichlorolactcrte boils at 115-11 7" under 12 mm. pressure and at 248-250" under the ordinary atmospheric pressure. Its sp. gr. a t 20° compared with water a t 4" is 1.51628.Isobutyl tri- chZorolactate boils at 111-i12" under 12 mm. pressnre and at 236-238" under the normal atmospheric pressure. I t s sp. gr. at 20" is 1.53216. The chloride is slowly decomposed by water yielding trichloracetic and trichlorolactic acids. These results indicate that the constitution of the chloride is represented by the formula CC;l,*y (OH) coo- >CC1.CCl,. " w. c. w. Derivatives of Ethyl Acetoacetate. By R. SCH~~NBRODT (AwnaZea 253 168-205).-Ethyl monochlor~~cetoacetate is formed by passing chlorine into ethyl cupracetoacetate suspended in chloro- form until the green colour of the compound changes to grey. By t h e prolonged action of chlorine a dichloro-substit'ution-product is obtained. Analogous resalts are produced when bromine is used instead of chlorine ; the sthylic salts of mono- and di-bromacetoacetic28 ABSTRACTS OF CHEMICAL PAPERS. acid have been described by Duisberg (Annalen 213 152 and 143).E t h y l iodacetoacetate prepared by the action of iodine on ethyl cupr- acetoacetate is a yellow oil miscible with ether and alcohol. The alcoholic solution gives a blood-red coloration with ferric chloride. The compound is unstable. I t decomposes at 25" in a vacuum and its sp. gr. at 1P" is 1.7053 compared with water at the same temperature. It is converted into ethyl monochloracetoacetate by the action of silver chloride but with silver cyanide it yields hydrogen cyanide and ethyl succinosuccinate. The product of the action of silver nitrite on ethyl iodacetoacetnte is a yellvw oil probably ethyl nitroacetoacetate.This substance gives an intense blood-red coloration with ferric chloride and strong snlphuric acid. It does noC yield an amido-com- pound on reduction with tin and hydrochloric acid nor does it form a solid compou'nd with hydroxylamine. It combines with phenylhydr- azine yieldingphenylmethylisonitrosopyrnzolone [ 1 3 4 51 described by Knorr (AWr. 1887,602). The same compound is formed by the action of phenylhydrazine on the ethylic salt of monochlor- brom- or iod-acetate. The reaction may be represented as follows CsFi,C103 Bender (Abstr. 1888 53) has shown that in the ethereal solution phenylhydrazine and ethyl monochloracetoacetate yield the ethylic salt of p-phenyl azocrotonate. The author confirms the accuracy of this observation.Ethyl sodacetoacetate reacts with ethyl iodacetoacetate yielding ethyl diwetosuccinate. Metallic silver eliminates the iodine from ethyl iodacetoacetate and forms the ethyl diacetofumarate described by Just (Abstr. 1886 141). Ethyl thiacetoacetate first prepared by Buchka (Abshr. 188.5 1200) is formed by boiling sulphur in a solu- tion of ethyl cupracetoacetate in benzene. I n the presence of alcohol phosphorus acts on ethyl cupracetoacetate forming ethyl acetoacetate and triethyl phosphite. Arsenic trichloride is reduced by the copper compound arsenic being liberated and ethyl mnochlorncetoacetate formed. Ethyl cupracetoacetate is not attacked by cyanogen. but nitro- gen peroxide acts on it with formation of the nitro-compound which is produced by the action of silvei.nitrite on ethyl iodoacetoacetate. Attempts to displace a hydrogematom by copper in ethyl mrth- ace toacetate were unsuccessful. w. c. w. + SNHPh*NHZ = CloHgN302 + 2NHzPh + NHdC1 + C,H,*OH. Ethyl Thiacetoacetate. By I(. BUCHKA and C. SPRAGUE (Bey. 22 2.541-2556 ; compare Ruchka Abstr. 1885 1200 ; Delisle Abstr. 1887 915 ; and Schonbrodt preceding abstract) .-Ethyl thi- acetoacetate is best prepared by Delisle's method; 100 grams of ethyl acetoacetate yield 60-70 grams of pure ethyl thiacetoacetate. Molecular weight determiiiations by Raoult's method in glacial acetic acid solution showd that the molecular formnla was C,,H,,O,S. It melts at about 76" b u t the melting point observed depends to a considerable extent on tlie rapidity of heating and on other conditions.The sodium-derivative C,,H,,O,SN& is formed when ethyl thiaceto- acet,ate is treated with sodium in ethereal solution. When ethyl thiacetoacetate is treated with phenylhydrazine hydrogen sulphide is evolved and phenylmethylpyrazolonsketv-ORGANIC CHEMISTRY. 29 phenyl hydrazon e ( pheny lme thyl p yrazolonenzobenzei~e) melting at 156O identical with the compound obtained by K n o x (Abstr. 1887 601) is formed together with a yellow substance which is insoluble in all ordinary neutral solvents. The compound obtained by Schon- brodt (Zoc. cit.) by treating ethyl chloro- bronio- or iodo-acetoacetate with phenylhydrazine is not phenylrnethylisonitrosopyrazolone as stated by him but is identical with the phenylmethylpyrazolone- ketophenylhydrazone referred to above.The yellow compound which is obtained together with phenyl- methg1pyrazoloncketophenylhydrazone (see above) when ethyl thi- acetoacetate is treated with phenylhydrazine is decomposed when heated but without melting ; it dissolves in alkalis and is reprecipi- tated on adding acids. It seems to have the composition C,,H,N,Sc) ; when heated with phenplhydraeine it is converted into phenyl- methyl pyrazoloneketophenyl hydrazone with evolution of hydrogen sulphide small quantities of di-phenylmethylpyrazolone being also formed. Para f olylmethy Ipyrazoloneketoparatolylhydrazone is formed w'hen et'hyl thiacetoacetate is Created wiGth qaratalylhydr- azine ; it crystallises from chlorofrom in orange needles melting a t 216-217". When excess of the hydrazine is employed in the above reaction a compound free from sul i)hur and probably corresponding with di-phenylmethylpyrazolone is also obtained. If only a small quan- tity of the hydrazine is used a sulphur compound which is only soluble in alkalis is formed ; .this substance is converted into tolyl- methylpyrazoloneketotolylhydraaone (im.p. 216-21 7") when heated with paratolylhydrazine and when heated with phenylhydmzine it yields a compound. probably tol.ylmethy1pyrazoloneketophenylhydr- azone which crystnllises i n rcd needles melting a t 1.86". E thyl %hiacetoacetate combines with a-naphthylhydrazine yielding similar compounds. I?. S. K. Dithioxamide (Cyanogen DimLphydrate). By J. FORM~NEK (Ber. 22 2655-26569. When a saturated solution of cupric sul- phate is treatod with ammonia untiltthe precipitate first formed is just redissolved potassium cyanide added in quantity just sufficient to discharge the blue colonr and then a rapid stream of hydrogen chloride passed through the solu+ion the latter becomes first yellow and then red; and if it is kept well cooled small red crystals of the formula NH,-CS*CS*NH gradually separate out.L. T. T. Hydroxycitraconic Acid and its Derivatives. By P. MELIKOFF and M. FELDMANN (Annalen 253,87-95 j.-In dilute solutions hypo- uhlorous acid unites with cibraconic acid to form chlorocitramalic acid which has been described by Morawski (this Journ. 1875 142) and by Gottlieb (Annalen 160,101 j. The acid prepared by Gottlieb's process melts a t 139". It is converted into Morawski's hydroxycitra- conic acid by the addition of potessium hydroxide in alcoholic solution.30 ABSTRACTS OF CHEMTCAL PAPERS.The precipitate of pot,assium chloride and hydroxycitrctconate i s washed with alcohol and ether. It is khen dissolved i n water the hydroxy-acid liberated by sulphuric acid and extracted with ether. The acid melts a t 162" as stated by Scherks (Abstr. 1885,513). The ethyl salt C,EI,O(COOEt) has the sp. gr. of 1.1376 at 0" and 1.1167 at 22" compared with water at the same temperatures. Hydroxycitraconic acid dissolves in strong hydrochloric acid a t 0" ; and ether extracts from this solution a monochlorinated hydroxy-acid CUOH*CH( OH)*CClMe*COOH crystallising in rhombic plates which is an isomeride of the acid formed by the union of hypochlorons acid and citraconic acid COOH.CMe(OH)*CHCl*COOH.This acid melts a t 162" and forms unstable salts. The compound which is formed by the addition of hydrobromic acid to hydroxycitraconic acid has already been described by Scherks (Zoc. cit.). Hydroxycit,raconic acid is a glycidic acid as it is converted into amidocitramalic acid by the action of alcoholic ammonia at 100". The amido-acid forms short prisms which seem to belong to the monoclinic system; it reddens litmus and decomposes carbonates. 100 C.C. of water at 18" dissolve 31 grams of the acid. It is almost insoluble in hot alcohol. The calcium and barium salts are amorphous. The hjdrochloride OH.CsH,( NH,) (COOH),,HCI forms transparent prisms soluble in water and alcohol. It melts a t 100" with decomposition.w. c . w. Acetonediacetic or Hydrochelidonic Acid. By J. VOLHARD (AnnuZen 253,206-236) .-The dilsctone of discetic acid is prepared by maintaining succinic acid in a state of slow ebullition for six hours. When a small quantity of the contents of the retort no longer solidifies on cooling but remains as a greasy mass the operation is complete. The crude product is repeatedly extracted with boiling chloroform ; on cooling succinic anhydride is deposited in crystals and the lactone remains in solution. The chloroform is removed by distillation the residue dissolved in water and the lactone is ngaiii extracted from this aqueous solution by chloroforni. The lactone forms transp3rent rhombic prisms u b c = 0.3649 1 0.9816 freely soluble in chloroform acetone ether alcohol benzene and ethyl acetate.It melts a t 75" and boils between 200 and 205"under 15 mm. pressure. The lactone dissolves in alkalis and in strong hydrochloric or hydrobromic acid yielding acetonediacetic acid CO( CH,*CH,*COOH) which is identical with the hgdrochelidoiiic acid of Liebenand Haitinger ( Monatsh. 5 353) and with Marckmald's propiondicarboxylic acid (Abstr. 1888 678) The acid forms rhombic plates soluble in hot water and in alcohol. It melts a t 143O and decomposes at a higher temperature. The normal salts of the alkali metals are very soluble in water and do not cr-j-st:~llise well. The acid potassium sodium and ammonium salts are anhydrous. The barium salt crjstallises with 2 and with 2; mols. H,O. The manganese salt C,H,MnO + fLH,O forms pale pink needles.The zinc and cadmium salts crjstallise in six-sided plates containing 2 mols. H20. The silver salt C7H8Ag?03 is crjstalline and insoluble inORUANIC CHEMXSTRY. 31 water. The dimethyl salt melts at 56' and boils with decomposition at 276-277" (uncorr.). The sp. gr. of the diethyl salt is 1.0862 at 13". Acetic chloride acetic anhydride and phosphoric anhydride convert the acid into the lactone. The phenylhgdrazide of acetonediacetic acid melts at 107 -108". The phenylhydrazide of the dimethyl salt melts a t 88-90' and dissolves in ether benzene and hot alcohol. The corresponding diethyl compound melts at 67". The oximeof the acid crystallises in prisms and melts with decomposition at 129". The oximes of the dimethyl and diethyl salts form needles and melt at 52" and 38' respectively. w.c. w. Alkyl-derivatives of Methyluracil and Nitrourscil. BJ- R. BEHREKD (Annalen 253,65-68).-Ethyl bromide does not react w i t h free methyluracil but it acts on potassium methylurscil forming mono- methyluracil and dimethyluracil. I t is probable that monethylmethyl- uracil is first formed. A portion of the monethylmethyluracil reacts with potassium methyluracil formingpotassium monethylmethyluracil. This is attacked by ethyl bromide yielding diethylmethyluracil. In a previous communication the author stated that methyl iodide acts on potassium methyluracil yielding trimethyluracil and the dihydride of methyluracil ; he now finds that the supposed dihydride is identical with the dimethyluracil described by Hoffmann (next Abstract).w. c. w. Alkyl-derivatives of Methyluracil. By J. HOFFMANN (Annalen 253 68-77).-Ethyl methyluracil and diethylmethyluracil are formed by the action of ethyl bromide or iodide (3 mols.) on potassium methyluracil (1 mol.) in sealed tubes at 150; the excess of ethyl bromide or iodide is removed from the crude product by distillation the residue is dissolved in water and the aqueous solution treated with chloroform. The chloroform extract is then dried and distilled and the residue dissolved in boiling alcohol ; on cooling crystals of ethyl- methyluracil are deposited. The mother-liquor contains monethyl- arid diethyl-methyluracil. The former is deposited as a crystalline crust but the diethyl-derivative can only be isolated by dropping a crystal of diethylmethyluracil into the mother-liquor when crystallisation takes place.fithylmethyZuraci1 is deposited from ethyl bromide in prisms and from alcohol in needles. It is freely soluble in chloroform and in ethyl bromide and is much more soluble in hot than in cold alcohol. A crystalline silver salt C,H,E tAgN20z is obtained when silver nitrate is added in sufficient quantity to produce a permanent turbidity t o a solution of ethylmethyluracil in a 10 per cent. solution of potassium hydr0xid.e. Diethylnaetl/y Zz~racil crystallises in rhombic plates and melts at 52-53" dissolves freely in chloroform alcohol ether and water and is decomposed by potassium hydroxide at the ordinary temperature with liberation of ethylamine. Methjl bromide acts on potassium methyluracil at 140" forming dimethyluracil and tri- methyluracil. !Z'~*imethylz~raciZ melts at lo>" crystallises in rbombic plates and is freely soluble in chloroform alcohol and water arid sparingly soluble i n ether. Di~niethyluracii is insoluble in ether but can32 ABSTRACTS OF CHEMICAL PAPERS.be reerystallised from hot alcohol. Methyluracil di-iodide C,H,N,O,I is formed by the action of iodine dissolved in strong hydriodic acid on methyluracil. It is an unstable compound dissolvinq with decompo- sition in water alcohol and chloroform. The di-iodide furms deep Nitrouracil-derivatives. By M. LEHMANN (Annalen 253 77-87).-Meth~lZnifrozcracil C,H,N30 + H20 is formed by the action of methyl iodide on potassium nitrolnracil in sealed tubes a t 140". It crystallises in long needles and is soluble in hot water.100 C.C. of water a t 20" dissolve 0.714 gram and 100 C.C. of alcohol a t 17" dissolve 0.115 gram of the substance. It is less soluble in ether chlorofsm benzene and methyl iodide than in water. The potassium silver and barium salts are crystalline; the silver and barium salts me almost insoluble in cold water. Methylisobarbitiiric acid C5H6N203 is deposited in crystals when methplnitrouracil is rediiced by tin and hydrochloric acid ; the mother-liquor contains methylamidoucacil in small quantiky. A neu,tral solution of methyl- amidouracil hydrochloride turns red on the addition of potassium cyanate ; the d o u r is destroyed by hydrochioric acid and methylhy- droxyxanthine C6H8N403 is deposited a s a yellow crystalline powder.100 C.C. of water a t 16" dissolve .0*16 gram of rnethylhydroxyxan- thine. Methylnitrouracil i s decomposed by baryta-water a t 160-1 70" with liberation of methylamine ; dimethylnitrouracil under similar treatment yields dimethylamine. Dimethylnitrouracil melts at 154.5" and is deposited from hot water in needles eontairling 9 mol. H20. It does not unite with bases to form salts. The constitntion of methyl- and dimethyl-nitrouracil can be represented by the formulae C o < ~ ~ e - ~ ~ NH'cH >C*NO and C O < ~ ~ ~ ~ ~ > C . S O . Methyhitro- methyluracil prepared by the action of methyl iodide on potassium nitromethyluracil crystallises in needles and melts a t 149". It unites with bases forming c r p t a lline salts. E t h y7nit rouracil C,H,N304 + H,O forms silky needles and melts at 194.5 ; it is de- posited from alcohol in anhydrous crystals and is soluble in hot water ether chloroform benzene and ethyl bromide.The potassium and silver salts crystalhe in needles. Ethylisobarbituric acid C,H,N,O melts at 250" but begins to decompose at 230". It is soluble m hot but almost insoluble in cold violet crystals. w. c. w. water. Ethylhdroz yxanthine crystallises in prisms which turn pink on exposure to the air. Etl~lllrnethy Znitrouracil CO<N~e.CO>C.N02 NFtCH crystallises from hot water in needles containing 1 mol. H,O. The crystals effloresce ; it melts at 109". itl;.thyleth~lnit,.ouracil CO<NEt.Co >C*SO melts at 73" and crystallises in rhonibohedra containing 1 mol. H20.The substance becomes anhydrous a t go' and remains liquid a t the ordinary temperature but solidifies on the addition of water. NMe-CH I t is freely soluble in alcohol and ether. w. c. w.ORGANIC CHEMISTRY. 33 FUCUSO~. By MAQUENNE (Compt. rend. 109 571-573).-Dried Fucus vesiculosus was heated in an oil-bath at 160" with 4.5 parts of sulphuric acid of 20" B and the product after neutralisntion was distilled and fractionated. Small quantities of water and acetone were obtained together with two fractions boiling a t 162-163" and 185-187" respectively. The fraction 162-163" consists of pure fur- furaldehyde the fraction 185 - 187" is methyIfurf.~raldehyde a liquid of sp. gr. 1.105 at 15". With ammonia it yields a crystalline product closely resembling furfuramide ; its hydrazone is an oily liquid ; with silver oxide i t yields methylpyromucic acid melting at 108-109". When treated with hydriodic acid it resinifies but does not carbonise and does not become green ; the product yields iodo- form when mixed with potassium hydroxide.With acetic anhydride in presence of fused sodium acetate it yields methylfurfuracrylic acid melting a t 157" and crystallising from boiling water or alcohol in small white needles which retain aboilt Q mol. H20. If methylfur- furaldehyde is heated with strong hydrochloric acid it becomes green a reaction which Stenhouse observed with fucusol. The following reaction serves to detect methylfurfuraldehyde in presence of a large proportion of furfuraldehyde. One drop of the liquid is dissolved i n 5-6 C.C.of alcohol of 90" and 1 C.C. of sulphuric acid of 60" is added slowly without agitation; a green coloration appears at the junction of the two liquids. The coloration persists even after agitation if the methylfurfuraldehyde is abundant but changes to grey if furfur- aldehyde is in excess. The reaction is similai- to that given by heptine (or its oxidation-products) from perseitol. This methylfurfuraldehyde is identical with that obtained by Hill from wood tar. Fucnsol is not a distinct compound as Stenhouse supposed but is a mixture of furfuraldehyde with about. 10 per cent. of methylfurfur- aldehyde. C. H. B. Relation between Sugars and Furfuran-derivatives. By MAQUENNE (Compt. rend. 109 603-606) .-Methylfnrfnraldehyde from Fucus (preceding Abstr.) yields acetic acid on oxidation and hence contains a terminal methyl-group and is one of the three isomerides which contain the methyl-group in the position 2 3 or 4 with respect to the aldehyde group. It has the same relation t80 isodul- citol or rliamnope C6HI2O6 m furfuraldehyde has to arabinose C5H,,05.Crystallised isodulcitol distilled with four times its weight of sul- phuric acid of 15 to 20" B yields a small quantity of acetone togetber with pure methylfurfuraldehyde identicltl with that from Fucus cesi- cutosus or wood tar but no furfuraldehyde is obtained. Fischer and Tafel have shown that isodulcitol is an aldehyde derived from normal bexane and according to Herzig it yields acetic acid on oxida- tion and hence contains a terminal methyl-group. Its conversion into methylfurfuraldehyde would involve the union of the chains 2 and 5 by means of an atom of oxygen the methyl-group occupying the Position 4.thus :- A VOL. LVIII. Li34 ABSTRACTS OF OHEMICAL PAPERS. Since furfuraldehyde is obtained from arabinose by dehydration it follows that isodulcitol is w-methylarabinose a relation which has often been suggested but has never previously been established The yield of methylfurfuraldehyde from isodulcitol is small but it suffices to detect the isodulcitol in substances in which its presence is not recognised by the usual methods and i t has been detected in several plants in which it was not known to exist. Since Fucus vesicu- losus yields methylf urfurddehyde (Zoc. cit.) it would seem that isodul- citol exists in marine plants.Selenium and Oxygen-derivatives in the Benzene Series. By C. CHABRII~ (Compt. rend. 109 568-570).-The action of nitric acid on phenyl eelenide (Abstr. 1889 1167) yields nitro-derivatives ; potassium permanganate or chromic acid yields indefinite oxidation- products ; hydrogen peroxide and hydrochloric acid yield compounds in which oxygen has been introduced into the phenyl-group. The action of selenious chloride SeOCI on benzene in presence of aluminium chloride yields two compounds according to the proportions of the reacting bodies. Diphenylselenone SeOPh is an amber-yellow liquid which boils at 230" under a pressure of 65 mm. ; sp. gr. a t 19.6 = 1.48. The other product PhSeO*C6HICl crystallises in white hexagonal prismatic lamellse with a fatty lustre ; it melts at 94" boils at 230" under a pressure of a few millimetres is insoluble in water but dissolves in alcohol and is attacked by cold nitric acid.Diphenylselenine when treated with bromine water yields the corn- pound SeO( C6H4Br).? which crystallises from alcohol in modified rhombic prisms melting a t 1'20". When mixed with hydrogen peroxide and hydrochloric acid and treated with a current of air diphenylselenine yields the compound SeO (c6HIc1)2 or Ph SeO*C6H,C12 which crystallises from boiling alcohol in small white prisms melts at 159" and is not attacked by cold nitric acid. The action of the compound Se(OH)&I2 on benzene in presence of aluminium chloride yields diphenylselenine and selenophenol. Action of Phosphorus Trichloride on Phenol.By R. ANSCH~TZ and W. 0. EMERY (Amer. C'hem. J. 11. 379-38i).-By the action of phosphorus trichloride on phenol the following three com- pounds were formed (compare Noack Abstr. 1883 735) and were separated by distillation under greatly diminished pressure :- Phenylphosphoryl dichloride PCl,-OPh ; sp. gr. 1.35412 at 20" (water at 4" = I) ; boiling a t 90' under 11 mm. pressure ; diphenyZphosphoryZ chloride PCl(OPh) ; sp. gr. 1,24378 a t 20" (water at 4" = 1) ; boil- ing at 172" under 11 mm. pressure ; tripheriyl p h o p h i t e P(OPh) ; sp. gr. 1.18428 at 20" (water at 4" = 1) ; boiling at 220" under 11 mm. pressure. The action of phosphorus pentachloride on the preceding com- pounds was investigated. In the cold no action takes place; at 100" crystalline compounds are formed soluble in chloroform and carbon tetrachloride.Chlorine additive-products were almost cer- tainty formed but they could not be isolated ; they were however C. H. B. C. H. B.ORGANIC CHEMISTRY. 35 obtained by passing dry chlorine over solutions of the phosphorous compounds in dry ether. Phenylphosphoryl tetrachloride PCl,*OPh prepared from chlorine and phenylphosphoryl dicbloride forms small plates soluble in chloroform and carbon tetrachloride insoluble in ether ; it is deliquescent and is decomposed by water normal phenyl pbosphate being formed. With sulphurous anhydride i t behaves like the corresponding phosphenyl compound giving thionyl chloride and the oxychloride POCl,-OPh boiling a t 121-122" under 11 mm. pressure. Diphenylphosphoryl trichloride PCl,(OPIi) formed from chlorine and diphenylphosphoryl chloride is a yellow oil solidifying to minute crystals soluble in chloroform insoluble in ether; it easily tlecomposes when heated and also when treated with water in which case phenyl phosphate is formed.Tt.~p~ie~zyll?li~~pla~j~yZ dichluride PC1,( OPh) prepared from chlorine and phenyl phosphite solidifirs a t a very low temperature ; when treated with water it decomposes into phenyl phosphate and hydrochloric acid. By the addition of dry bromine to etliereal solutions of the monn- and di-chlorides the compounds PC12Br2*OPh and PClBr,(OPh) were obtained ; these are very unstable substances. Phenylphosphrvl thiochloride PSC12*OPh was obtained by heating phenylphosphoryl dichloride with sulphur at 190" ; it has a sp.gr. of 1.40393 at 20" (water at 4" = I) boils at l19-i20° under 11 mm. pressure and is a highly refractive liquid soluble in ether and chloro- form. DipTien!il~jhosplioryl thiochzoride PSC1( OPh) prepared from diphenylphosphoryl chloride and sulphur heated aat 190" ; melts a t 63-64" and boils at 194" under 11 mm. pressure. Attempts to obtain the preceding two compounds by heating togeiher phenol and phosphorus thiochloride were unsuccessful hydrogen chloride and normal phenyl phosphate being formed. Tr+hen yl thiophosphate PS( OPh) was obtained by heating phenyl phosphite with sulphur at 190" ; it forms crystalline needles melting at 49-50" and boiling at 245" under 11 mmpressure; sp. gr. = 1.24411 at 20" (water at 4" = I). It is found that these thio-compounds have very nearly the same melting points and boiling points as the correspondiiig oxy-com- pounds.The existence of the compound PC14*OPh leads to the following view of the action of phosphorus pentachloride on hydroxj-com- pounds :- R-OH + PC1 = HC1 + RO*PC14 and RO-YCI = POCl + RC1. C. B. B. Apiole. By G. CIAMICIAN and P. SILBER (Bey. 22 2482-2490; compare Abstr. 1888 Ilc;O).-The authors give the name apionole to the tetrahydroxybenzene which forms the basis of apiole ; the dimethyl ether of tetrahydroxybenzene is therefore dimethylapionole and '' apiorie " is dimethylmetbyleneapionole Dimethylapionole C6Hz(0H),(OMe)2 is obtained when apiolic acid (2.5 grams) is heated at 180" for 4 to 6 hours with potash (8 gramP) and alcohol (10 c.c.).l u aqueous solutions ferrous sulphate produces after some time a blue coloration lead acetate a gelatinous precipitate ai:d silver nitid e a It melts a t 105-106" and boils at 298". d 236 ABSTRACTS OF CHEMICAL PAPERS. crystalline precipitate which immediately turns black. It dissolves in concen hated sulphuric acid yielding a yellow solution which quickly turns red and on warming becomes violet. The diacetyl- derivative C6H2(OMe),( crystallises from alcohol melts a t 144' and is soluble in ether warm alcohol and glacial acetic acid but only sparingly in hot and insoluble in cold water. It dissolves in warm concentrated sulphuric acid yielding a colourless solution which turns yellow and then brown on heating more strongly. Tetramethy lapioriole C6H2 ( OMe)4 prepared by treating the di- methyl-derivative with methyl iodide in methyl alcoholic potash solution crystallises from hot water in colourless needles melts at 81" and is readily soluble in alcohol ether benzene acetone and acetic acid but only sparingly in water. It dissolves in concentrated sul- phuric acid yielding a colourless solution which turns brownish-red on warming and in concentrated nitric acid with a yellow coloration.It is not acted on by hydrochloric acid a t loo" but at higher tem- peratures it is decomposed with evolution of methyl chloride. Apioneacry Eic acid CH2:O2:C6H( OMe) ,*CH C H *C 0 0 H prepared by boiling apiolaldehyde with acetic anhydride and sodium acetate crystal- lisea from hot alcohol in small jellow needles melts at 196" and is readily soluble in hot glacial acetic acid benzene and alcohol but only sparingly in ether and hot water and almost insoluble in cold water.It dissolves i n concentrated sulphuric acid with a yellow coloration the solution turning brown on warming. The sodium salt crystallises in microscopic needles and is readily soluble in water; in an aqueous solution of the sodium salt lead acetate barium chloride calcium chloride or zinc sulphate produces a colourless nickel nitrate or copper sulphate a green cobalt nitrate a red silver nitrate a light yellow and ferric chloride a reddish-brown precipitate. Apionecrotonic acid C Hz 0, CGH (OMe),*C H C Me-C 0 OH prepared from apiolaldehy de in like manner crystallises from alcohol in light yellow needles melts at 209" and is almost insoluble in water but soluble in ether hot alcohol and hot acetic acid.It dissolves in cnn- centrated sulphuric acid with a yellow coloration the solution turning bluish-green on warming. The sodium salt is readily soluble in water. The calcizim salt (C13H,306)2Ca + 5H20 crystallises from hot water in broad colourless needles and loses iCs water a t 100". The silver salt C13H13@6Ag is colourless and very sparingly soluble in water. In aqueous solutions of the sodium saIt barium chloFide magnesium sulphate or zinc sulphate produces a white. crystalline precipitate arid solutions of copper nickel cobalt and ferric salt8 also give a precipitation. When the calcium salt is distilled with lime a small quantity of a crystalline compound melting a t 83" is obtained.When calcium apiolate is distilled with lime it yields a mixture of substances some of which are volatile with steam ; the non-volatile residue crystallises from alcohol in needles melts a t 71-72' and seems to hare the composition C,H,O,. The nitro-compound (m. p. 117-118*) previously described (loc. cit.) and obtained by treating apiolic acid with nitric acid of sp. gr. 1.4 in glacial acetic acid solution has the composition C,H,N,O not C9H8N20 as previously given arid is probably dinitrapione.ORGANIC CHEIIJSTRY. 37 The nitro-compound (m. p. 116O) prepared from isapiole by Ginsberg (Abstr. 18F8 722) is probably identical with dinit'rapione and the compound (m. p. 137-138") obtained by the authors from apiolaldehyde is probably st nitro-derivative of apiolaldehyde.Chlorination and Bromination of Aniline Orthotoluidine and Paratoluidine in presence of Excess of a Mineral Acid. By R. HAFNER (Ber. 22 2524+-2541).-When chlorine is passed into an ice-cold solution of aniline in excess of 97 per cent. sul- phuric acid for about 18 hours almost the whole of the aniline remains unchanged only small quantities of parachloraniline being formed. Under the same conditions but employing 65 per cent. sul- phuric acid symmetrical trichloraniline (rn. p. 77") traces of a com- pound melting a t 63-64" probably trichlorophenol (m. p. 67-68') and considerable quantities of resinous products are formed but a large quantity of aniline remains unchanged. Chlorine acts energetic- ally on aniline in 40 per cent. ice-cold sulphuric acid solution ; the principal product is trichloraniline but trichlorophenol resinous products and traces of other compounds probably chloraniline and dichloraniline are also formed.When chlorine is passed into an ice-cold solution of aniline in excess of very concentrated (40 per cent.) hydrochloric acid for about 18 hours most of the base is converted into parachloraniline and tri- chloraniline but considerable quantities remain unchanged. Tri- chloraniline is also formed when chlorine (6 mol.) is passed into a solution of aniline (1 mol.) in ice-cold concentrated hydrochloric acid. In 30 per cent. ice-cold hydrochloric acid solution chlorine acts on aniline much more readily ; parachloraniline dichloraniline symmetrical trichloraniline and other compounds probably chloro- derivatives of phenol are formed and none of the base remains Unchanged.I n 20 per cent. hydrochloric acid solution under the same conditions trichloraniline chlorophenols and large quantities of resinous products 'itre formed. Bromine even when added in large excess has no appreciarble action on aniline in 97 per cent. sulphuric acid solution ; after four months' time only small quantities of symmetrical tribromaniline are formed. If a small quantity of iodine is mixed with the bromine the formation of tribromaniline takes place rather more readily. Tn 65 per cent. and i n 40 per cent. ice-cold snlphuric acid solution aniline is acted on by excess of bromine considerable quantities of tri- bromaniline being formed ; in the latter case small quantities of a compound probably tribromophenol are also formed.When aniline is treated with excess of bromine in 40 per cent. hydrochloric acid solution a reaction immediately takes place and the whole of the base is converted into tribromaniline ; in 20 per cent. hydrochloric acid solution small quantities of tri bromophenol are also formed. Aniline hydrobromide is completely converted into tribromaniline when treated with excess of bromine in a concentrated ice-cold soh- tion of potassium bromide ; the yield of the pure product is 90 per cent. of the theoretical quantity. Wheu chlorine is passed into an ice-cold 97 per cent. sulphuric acid F. S . I(.38 ABSTRACTS OF CHEMICAL PAPERS. solution of paratoluidine for about 24 hours metacliloroparatoluirline [Xe C1 NH = 1 3 41 and larger quantities of orthochloropara- toluidine [Me C1 NH = 1 2 41 are obtained but a consider- able quantity of the base remains unchanged. In 40 per cent.hydro- chloric acid solution the whole of the paratoluidine enters into reaction yielding metachloroparatoluidine metadichloroparatolnidine [Me Cl NH = 1 3 5 41 a crystalline compound probably orthochloroparatoluidine and oily products probably chlorinated de- rivatives of cyesol. When pal-atoluicfine is treated with excess of bromine in 39 per cent. ice-cold hydrochloric acid solution it is almost. completely con- verted in to met adibromoparaholui din e me 1 t ing a t 73 - 74" very small qiinntities of a bromocresol being also produced. I n 65 per cent. sulphuric acid solution under the same conditions large quantit,ies of metadibromoparatoluidine are formed.When orthotoluidine is treated with excess of chlorine in 913 per cent. ice-cold sulphuric acid solution it is partially converted into a chlorotoluidine ; bromine under the same conditions has no appre- ciable action even after eight days' time. Action of Nascent Nitrous Acid on varims Amines and Phenols. By A. DENINGER (J.pr. Chem. [el 407296-308).-When sodium nitrite ( 3 mols.) acts on an aqueous acid solution of aniline ortho- and para-nitrophenol and some resinous su bstarices are pro- duced in quantities dependent on the concentration acidity and temperature. The qaantity of orthonitrophenol produced is greater the more rapid the reaction and the higher the temperature above 65" ; i t varies from 0 to 50 grams whilst that of paranitrophenol varies from 0 to 33 grams per 100 grams of aniline.Air blown through the liquid diminishes the quantity of phenols produced as also does the presence of oxidising or reducing substances. The nature of the acid has no apparent effect. To obtain the best yield 10 grams of aniline 20 C.C. of sulphuric acid and 80 C.C. of water are mixed and cooled to 15" ; 300 grams of sodium nitrite in 100 C.C. of water are then added the solution heated in w water-bath and a large quantity of hot dilute sulphuric acid (1 1) immediately added. Alter the reaction the ortho-compound is distilled over with steam and thc para-compound crystallised from the residue. Nitric oxide alone appears to be evolved during the reaction.If orthotoluidine (10 grams) be substitued for aniline in the above process orthonitrocresol [Me OH NO = 1 2 31 (5to6 grams) melting a t 68-69' is obtained. By using a more dilute solution and allowing it t o stand for 14 days at 15-2b" paranitrocresol [Me OH NO = 1 '2 51 melting a t 96' is obtained. With paratoluidine (100 grams) only one nitrocrcsol (138 grams) melting a t 33-34" is obtainable. By acting on diamidoparadiphenyl and diamidoparadit)olyl respec- tively with sodium nitrite (6 mols.) in the way described above dinitrodiphenol (m. p. 260") and dinitrodicresol (m. p. 270') are pro- duced respectively. The subhate of diamidodicresol (dbstr. 1588 838) obtained by F. S. K.ORQANIC CHEMISTRY. 39 reducing the dinitrocresol is sparingly soluble in water ; by diazo- tising it and decomposing with hot sulphuric acid tetrahydroxyditolyl is obtained as a pleasant-smelling oil which is volatile with steam ; its aqueous solution gives a y ellowish-white precipitate with ferric chloride.With naph thylamine the above treatment yields dinitronaphthol and a little nitronaphthol ; when a-naphthylamine is treated with 2 mols. more sodium nitrite than is necessary for diazotising and distilled at once with steam P-nitro-+naphthol (m.p. 128") is ob- tained ; but i€ allowed to stand for 14 days at 10-15" a-nitro-a- naphthol is formed. /3-naphthylamine yields a-nitro-@-naphthol (m. p. 103"). Sulphanilic and orthotoluidinesulphonic acids yield by this treat- ment garnet-red crystals which lose the sulphonic acid group when treated with super-heated steam and yield nitrophenol and nitro- cresol respectively.Naphthionic acid yields nitronaphtholsulphonic acid. Salicylic acid and its ethereal salts yield nitrosalicylic acid and its ethereal salts. A new substance is obtained when paraphenolsulphonic acid is treated with sodium nitrite and sulphuric acid ; it is still under in- vestigation. A. Q. R. Some Nitrated Diazoamido-compounds. Ry S. NIEMEN- TOWSKI (Ber. 22 2562-2567).-When metanitraniline is diazotised in the manner described by Sandmeyer for paranitraniline (Abstr. 1885 981) a resinous precipitate is formed the moment the sodium nitrite solution is added This can be afterwards separated from the metanitrobenzonitrile by steam distillation. It crystallises from amyl alcohol in lustrous golden needles which melt a t 191-1'32" with decomposition.It has the formula C,,H,N504 and is identical with Griess' metadiazoamidonitrobenzene (m. p. 195.5 AnnaZen 121 2i2) and with Hallmann's dinitroamidoazobenzene (m. p. 175-176" Ber. 9 389). I n order to determine the constitution of the compound a qustntit'y of it was prepared by Hallmann's method ; the substance prepared by this method when crystallised from amyl alcohol also gave the m. p. 195". When the compound is heated with hydrochloric acid (sp. gr. = 1.17) for 10 hours at 185' meta- chloronitrohenzene is formed. Amy1 alcohol decomposes it at 185" with formation of metanitraniline and nitrobenzene. These reactions and the behaviour of the substance towards aromatic amines and phenols with which it yields dyes show that the compound is diazo- amidonitrobenzene.Hallmnnn's method (Zoc. cit.) is a very con- venient one for the preparation of nitrated diazoamido-corn- ponnds. DiuzoamidonitrotoZuene CI4H,,N,O4 (from metanitroparatoluidine) is prepared by treating metanitroparatoluidine (m. p. 114" 30.4 grams) suspended in alcohol (250 grams) with nitric acid (sp. gr. 1.52 7.5 grams) and with a saturated solution of potassium nitrite (8.5 grams). It crystallises from am371 alcohol in dark reddish-brown branched needles melts ah 169 dissolves very sparingly in alcohol,40 ABSTRACTS OF CHEJIICAL PAPERS. more readily in ether and carbon bisulphide and very easily in cold benzene acetone aiid chlorofwm. When heated with alcohol a t 1 70° it is decomposed into metanitroparatoluidine and metanitro- toluene.Diazoanzido?zitroto?zcene (from paranitro-orthotoluidine m. p. 107") crystallises from alcohol in long bright pellow needles melts at 212" with decomposition and is readily soluble in acetone benzene and chloroform. N. H. 31. Trinitrohydrazobenzene. By E. FISCHER (Annulen 253.1-5). -The author's process for preparing trinitrohydrazobenzene from picryl chloride and phenylhydrazine has been criticised by Willgerodt and Ferko (Abstr. 1888 830). In reply the author maintains that the process yields good results if the necessary conditions are observed. Symmetrical Nitrophenylhydrazines of the Aromatic Series. By C. W ILLGEEOUT ( J . pr. Cliem. [2] 40 264-270).-SSymmetrical picrylhydrazines are obtained by cohabating picryl chloride and the hydrochloride of the aromatic hydrazine (in molecular proportion) in alcohol a t the ordinary temperature. Picrylphenylhydrazine picr!j 1 ort hotoly 1 hydruzin e y icry lparatoly hydrazine and picryl -a-naph- thyEhydrazine have been thus obtained.All these decompose before they melt a t temperatures dependent on their state of division ; tbus picrylphenylhjdrazine in powder decomposes a t 177" whereas its crystals decompose at 181" (compare Abstr. 1888 829). T1.e author has studied the action of heat on the nitrophenyl- hydrazines in presence of various liquids and finds that the decom- positions which occur may be classified as follows :-(l.)- The liquid does not decompose the nitrohydrazineperse; in this case the hydrazine hydrogen reduces the nitro-group to 8 nitroso-group ; such liquids are water dilute hydrocliloric acid benzene and glacial acetic acid.(8.) The liquid is an oxidising agent ; the nitrobydrazine is oxidised to a nitroazo-compound. (3.) The liquid decomposes the nitro- hydrazine altogether. (4.) The liquid acts as a reducing agent such liquids being ethyl and methyl alcohols formic acid and acetone ; the first two and acetone convert picrylhydrazine into dinitrosonitroazo- benzene melting a t 219-220" ; formic acid converts it into a mixture of two substances melting a t 225" and 233". (5.) The liquid is an organic base ; in this case the nitrohydrazine is first converted into nit ro-nitroso-azo-compounds and these into polyazo-con1 pounds. The paper conclnde,s with a reply to Freund (Abstr.1889,977) whc criticises the author's and Ferko's former work (Abstr. 1888 829). A. G. B. w. c. w. Phenylhydrazone. By E. FISCHER and F. ACH (Annnlen 253 5 7-65) .-Acetor?Rdi?Litroplienylhydrazone CBHIONIOI is prepared by slowly adding acetonephenjlhydraeone (12 grams) to strong colour- less nitric acid (25 grams) Rurrounded by a freezing mixture ; this solution is allowed to drop into 100 grams of well-cooled f u z i n g nitric acid and the mixture is poured into ice water ; the product isORQANIC CHEMISTRY. 41 extracted with small quantities of ether and the residue purified by recrystallisation from alcohol. It melts a t 127" (uncorr.) is soluble in benzene chloroform ether and in hot alcohol and is quickly decomposed by hot alkaline solutions b u t less readily by acids.Phenylhydrazonelevulinic anhydride is converted into the paranitro- derivative N02*C6H4*N<,~,CH2>CH2. by fuming nitric acid. This snbstance crystallises in flat needles of a yellow colour is soluble in hot alcohol benzene and glacial acetic acid and melts a t 118-119". The alcoholic solution is converted into paraphenylenediamine by reduction with zinc-dust and acetic acid. Warm alcoholic potas- sium hydroxide or warm concentrated hydrochloric acid converts the anhydride into paranitrophenylhydrazonelevulinic acid NO2.C6H4.NH.N :C Me*C2H4*C 0 0 H. This acid forms orange-coloured needles soluble in acetone and hof alcohol; i t also dissolves in alkalis forming intense deep-red solutions. It darkens a t 190' and melts with decomposition a t 200".The ethyl salt melts at 156-157" with slight decomposition. It crystitllises in needles and dissolves freely in hot alcohol benzene and glacial acetic acid. The hydrazones of acetone and of acetaldehyde propaldehyde and oenanthaldehjde are decomposed by gently warming with pyruvic acid ; acetone or aldehyde is liberated and phenylhy drazonepyruvic acid is produced. The ketones and y-ketonic acids behave in the same way. Paranitropli,enyl?zydrmon ep yruvic acid N0,*C6H4*NH*N:CMe-C 0 OH is precipitated when pyruvic acid is added to a hot dilute solution of nitrophenylhydrazonelevulinic acid in hydrochloric acid. The acid is soluble in acetone and in warm alcohol and is decomposed by heat. N ' CMe w. c. w. Amidoximes and Azoximes.By F. TIEMANN (Ber. 22 2391- 2395 ; compare Abst. 1886 875).-The conversion of nitriles into amidoximes by the action of hydroxylamine may be considered to be a general reaction a s hitherto it has been found to apply to all cases except that of nitriles such as pentamethylbenzonitrile which cannot be or are only with difficulty converted into the' corresponding acid by the usual reagents. As a rule the formation of the amid- oxime takes place much more slowly with nitriles of high molecular weight and rich in carbon and the acid character of the product is less marked. The amidoximes combine readily with hydrogen cyanate phenyl- carbimide and phenylthiocarbimide yielding uramidoximes phenyl- uramidoximes and phenylthinramidoximes. The ethyl-derivatives of the amidoximes also combine with phenylthiocarbimide aud with phenylcarbimide.F. S. K. Phenylallenylamidoxime-derivatives. By H. WOLFF (Rer. 22 2395-240 1 ; compare Abstr. 1886 798) .-Phenylallenylethoxirne nitrite CHPh:CH*C(N*OEt)-O*NO separates in colourless needles when a solution of phenylallenylamidethoxime (1 mol.) in dilute sulphuric acid is treated with sodium nitrite (2 mols.) in the cold.48 ABSTRACTS OF CHEMICAL PAPERS. It turns yellow after a short time and is very unstable exploding alightly when treated with concentrated sulphuric acid or wben heated quickly. It melts at 61" is readily soluble in alcohol chloro- form benzene and ether but only sparingly in light petroleum and almost inPoluble in water. I t can be crystallised from alcohol a t temperatures below 55" but slight decomposition occurs.It is decomposed b y acids or alkalis yielding cinnamic acid. The chloride CHPh:CH.CCl:N*OEt separates as a yellowish oil when the amid- ethoxime is dissolved in excess of hydrochloric acid and the solution treated with sodium nitrite. It is soluble in ether alcohol benzene and chloroform but only sparingly soluble in light petroleum and carbon bisulphide and almost insoluble in water; it is not decom- posed when warmed for a short time with acids or bases. Phen y 1 dibromoprop eny lethoxime chloride C HBrP h- CHBr C CKN* OE t prepared hy warming the chloride with a slight excess of bromine is a solid compound readily soluble in ether benzene and chloroform but only sparingly in light petroleum and insoluble in water.Pheny la1 len y Ipheny luramidet Iioxime CHPh:CH*C (NOE t)*NH*CO*NBPh obtained by treating phenylallenylamidethoxime with phenylcarb- imide crystallises from dilute alcohol in colourless needles melts a t 155-156" and is readily soluble in alcohol ether benzene and chloroform but only sparingly in light petroleum hot water and hydrochloric acid and insoluble in potash and cold water. Phenylalleruy lp h enyluramidoxime CHPh:CH*C (NO H)*NH*CO*NHPh prepared in like manner from phenylallenylamidoxime crystallises from dilute alcohol in colourless needles melts a t 158-159" and is readily soluble in ether but only moderately so in benzene and chloroform sparingly in light petroleum and insoluble in cold water ; i t is only very sparingly soluble in acids and alkalis.Pheny 1 all eny luramidoxim e C H Ph CH*C (PU'OH) *NHX 0 -NH sepa- rates in colourless needles when an aqueous solution of phenylallenyl- amidoxime hydrochloride is treated with potassium cyanate ; it melts a t 158-159" and is readily soluble in alcohol and ether but only moderately in benzene and chloroform and sparingly in light petro- leum and cold water. It forms salts with acids and dissolves unchanged in alkalis but when treated with concentrated acids or alkalis a t the ordinary temperature it is reconverted into the amid- oxime. The platinoch7oride ( C,,HllN,O,),,H,PtC1 is crjstalline. E t h y l pJ~ei~ylallenylainidoximecarboxylu te CH Ph C €3- C (N H,) :N.O-CO OE t is obtained together with the hydrochloride of the amidoxime when phenylallenylamidoxime (2 mols.) is treated with ethyl chlorocarb- onate ( I mol.) in benzene solution.It is a crystalline unstable compound melts at 101" and is readily soluble in erher alcohol chloroform and benzene but only sparingly in light petroleum and insoluble in water.ORGANIC CHEJlISTRY. 43 Phen~lallen~lcarbonyli.nzidoxime CHPh:CH*C<gzg> is formed when the preceding compound is warmed with alkalis or heated above its melting point. It crystallises from dilute alcohol in slender needles melts a t 199-2200" and is readily soluble in alcohol ether benzene and chloroform but only sparingly in light petroleum and is insoluble in cold water. It has an acid reaction and in neutral solu- tions of the ammonium-derivative silver nitrate produces a white and copper sulphate a green precipitate.F. S. K. Substituted Amidoximes. By H. M ~ L L E R (Ber. 22 2401- 2412 ; compare Abstr. 1€W 875) .-Benzenylphenylcarbonylimid- oxime melting a t 166-1 67" is formed together with benzjlanil- idoxime hydrochloride when benzenylanilidoxime is treated with carbonyl chloride in benzene solution. Benzenylanilidoxime combines with chloral in the cold forming a colourless flocculent compound NHPh.CPh:NOH,C,C130H which melts a t 128-130" is readily soluble in alcohol ether chloroform and benzene and is decomposed by concentrated acids and boiling water . Ethylbenzamide COPh-NHEt prepared by gradually adding benzoic chloride to an ethereal solution of etbylamine in the cold separates fieom ether in large crystals melts a t 69-70" and is soluble in water tenzene chloroform and alcohol but only sparingly in light petroleum ; i t is moderately easily soluble in hydrochloric acid but insoluble in soda.Uenzoparutoluidide COPh*NH*C,'R,Me prepared from benzoic chloride and toluidine in like manner crystallises in plates and melts at 157-1563". Thiobenzoparatoluidide CSPh*NH*C,H,Me is hest prepared by warming the preceding compound with phosphorus pentasulphide ; it crystallises from dilute alcohol in long yellow needles melts a t 128-129' and is readily soluble in alcohol ether chloroform benzene light petroleum and soda but insoliible in water. Benzenylpuratoluidoxirne NOH:CPh*NH*C6H,Me prepared by heating t hiobenzotoluidine with hJdroxy1amine hydrochloride and sodium carbonate in dilute alcoholic solution ~rpt~nllises from dilute alcohol in long colourless needles melts at 176' and is readily soluble in ether chloroform benzene acids and alkalis but only moderately so in hot water.The hydrochloride C,4HliNz0,HCI crystallises in colourless needles and is sparingly soluble in water. Be~tzenylparafoluy lcarbontlli?nidozime C6&Me< >NO pre- pared by treating benzenyltol~iidoxime with ethyl chlorocarbonate in chloroform solution crystallises from dilute alcohol in yellowish needles melts at 163" and is readily soluble in ether chloroform benzene and light petroleum but insoluble in water acids and a1 kal i 9. Ethenylanilidoxime NOH:CMe*NHPh (m.p. 120-121"). is obtained when thiacetanilide is boiled with an alcoholic solution of hydroxyl- ainine hydrochloride and sodium carbonate.The hydyochloride CPh44 ABSTRACTS OF CHEMICAL PAPERS. CsHloNzO HCJ crystallises in colourless needles. The pZatinochZoride ( C8H,oN20),,H,PtC16 crystallises in slender yellow needles. The henzoyl-dei-ivative NOBz:CMe*NHPh crystallises from dilute alcohol in colourless needles melts a t 110" and is soluble in benzene chloro- form and ether but insoluble in water and light petroleum. Methenylanilidoxirne NOHlCH-NHPh prepared in like manner crystallises from a mixture of benzene and light petroleum in colour- less needles melts a t l l G o and is moderately easily soluble in water alcohol ether chloroform and benzene but almost in soluble in light petroleum. The hydrochloriide C7H8N20,HCl crystallises in needles. The pZatinocl~Zoride (C,H,N,O),,H,PtCI crystallises in yellowish needles.The benzoyl-derivative NOBz:CH*KHPh crystallises in colourless needles melts a t 14&-145" and is moderately easily soluble in alcohol ether chloroform and benzene but almost in- soluble in water and light petroleum. F. s. K. Action of Acetaldehyde and of Ethyl Acetoacetate on Benzenylamidoxime. By F. TIEMANN (Ber. 22 2412-2417).- prisms when an aqueous solution of acetaldehyde (1 mol.) and benz- enylamidoxime (1 mol.) is kept for some time in a warm place. It melts a t 82" and is readily soluble in alcohol ether acetone and benzene but only sparingly in hot and insoluble in cold water ; it is decomposed when heated with acids. The hydrochloride CgHloN,O,HCl prepared by passing hydrogen chloride into an ethereal solution of the base is crystalline.The platinochlorida ( C9H,,N,0),,HzPtCI is an orange-yellow compound fioluble in alcohol and decomposed by water. The base is converted into benzenyletheny lazoxime by potas- sium permanganate in cold dilute sulphuric acid solution. BenzenyZacetoetiienyZazoxirne CPh<Ng>C*CH,Ac - prepared by heating benzenylamidoxime with ethyl acetoacetate crystallises from boiling water in short yellowisli prisms melts a t 86" and i s readily soluble in alcohol ether benzene and acetone b u t only sparingly in light petroleum and boiling water ; it dissolves freely in alkalis but is insoluble in acids. When boiled with alkalis it is decomposed into benzenylethenylazoxime and acetic acid. The oxime CllHllN302 crystallises from alcohol in colourless needles melts at 80" and is soluble in ether benzene and hot water but almost insoluble in light petroleum and cold water.It is a feeble acid and reduces Fehliog's solution on warming. The hydrazone C1,H16N40 prepared by heating the ketone with phenylhydrazine crystallises from dilute alcohol in yellowish needles melts a t 126" and is insoluble in water and light petroleum but readily soluble in alcohol ether benzene and acetone. Paranitrobenzenylamidoxirne and Paramethylorthonitro- benzenylamidoxime. By J. WETSE ( B e y . 22 2418-2432).- Paranitrobeizzeriylamidoxime NO,*C,HI*C(NHz) :NOH is obtained together with paranitrobeneamide (m.p. 197") when paranitrobenzo- ni trile prepared from paranitraniline by Sandmeyer's method is Ethylidenebenxeny Zamidoxime CPheNH>CHMe NO separates in rhom- F.S. K.ORGANIC CHEMISTRY. 45 digested with hydroxylamine hydrochloride and sodium carbonate in aqueous solution. It crystallises in yellow needles melts at 169" distils without decomposition and gives all the reactions of amid- oximes ; it is moderately easily soluble in alcohol and hot water but rather sparingly in benzene ether and chloroform and insoIuble in light petroleum. The hydrochloride C7H7N303,HC1 crystallises from water in colonrless hygroscopic needles melts at 185" with decompo- sition and is soluble in alcohol but is reprecipitated ou adding ether. The ethyl-derivative NO2.C6H4*C(NH2):N*OEt is obtained by treating the amidoxime with sodium etboxide and digesting the resulting deep-red solution with ethyl iodide ; it is best obtained in a pure state by decomposing the hydrochloride with dilute soda.It forms large yellow prismatic crystals melts at 59-60' and is readily soluble in alcohol and ether but only moderately so in benzene and sparingly in light petroleum and hot water. The hydrochloride separates from akoholic ether in colourless crystals. Paranitrobenzenylethenylazoxime NO,*C,H,*C<- N>CMe prepared by dissolving the amidoxime in acetic anhydride crystallises in colourless plates melts a t 1U0 and is readily soluble in alcohol ether and benzene but only very sparingly in hot water. The corre- NO -.T sponding benzen,yl-compound N02*C6H4*O<~~>CPh prepared by warming the amidoxime wi t8h benzoic chlo~ide crystallises from alcohol in small colourless needles melts at 198" and sublimes wit'h- out decomposition when heated slowly but explodes when heated quickly. It is insoluble in light pet,roleum and only moderat.ely soluble in alcohol but readily i n ether benzene and glacial acetic acid.Eth y 1 parnnitro b enzen ytnmidoximecarbox y lnte NO,*CsH,*C (NH,)XO*COOEt is €ormed when the amidoxime is treated with ethyl chlorocarbonate in cold chloroform solution. It crystallises from cold dilute alcohol in small needles melts at 169" and is moderately easily soluble in alcohol ether benzene and chloroform but only very sparingly in water and insoluble in light petroleum. ParunitrobPnzenylcarbonylimidc~xime N02C,H4*C<NH>C0 is ob- tained when the preceding compound is boiled with alkalis or heated alone; it separates from alcohol in small yellow needles melts a t 286" and is insoluble in light petroleum and only very sparingly soluble in hot water but more readily in alcohol ether and benzene.It is a very stable compound and dissolves freely in alkalis; in a neutral solution copper sulphate produces 8 green precipitate. NO Carbon y ldi-purani t r o b enzen y 1 amidoaim e prepared by *treating the amidoxime with carbonyl chloride in benzene solution at the ordinary temperature crystallises in small jellowish needles melts at 236" and is very readily soluble in alcoholj46 ABSTRACTS OF CHEMICAL PAPERS. and moderately so in hot water but more sparingly in benzene and ether and insoluble in light petroleum ; it is converted into pnranitro- benzenvlcarbonvlamidoxime when warmed with alkalis.d Y E t h y 1 idm9para nit ro benz e mjla in idozi me N 02*C6 H,<g; > C HMe separates in dark yellow crystals when an aqueous solution of the amidoxims is treated with a slight excess of acetaldehyde and kept for some days ; it crystallises in needles melts at 153" and is readily soluble in alcohol ether benzene and chloroform but only sparingly in hot water and insoluble in light petroleum. It is not acted on by dilute acids or alkalis in the cold but oxidising agents convert it quantitatively into the a.zoxime. It is decomposed into its con- stituents when warmed with dilute hydrochloric acid. A yellow flocculent compound separahes from the solutiou when etbylidene- paranitrobenzenylamidoxime is treated with warm dilute soda.This substance melts a t 252" is very stable and is insoluble or onlyvery sparingly soluble in most ordinary solvents. It dissolves uncliaiiged in concentrated sulphuric acid and is not acted on by reducing or oxidising agents or when heated at 150" with concentrated hydro- chloric acid; it is decomposed by fuming nitric acid yielding a neutral compound which melts at about 180" and seems to be R dinitroethenylazoxime. Chloreth~lidelwparanit robelzzen~ilamidoairne NO NO,*C 6H4*C<NH > C H*C H2C1 is formed when the amidoxime is boiled with dichlorethyl ether in aqueous solutions. It crystsllises from dilute alcohol in yellow plates melts at 176" and is very readily soluble in alcohol but only mode- rately easily in benzene ether and water and insoluble in light petroleum.It re3embles the preceding compound in its chemical behaviour and yields a complex condensation-product when warmed with alkalis. EtA yiparaizitrobenzen ylozinie nitrite N02*C6H,*C( NOE tr).O*NO pre- pared by treating the amidoxime with sodium nitrite in cold dilute sulphuric acid solut'ion is a yell0 w very unstable flocculeiit com- pound melting a t 55" with explosive violence ; it is soluble in alcohol and ether but insoluble in water. It decomposes slowly a t the ordinary temperature with evolution of oxides of nitrogen and explodes when heated with water or when treated with concentrated sulphuric acid. > C*CH2Ac is formed when the amidoxime is digested with ethyl acetoacetate. I t crystallises from d-ilute alcohol in golden plates melts a t 140" and is readily soluble in alcohol and ether but only moderately so in benzene very sparingly in water and insoluble in light petroleum.When heated with alkalis it is quickly decomposed into acetic acid and nitrobenzenylethenylazoxime. Paramidobenien ylamidoxime NH?*C6H,*C(NH2):XOH prepared by reducing the nitr+compound with stanuoos cbloride and hydrochloric NO Paranitro benzeny lacetoet heny lazoxirne N D2*C H,*C<ORGANIC CHEMISTRY. 47 acid and decomposing the resulting salt with sodium carbonate crys- tallises in yellow plates turnx brown at lGO" and melts at 174" with decomposition. It is very readily soluble in alcohol but only mode- rately easily in benzene and ether sparingly i n hot water and in- soluble in light petroleum ; it gives the reactions of amidoximes and dissolves freely in alkalis.Paramethylorthonitrobenzonitrile [ CN NO2 Me = 1 2 41 pre- pared from metanitroparatoluidine by Sandmeyer's method crgstal- lises from water in long yellowish needles melts at 99" distils without decomposition and is readily soluble in alcohol ether benzene and chloroform but only sparingly in hot water and almost insoluble in light petroleum. Paramet hy lort honitrobenzeny lamidoxiime N02*C6H3&1e*C (NH?) :NOH is obtained by digesting rnethylnitrobenzonitrile with hydroxylamine in alcoholic solution and is best prepared in a pure state by decom- posing the copper-derivative with hydrogen sulphide. It crystallises in long yellow needles melts at 161" and shows the properties of an amidoxime ; it is moderately easily soluble in alcohol and hot water but only sparingly in benzene ether and chloroform and is insoluble in light petroleum.The hydrochloride CBHSNYOS,HC1 is a colonrless crystalline compound soluble in alcohol but reprecipitated on adding ether. Paramethylorthonitrobenzamide [CONH NO2 Me = 1 2 41 is formed in the preparation of the preceding compound. It crystallises from water in long yellow needles melts at 152" and is readily soluble in alcohol ether and benzene but almost insoluble in light petroleum ; it is converted into the corresponding acid when boiled with alkalis. Para rneth y 1 orthamidoben,zeny lamidoxime is produced in small quantities when methylnitrobenzenylamidoxime is reduced with stannous chloride and hydrochloric acid.It is a brown flocculent compound melts at about 166O and gives the reac- tions of aniidoximes. The hydrochloride is a colourless crystalline hygroscopic compound soluble in alcohol but reprecipitated on adding ether. F. S. K. Para- and Ortho-homobenzenylamidoxime and their De- By L. H. SCHUBART (Bey. 22 2433-2440; comparz rivatives. Abs tr. 1886 79 7) .-Parahomo benz eny letheny lazoxime prepared by boiling the amidoxime with acetic anhydride crystallises in colourless prisms melts at 80° and is readily soluble in alcohol ether chloroform and benzene but insoluble in acids and alkalis. Parahomobenzenylethoxime chloride C6H4Me*CCl:NOEt obtained by treating the amidethoxime with hydrochloric acid and sodium nitrite is a ,yellow oil boils at about goo" a.nd is soluble i n aloollol and ether. The corresponding bromide prepared in like manner is a48 ABSTRACTS OF CHEMICAL PAPERS.heavy brown oil; it decomposes at 155" and is readily soluble in ether chloroform and benzene. Parahomobenzenylp-openylazoxime-w-carboxylic acid C6H4Me*C<- "0 y>C*C2H4-COOH. A is formed when the benzenylamidoxime is melted with succinic an- hydride. It crystallises from boiling water in colourless needles melts at 138*5" and is soluble in alcohol ether chloroform and benzene. Parahomobenzenyluramidoxime C,H,Me*C(NOH)*NH*CO.NH pre- pared by treating the hydrochloride of the atnidoxime with potassium cyanate in aqueous solution crystallises in colourless needles melts a t 170" and is readily soluble in alcohol ether and benzene but only sparingly in water.The thiowuinidozime C,H,Me*C (NOH) *NH*CS.NHPh prepared by treating the amidsxime with phenylthiocarbirnide crys- tallises from hot water in colourless needles melts ot lYO" and is readily soluble in alcohol and ether but more spariiigIy in chloroform and benzene. Para<horno b enzen y lpheny luvani idoxime C6H4Me*C( NOH)*NH*CO*NHPh prepared from phenylcarbimide in like manner separates from dilute alcohol in colourless crystals melts a t 155" and is readily soluble in rtlcohol ether and hot water. Ethyl pamhornobenzenylnnzidoximecarboJ.ylate C6H4&fe-C (NH,):NO*COOEt is obtained by treating the amidoxime with ethyl chlorocarbonate i n chloroform solution ; it crystallises from dilute alcohol i n colourless needles melts a t ISO" and is readily soluble in alcohol ether chloro- form and benzene but only sparingly in light petroleum and water.PnrahomobenzenyEcarBonyZirnidoxime C6H4Me*CWNH>C0 NO crystal- lises from hot water in colourless needles melts at 220" and is soluble in ether alcohol and alkalis. Diparahomobenzenylnzoxime C6H4Me*C< >C*C6H4Me is formed when the amidoxime is heated with glacial acetic acid. It crystallises from dilute alcohol in long colourless needles melts a t 135" and is insoluble in water but readily soluble in ether benzene chloroform and light petroleum. C6H4Me*CeK NO I-_i > CHM e melts a t 127.5". and is readily soluble in alcohol ether and benzene but only sparingly in hot water. NO Etlr ylidenepara.12omobenz eny lainidonime Parahomobenzenylacetoetheny lctzoxinze C6H4Me*C<L YO N>C.CH2Ac - pared by treating the amidoxime with etbpl acetoacetate crystallisesORGANIC CHEMISTRY. 49 from boiling water in colourless needles melts at 97" and is readily soluble in alcohol ether and benzene.Orthohomobenzeny Zaniicloxime CsH,&Ie*C (NH,) :NOH obtained from homobenzonitrile (b. p. 195") crystallises from hot water in yellowish needles melts at 149.5" is readily soluble in alcohol ether and benzene and shows the characteristic reactions of amidoximes. The ethyl-derivative C,,H,,N,O forms colourless prismatic crystals melts at 140° and is readily soluble in ether alcohol and benzene. The benzoyl-derivative C,5Hl,Nz0 crystallises from dilute alcohol in needles melting at 145". Orthohornobenzenylbenzeny luzoxime C 6 H ~ e * C < ~ ~ > c P h prepared by dissolving the benzoyl-derivative (see above) in cold concentrated sulphuric acid crystallises in long colourless needles melts at 80° and is insoluble in acids alkalis and cold water but readily soluble in alcohol ether benzene and chloroform.F. S. I(. Action of Carbon Bisulphide on the Potassium Compound of Parahomobenzenylamidoxime. By L. H. SCHUBART (Ber. 22 2441-2442) .-A compound CSH,N,S2 is formed when parahomo- henzenylamidoxime (1 mol.) is dissolved in alcoholic potash and the solution boiled for about three hours with carbon bisulphide (1 mol.). It crystallises from alcohol in yellow needles melts at 165" and is soluble in ether chloroform benzene and alkalis. The compound C,H6N2S2 can be obtained from benzenylamidoxime in like manner.It crystallises from alcohol in yellow prisms and melts at 160". F. S. K. Xylenylzmidoxime and its Derivatives. By E. OYPENH EIMER (Ber. 22 'L442-2449).-Xylylonitrile [CN Mez = I 2 41 pre- pared from xnet3axylidine by Sandineyer's method separates from cold dilute alcohol in long colourless crystals melts a t 23-24' is volatile with steam and is readily soluble in alcohol and ether (compare Oasiorowski and Mere Abstr. 1885 772). Xylenylumidoxime CsH,Mcz.C( NH,):NOH is obtained when the preceding compound is heated with hydroxylamine for 5 to 6 hours at 80-85". It crystallises in colourless needles melts at 178" and is readily soluble in alcohol ether chloroform and hot water but only sparingly in cold water; it gives all the characteristic reactions of aruidoxirnes.The ethyl-derivative CI,H,,J,O crystallises in colourless iieedles melts at 172" and is readily soluble in alcohol ether chloroform benzene and hot water but only sparingly in cold water. The benzoyl-derivative CI6H,,N,O separates from dilute alcohol in colourless crystals melts at 158" and is only sparingly soluble in waher and light petroleum but readily in alcohol ether and chloro- f x m . Xy 1 en y Zb enzen y Zuzoxime CsH,Me2*C< N>C Ph prepared by heat- ing the beuzoyl-derivative described above crystallises in yellowish scales melts at 98" sublimes readily and is volatile with steam ; it is readily soluble in alcohol ether chloroform and benzene. NO VOL. LVIIT. e50 ABSTRACTS OF CHEMICAL PAPERS. Acety Zxy Zeny lamitloxime C6H3Me2-C(NHz) :NOAc obtained by treating the amidoxime with acetic chloride in ethereal solution crystallises from cold alcohol in colourless needles melts at 189" and is readily soluble in alcohol and chloroform but only sparingly in ether.The corresponding ethenyluzoxinte C,,H,,N,O is prepared by heating the amidoxime with acetic anhydride and distilling the product with steam; it separates from alcohol or ether in crystals and melts at 89". Xylenylazoximepropeql-w-carboxylic acid C 6 H 3 M e 2 0 C ~ ~ ~ ~ C ~ C 2 H 1 * C O O H prepared by fusing the amidoxime with succinic anhydride crys- tallises in long colourless needles melts at 112" and is readily soluble in alcohol ether benzene and chloroform ; it forms crystal- line salts with bases. SEth?/Z xyZenyZamidoxirr,ecarboxyZate C6H3Me*C(NHz):NO*COOEt is obtained by treating the amidoxime with ethyl chlorocarbonate in chloroform solution.I t crystallises from dilute alcohol in colourlesa needles melts at 142" and is readily soluble in alcohol ether and chloroform but only sparingly in light petroleum; it has feeble basic properties. Xy Zeny 1 carbon y lamidoxime C6H3Mez* CfNH > C 0 prepared by heating the preceding compound crystallises from hot water in needles melts at 182" and is readily soluble in alcohol and ether; it has acid properties. The compound CeH,2Nz0,CCI,*COH is formed by the direct combin- ation of its constituents ; it separates from a mixture of benzene and light petroleum i n crystals melts at 112" and dissolves unchanged in alcohol and ether but is decomposed by water and by dilute acids.Xylenyluramidoxime CsH,Me2*C(NOH).NH.CO*NHz separates in coiuiwless crysta,ls when the hydrochloride of the amidoxime is treated with potassium cyanate in ethereal solution. It melts at 155" is readily soluble in ether alcohol benzene and light petroleum but onlg sparingly in water; it combines with acids and also but less readily with bases. C6H3Mez.C(NOH)*NH*C0.NHPh crystallises from alcohol in light yellow scales melts at 138" and is soluble in alcohol ether benzene chloroform hot water and acids. XyZenyZphenyZthiuramidoxime C6H3Mez*C(NOH)*NH-CS*NHPh separates from dilute alcohol in light yellow crystals meIts at 150" and is soluble in alcohol ether benzene acids and boiling water but almost insoluble in alkalis.F. S. K. NO The phenyl-derivative Action of Sulphuric Acid and Selenic Acid on Aromatic Compounds. By ISTRATI (Bull. Xoc. Chim. [3] 1 480-481).- Finding that the prolonged action of sulphuric acid on benzene pro- duced a sulphonic acid sulphobeneide and a francein the author heated selenic acid sp. gr. 1.4 (200 grams) with pure benzene (50 c.c.)ORGANIC CHEMISTRY. 51 for 32 hours at 80" ; neither selenobenziile nor a francei'n was produced but after neutralisation of the acid by barium carbonate a small quantity of a crystalline organic compound which the author believes to be phenyl selenide (comp. Abstr. 1889,41) was extracted from the barium salt by hot water. Pentachlorobenzene similarly treated gave a corresponding result. New Data relating to France'ins.By ISTRATI (BUZZ. Xoc. Chiin. [3] 1 481487 ; compare Abstr. 1888 591).-When snlphuric acid is heated with halogen-derivatives of benzene it causes the migration of halogen-atoms and this determines the formation from the initial corn- pound of france'ins whose chlorine values differ. Thus from 1 2 4- trichlorobenzene three franceins resulting from the oxidation of di- tri- and tetra-chlorobenzenesulphonic acids are produced and these are accompanied by a small quantity of 1 2 4 5-tetrachloro- henzene. From 1 2 4 5-tetrachlorobenzene a francein is ob- tained which is separable into five france'ins of varying solubilities and compositions. Numerous analSses are given. T. G. N. Francei'n from 1 2 4 Trichlorobenzene. By ISTRATI ( B d . ~ O C .Cltinz. [3] 1 4.88-492) .-From comparative experiments which he has made as to the formation of france'ins from 1 2 4-tri- chlorobenzene the author finds that the yield of francein is de- pendent on the temperature and varies inversely as the amount of sulphonic acid remaining in the mixture a t the close of the operatmion. Action of Heat on a Mixture of Sulphuric Acid and Sul- phonic Derivatives. By ISTR~ATI (BUZZ. SOC. Ckim. [3] 1 49%- 496).-From experimental observations the author concludes that when a mixture of excess of snlphuric acid and a sulphonic acid or a sulphonate is heated regeneration of hydrocarbons with formation of water and of pyrosulphuric acid respectively occur while sulpho- benxide is formed as a condensation-product and a decomposition of the sulphonic acid into sulphurous anhydride hydrocarbon and oxygen determines the formation of a franceiin by the oxidation of unaltered sulphonic acid.T. G. N. T. G. N. T. G. N. a-Ketoaldehydes. By H. MGLLER and H. v. PECHMANN (BPT. 22 2556-2 56 1 ).-Benzoy lf ormaldehy de C OPh . CO H (Abstr. 18e8 146) is prepared by dissolving nitrosoacetophenone (30 grams) in a 35 per cent. solution of sodium hydrogen sulphite (120 grams) contained in a litre flask. When cold the whole solidifies to a yellowish crystalline mass and is then stirred with alcohol and glacial acetic acid (1 c.c.) and after some time filtered by suction. The product (30 or 40 grams at a time) is boiled with 11 parts of 17 per cent. sulphnric acid in a flask fitted with an upright condenser until one quarter of the liquid is boiled off.On cooling crystals of phenylglyoxal hydrate separate and are purified by crystallisation from boiling water. It dissolves in about 35 parts of water at 20". When heated with nitric acid (sp. gr. lath) benzoglformic acid is formed. When an aqueous solution is treated with phenylhydrazine dissolved in dil ntu ( phen ylglyosal) e S52 ABSTRACTS OF CHEMICAL PAPERS. acid thea-hydrazone NHPh*N:CPh*COH separates as a brown cryetal- line precipitate which may be obtained from alcohol in yellow plates melts a t 142-143",and is readily soluble in most solvents. The osazone C,,H18N is obtained by heating phenylglyoxal with phenylhydrazine acetate (2 mols.) or more conveniently from nitrosoacetophenone and an excess of phenylhydrazine ; it is identical with Laubmann's compound from benzoyl carbinol and phenylhydrazine (Abstr.1888 366). When the aldehyde is dissolved in aqueous soda and b:ded for a few minutes sodium lnandelate is formed. It is probable that i n the formation of mandelic acid from benzoylcarbinol (Rreuer and Zincke Abstr. 1880 645) and from acetophenone dibromide (Engler and Wohrle Abstr. 188'7 948) benzoylformaldehyde is formed as intermediate product (compare Zinoke Annalen 216 31 5). When phenylglyoxal is treated with ammonia a compound of the formula C,,Hl,N30 or C,H,,N,O is obtained. This crystallises from dilute alcohol in yellowish-white lustrous plates melting a t 192-193" and can be distilled; i t is soluble in alkalis and is not changed by sulphuric acid.Phenylglyoxal reacts with hydroxylamine yielding the cnnipound C16H,3N403. The latter melts a t 219' dissolves in alkalis and is pre- cipitated by acids as a white powder which becomes yellow when exposed to light. A7itrosomethyZ paratol!/Z fietone C6H4Me.C0.CH:NOH prepared by Gaiseti's method crystallises from benzene in colourless needles melting a t 100'. ParatohjZgZyoxaZ hydrate C6R,Me*CO.CH(OH) is prepared from the a,bove compound in a manner similar to phenylglyoxal. It crys- tallises from water in white matted needles softens at 95" melts a t 1OO-l0'Lo and is readily soIuble in alcohol ether and benzene but less soluble in water and light petroleum. When shaken with benzene containing thiophen and salphuric acid the latter becomes green. The aldehyde behaves towards alkalis like the phenyl-compound is oxidised by nitric acid (sp.gr. 1.4) to toluylformic acid and by per- mariganate to paratoluylic acid (m. p. 180'). The osazone C21H20N1 obtained by heating a solution of the aldehyde with an excess of phenylhydrazine acetate for 30 minutes on a water-bath crystallises in yellow needles melting a t 145". Naphthyl methyl ketone C,,H,,O melts a t 51-52' boils at .300-301" and when oxidised yields /3-naphthoic acid. It is not identical with the compound obtained by Claus and Feiss (Abstr. 1887 271) but possibly is with Pampel and Schmidt's (Abstr. 1887 252) compound. N. H. M. Isomeric Dinitroparatoluic Acids. By B. ROZA~SKI (Bey. 92 2675-268'2) .-By nitrating orthonitroparatoluic acid (Abstr. 1888 l088) two dinitro-derivdires were ohtnined and their consti- tution establisbed from the corresponding dinitrotoluenes.2 5-DinitroparufrnZiiic acid (COOH NO Me NO = 1 2 4 5 ) is very sparingly soluble in cold water easily in alcohol and acetone crystallises in needles and melts a t 158". The sodiu,nz salt (with 3H,O) forms glistening je:low scales ; the bui*ium saltORGANIC UHEJIIS'I'RT. 53 (with 2&H20) sIrlaI1 yellowish-white needles ; the calciimt salt (with 2H20) reddish-brown scales ; the ammonium salt lemon-yellow scales ; the siher salt a white amorphous powder; the copper salt a light- green powder ; the mercuric lead and i r o n salts white precipitates. 2 3-Dinitroparatoluic acid [COOH NO NO Me = 1 2 3 41 forms yellowish prisms soluble in alcohol and melts at 249".It a i d its salts are less soluble in most solvents than the 1 2 4 5 acid. The bariwn saZt (with 4H,O) forms pale-yellow needles; the calcium salt (with H,O) pale-yellow scales. The other salts are similar to those of the isomeric acid. L. T. T. Acetometanitrobenzoic Anhydride. By W. H. GREENE (Airier. Chenz. J. 11 414-415).-When dry silver metaniirobenzoate is treated with excess of cold acetic chloride and the product poured into water metanitrobenzoic acid is regenerated ; Liebermann's statement (this Journal 1877 ii 617) that metanitrobenzoylacetic acid (acetometanitrobenzoic anhydride) is formed is incorrect. Acetometanitrobenzoic anhydride is however obtained by treating sodium or silver metanitrobenzoate with acetic chloride and extract- ing the product with ether.It forms colourless needles which melt a t 45". It is insoluble in water but the presence of either water o r alcohol in the ether used for extraction CiLuSes complete decomposi- tion of the anhydride Action of Phosphorus Trichloride on Salicylic Acid. By R. ANSCHUTZ and W. 0. EMERY (Airier. CRein. J. 11 387-392).-When salicylic acid is heated with excess of phosphorus trichloride a t iO-8rj0 and the product distilled first at the ordinary pressure to get rid of tlie excess of phosphorus trichloride and then under reduced prfssure snlicyloplzosphorus chloride C7H403PCl. solidifies in the re- ceiver. This melts st 36-37" boils a t 127" under 11 mm. pressure decomposes under ordinary pressure a t about 245" and is soluble i n ether chloroform and benzene. With phosphorus pentachloride or with chlorine i t gives an additive-compound C7H403PC13 of sp.gr. = 1.5587 a t 20" (water at 4" = l) boiling at 168" under 11 nim. pressure ; this compound can also be obtained by the action of phos- phoieus pentachloride on salicylic acid. With bromine a similar com- pound CiH1O3PCIBr2 is obtained of sp. gr. 1.8852 a t 20" (water a t 4' = l) and boiling at 18.5-188" under 11 mm. pressure. Tlie following are given as the most probable formulae for salicylophos- p horus monochloride and its chlorine additive-prodxct respectively :- C. F. 13. C. I?. B. Constitution of Isoeuxanthone. By C. ARBENZ (Chem. Centr. 18H9 ii 73; from A r c h . Sci. p h y s . mat. Gen6z.e [3] 21 3'75).- Phenylsalicylic acid is converted by nitric acid into the dinitro- derivative NO,.CsH1(O.CsH,.NO,).COOH which may be split up into paranitrophenol and pararlitrosalicylic acid proving that bot 11 nitro-groups are in the para-position.Sulphuric acid converts the51 ABSTRACTS OF CHEMICA\L PAPERS. dinitro-derivative into dinitrodiphenyleneketona oxide which may be reduced to the diamido-derivative isoenxanthone. J. W. L. Oxidation of Orthocarboxycinnarnic Acid. By E. EHRLICH (Illonatsh. 10 574-577 ; compare Abstr. 1888 842).-The author has previously shown (Abstr. 1888 1306) that in alkaline solution &naphthol when oxidised with a limited quantity of permanganate gives rise to orthocarboxycinnamic acid COOH*CH:CH.CsH,*COOH ; whilst the employment of an excess of the oxidising agent leads to the formation of orthocarboxyphenylglyoxylic acid CO OH*C0.CsH4.C 0 OH.Thq former acid however is not to be regarded as an intermediate ~wnduct for when a 2 per cent. solution of permangaiiate is slowly run i 1 1 tj) a solution of orthocarboxycinnamic acid (10 grams) and potash ( I 0 grams) in water (1 litre) decolorisation ceases when about 80 per cent. of the permanganate theoretically required to convert it into orthocarboxyphenylglyoxylic acid has been added and the solution contains only orthobenzaldehydecarboxylic acid COH*C6Ho*COOH (yield 50 per cent.) which melts a t 98-99' reduces an ammoniacal solution of silver. and furnishes a compound with phenylhydrazine melting a t 107-108". The author has not succeeded in his endeavour to obtain orthobenzaldehydecarboxylic acid by the direct oxidation of /3-naphthol.G. 3'. M. Isomeric Derivatives of Ethylbeneene. By L. SEMPOTOWSKI (Ber. 22 2862-2G74).-When ethylbenzene is heated to boiling an equal volume of sulphuric acid added and then after cooling the mass is treated with a small quantity of ice-cold water only para-ethyl- 7,eueenesulphonic acid is formed ; this crystallises in long colourless deliquescent needles is sliyhtly soluble in water and has a rough bitter taste. The barium saZt (with H,O) forms colourless silky needles; the calcium salt silvery scales ; the coyper salt (with 4+H,O) light-bliie glistening scales decomposing a t 170'; the cadmium salt (with 7H,O) large transparent quadratic plates ; the potassium salt (with +H,O) micaceous scales decomposing at 150".All these salts are soluble in water. The sic@haniide C6H4Et.S02NH,[Et SO,NH = 1 41 crystallises from alcohol in flat micaceous prisms easily soluble in ether sparingly so in water and melting at 109". The constitution vas proved by the fusion of the potassium salt with potash when parahydroxybenzoic acid was formed. With a shorter fusion para- etltyZpheno2 C6H4Et.0H was obtained ; this forms long needles which melt at 45-46' boil a t 21:-3-214" and are sparingly soluble in water.* It is very soluble in alcohol and ether and its aqueous solution gives a violet-grey coloration with ferric chloride and a jellowisli-white precipitate with bromine-water. The metnsuZphoizic acid CsH,Et(S03H)*OH[Et S03H OH = 1 3 41 is formed both at high and low temperatures.It. is a * Probably identical with the a-ethylphenol of Beilstein and Kuhlberg rind of Fittig and Kiesow.-Abstmrtor.ORQASIC CHEMtS'l'RY. 55 reddish oil of phenol-like odour and miscible with water. The b a r i m salt forms colourless hexagonal plates decomposing a t 120" ; the potassium salt silky needles ; the calcium saEt colourless needles. On fusion with potash the acid yields protocatechuic acid proving the correctness of the constitution given. Netaparadihydroxyethylbenxene C6H,Et(OH) [Et OH OH = 1 3 41 is a liquid boiling at 295" and soluble in water. Its aqueous solution is coloured green by ferric chloride and this colour passes on the addition of soda through blue to claret colour. Orthobyomethy lbenzenemetasulphonic acid [Et Br SOsH = 1 2 3 or 51 was obtained by the sulphonation of bromethylbenzene. Its barium salt (with 3HzO) iorms colourless plates sparingly soluble in cold water; its potassium salt (with $H,O) colourless scales ; and the sulphamide glistening prisms melting at 104-105".Parabromethylbenzeneorthosulphonic acid similarly formed yields a crystalline barium salt (with 4H20) easily soluble i n water. The potas- sium salt forms easily soluble scales the sukhonamide large micaceous scales melting at 123-124". Barium orthoethylbenzenesulphonute (with H20) formed by debrom- inating the bromine-derivat'ive forms soluble scales ; the cadmium salt long soluble needles ; the potassium salt very soluble glistening scales. Barium o~thoethylphenolrnetasulplLonate forms microscopic scales.Barium nteta-ethyll~en~zenesulplzor~nte (with 2H20) obtained by debromin- d i n g the bromine-derivative forms crystals easily soluble in water ; the potassium salt easily soluble scales ; the sulphonarnicle glistening scales melting at 85-86" When fused with potash this acid yields meto-ethylphenol which forms a colourless oil liquid at -20" and boiling at 202-204". Barium meta-ethylphenolsulphonate forms easily soluble crystals. L. T. T. Disulphones and Trisulphones. By E. FROMM (Annnlen 235 135-167) .-Baurnann and Escalcs (Abstr. 1887 123) obtained ethylidenediethylsulphone by oxidising a-dithioethylpropionic acid. It is more conveniently prepared by acting on a mixhure of acetalde- hyde and ethyl mercaptan with zinc chloride. The resulting ethyl mcrcaptal of acetaldehyde (b.p. 186") is oxidised by agitation with a solution of potassium permanganate containing sulphuric acid. E thylidenediethylsulphoiie melts at 75" and boils at 3.20" with decomposition. The bromide melts at 115". Attempts to obtain substitution-products by the action of alkalis sodium ethoxide mer- captan or aniline on the bromide were unsuccessful (Abstr. 1888 357). Ethylidenediethylsulphone chloride CMeCl( S02Et) and sodium phenylsulphini te are formed by the action of benzenesulphonio chloride on ethylidenediethylsulphone and sodium ethoxide. The chloride can be prepared by exposing to direct sunlight for several days an aqueous solution of ethylidenediethylsulphone saturated with chlorine. It is deposited from an aqueous solution in needles which melt at 102-103".The iodide is prepared by boiling the disul- phone with an excess of iodine the crude product being treated56 ABSTRACTS OF CHESlICAT PAPERS. with a cold ~olution of sodium hydroxide then washed with coId water and finally recrystallised from boiling water. The iodide crystallises in needles and melts at 128-129" ; a t a higher tempera- ture it gives off iodine. Diethylsulphonedimet hylmethane has been described by Baumann (Abstr. 1887 123). It can be prepared by the action of methyl iodide on an alkaline aqueous solution of ethylidenediethylsulphone. Diethylsulphoneth ylrnethylmefhane is formed by boiling a mixture of sodium ethoxide ethyl iodide and ethylidenediethylsulphone in a flask with a reflux condenser. It forms quadratic crystals and melts at 76".The ethjl mercaptal of propaldehyde is lighter than water and boils between 196" and 200'. On oxidation with permanganate it yields propylidenediethylsulphone CH,*CH,.CH( SO,Ett) ; t'his crys- tallises in silky needles and melts a t 77-78". The ethyl mercaptal of isobiitaldehyde boils between 200 and 210"; i t is lighter than water. lsobut~lidenedie~hylsulphone melts a t 94" and crystal- lises in needles; it is almost insoluble in cold water. The ethyl mercapkal of benzaldehyde PhCH( SEt) is lighter than water and boils with decomposition a t 250-253". Benz~lidenedieth~7sul- phone melts at 133-134"; it is insoluble in cold water but is soluble in cold solutions of the alkalis. €37 the action of sodium ethoxide and methyl iodide i t is converted into diethjlsulphone- methylmethane.Diethylsulrphonemethnne prepared by the oxidation of the ethyl mercaptal of formaldehyde (from methylene chloride and sodinm ethyl mercaptide) is identicai with the disulphone Raumann ob- tained from ethyl orthothioformate (dbstr. 1887 124). It is converted into diethylsulphonedimethylmethane (sulphonal) by the action of methyl iodide in the presence of an alkali; this melts a t 12.5-126". D~ethillsul?,honedi~thyli,?ethniie is more difficult to prepare. It melts at 86-88'. An aqueous solution of diethylsulphonemethane readily absorbs chlorine formiug the dichloride CCl,(SO,Et),. It crystallises in needles and melts a t 98-99'. The corresponding diethylsulphonedibromomethane has already been described by Bau- mann (loc.cit.) . Diethyhdphonedi-iochmethane melts a t 176-177" b u t begins to turn brown at 170". It crystallises in needles and is sparingly solnble in hot water. DiphenylsuZpphonemethane CH,(SO,Ph) prepared by oxidising the phenyl rnercaptal of formaldehyde crystallises in needles and me1 ts a t 118-119". It is soluble in benzene and hot alcohol Diphenylsul- phonedimethylmethane melts at 128" and is soluble in hot alcohol. The corresponding diethyl-derivative melts at 130-131" and is sparingly soluble in hot alcohol. When diethylsulphonedibromomethane (1 mol.) is boiled with phenyl mercaptan (I mol.) and an aqueous solution of sodium hydroxide (rather more than 3 mols.) phenyl bisulphide and diethylsulphone- thiophenylmethano are formed. The former is deposited from the solu- tion on cooling whilst the latter separates out on acidifying the filtrate ; i t is washed with cold water and recrystallised from absolute alcohol.ORGANIC CHEIJTSTR Y.57 Diethylsulphonethiophenylmethane PhSCH( S02Et) crystallises in plates and melts at 86". It is sparingly soluble in hot water and .more readily soluble in a solution of sodium hydroxide. On oxidation by perman ganat e diet h y Isu 1 phonep h eny lsu Zpiokonern ethane PhSO,*CH( SO,E t) 2 is produced. This trisulphone melts a t 1ti5". It is less soluble in alcohol than in water and is precipitated from its aqueous solution by strong acids. The aqueous solution turns litmus red and decomposes carbonates. w. c. w. Phenylated Indoles. By W. H. TNCE (Annrzkn 253 35-44).- 3'- Pheriylindole yields a crystalline picrate soluble in benzene ether acetone and alcohol and melts at 105".The nitrosamine C14H,,N,0 forms minute yellow needles and melts a t 60-61"; it is freely soluble in benzene acetone ether and chloroform but is insoluble in Rolutioris of caustic alkalis. Phenylacetaldehydemethylphenylhydr- azone is formed by the interaction of phenylacetaldehyde and methyl- phenylhydrazine. The alcoliol ic solution of t h i s compound is decomposed by an alcoholic solution of hydrogen chloride with deposition of ammonium chloride. The liquid is neutralised with ammonia and evaporated leaving a residue of impure 1'-3'-methyZ- phenylindole; t h i s is purified by solution in etherand distillation in a vacuum. The pure indole dissolves i n benzene alcohol and ether ; its alcoholic solution gives a blue colour to a pine chip moistened w i t h hjdrochloric acid.The picrate forms dark brown needles and melts a t YO". Fischer and Schmidt (Abstr. 1888 958) pointed out that zinc chloride a t 170" converts 3'-phenylindole into 2'-phenylindole. In the same way zinc chloride a t 220" transforms 1'-3'-methylphenylindole into the 1'-2'-methylphenylindole described by Degen (Abstr. 1887 149). 3'-PhenyZ-13-nap72thindoZe is obtained by the action of alcoholic hydrogen chloride on the hydrazone produced by the inter- action of phenylacetaldehyde a n d /3-naphthylhydrazine ; it crystal- lizes in glistening needles and melts with decomposition a t 211" is soluble in benzene alcohol ether acetone and hot light petroleum and stains a pine chip green.The picrate forms reddish-brown needles melts a t 219-120" and is holuble in benzene acetone chloroform alcohol and ether. The 3'-phenyl-/3-naph t hindole is con- verted into 2'-phenyl-@-naphthindole by treatment with zinc chloride at 130". 2'-Phenyl-P-naphthindole can be more conreniently prc- pared by the action of zinc chloride on acetophenone-p-naphthgl- hydrazone obtained by the condensation of acetopbenone and j?-naphthylhydrazine. The hydrazone melts a t 150" but it begins to turn brown a t 117". /3-?zLtphthindoZe melts a t 129-1S0° and is freely soluble in alcohol ether and benzene. It forms a crystalline picrate (m. p. 165-166") which is soluble in benzene and ether. Benzidine- and Benzidinesulphone-sulphonic Acids. By P. GRIESS and C.DUISBLRG (Rer. 22 2459-2474).-l?enzidiwe- sulphonic acid NH,.C6H4*C6H3( NH,) .SO,H is formed in small quanti- w. c. w.58 ABSTRACTS OF CHEMICAL PAPERS. ties in the preparation of the disulphonic acid (compare Griess Abstr. 1881 428) and it can also be obtained in larger quantity by heating benzidine sulphate for 1& to 2 hours a t 1 70" with sulphuric acid mono- hydrate (about 6 parts). It is best prepared by heating benzidine sulphate at 170" for about 24 hours (D.R.-P. No. 44,779). It forms anhydrous crystals and is very sparingly soluble in boiling water and practically insoluble in alcohol and ether; it is decomposed when heated yielding a small quant'ity of benzidine. The hydrochloride C12H,,N2S0,,HCl separates from hot dilute hydrochloric acid in greyish nodular anhydrous crystals and is decomposed by boiling water.The barium salt (C,2HlIN2S03)2Ba + 5H20 is moderately easilg soluble in hot water and separates on cooling in small needles or plates. The tetrazo-compound is obtained when an excess of hydrochloric acid and a slight excess of sodium nitrite are added to an ice-cold alkaline solution of the sulphonic acid. It is readily soluble in water and combines with phenols hydroxysulphonic acids and aromatic hydroxycarboxy lic acids in alkaline solution and with arnines and amidosulphonic acids in sodium acetate solution forming yellow red and purple dyes. The compounds obtained with the hydroxycarbosylic acids phenols and amines respectirely are sparingly soluble ; the other dyes are readily soluble in water.They all dye unmordanted cotton wool in am alkaline bath and generally the shade produced is more distinctly purple than that obtained with tetrazodiphenyl dyes but not so much so as that produced with tetrazodipheny ldisulphonic acid colouring matters. Benzidinemetadisulphonic acid (compare Griess Zoc. cit.) is best prepared by heating benzidine sulphate (1 part) with sulphuric acid (2 parts) at 210" for 36 to 48 hours ; the yield of the pure compound is 90 per cent. The azo-compounds derived from the tetrazo-derivative do not dye vegetable fibres as readily as those obtained from the tetrazomonosulphonic acid but they have a more decided blue shade. Benzidine is not acted on by fuming sulphuric acid a t temperatures below 100-120" but the azo-compounds obtained from tetrazo- diphenyl and naphthylamines react with fuming sulphuric acid in the cold the hydrogen in the benzidine being substituted.Benzidinetrisulp7zoiLic acid C6H,(NH,)(S03H)2~C6H3(NH2)*S03H + 2H20 is obtained together with the tetrasulphonic acid when benzidine sulphnte is heated for a long time at 180-190" with sul- phuric acid monohydrate or when a solution of benzidine in a little hulphuric acid monohgdrate is heated at 160-1T0° poured into fuming sulphuric acid and heated again until a small portion gives only a slight precipitate when treated with water. The product is poured into water the solution filtered to separate small quantities of the disulphonic acid and neutralised with barium carbonate. The barium salt of the trisulphonic acid is readily soluble in cold water and can be easily separated from the salt of the tetrasulphonic acid which is only sparingly soluble.Benzidinetrisulphonic acid is pre- cipitated in soft colourless plates on adding concentrated hydro- chloric acid to a moderately concentrated solution of the barium salt. It is readily soluble in cold water but only sparingly i i i alcohol andORGANIC CHEMISTRY. 59 is reprecipihated from the alcoholic solution on adding ether; it is completely decomposed when heated. ci-ystallises in small colourless prisms and is precipitated from its coilcentrated aqueous solution on adding alcohol. The ba.rium salt (C,,H9N2S30,)2Ba3 + 12H~0 /2enzidiizetetrasulp~o~,ic acid CsH?(NH,) (SO,H)z.CsHz(NH,) (SOB) is precipitated in small colourless needles on adding hydrochloric acid t o a concentrated aqueous solution of the barium salt; it is very readily soluble in cold water and is also soluble in alcohol.The barium salt Cl?H8S10,,Ba + €?H,O cryst,allises in colourless needles or prisms aiid is very sparingly soluble in hot water and insoluble in alcohol. Benzidin esulp hone ?6H3(NH2)>SO? is best prepared by gradually adding benzidine sulphate (1 part) to a 20 per cent. sulphnric acid solution of sulphnric anhydride. and heating the mixture on the water- bath until i t is free from unchanged benzidine ; the product is poured on to ice and the benzidinesulphone sulphate is separated by filtrntiou and decomposed with soda. It crystallises in very small yellow anhydrous needles melts above 350° and is almost insoluble in boil- ing water and insoluble in alcohol ether and benzene.The salts are decomposed by water. The hydrochloride C12HloN2S02,2HC1 crystal- lises from hot dilute hydrochloric acid in which it is moderately easily soluble in almost colourless plates. crptallises in grey or colourless needles or plates and is only sparingly soluble in hot dilute sulphuric acid. The platinochZoride crystallises in small dark yellow plates and is insoluble in water. ,4 h ydroxybenzidine C12HllN2.0H is formed when the sulphone is heated a t 180" with caustic soda; it is a grey compound very sparingly soluble i n water but readily i n soda. The sulphate and l~ydrochloride are sparingly soluble in water. When benzidinesulphoiie hydrochloride is treated with sodium nit'rite in aqueous Eolution and the resulting brown amorphous tetrazo-compound reduced with stannous chloride and hydrochloric acid the hydrazine is obtained in small yellow needles sparingly soluble in water.The latter is decomposed when boiled with copper sulphate solution yielding a diphenylenesulphonic acid melting a t 2:'8" and identical with the compound obtained by Stenhouse (Annalen 156 332) from diphenylene sulphide. The azo-dyes obtained from benzidinesulphone differ from those of benzidine and benzidinesulp honic acids in possessing a marked blue shade. C,H3(NH,) The s u b h a t e CVZHIJ?~SO~,H2SOd + 1iH20 Beizzidi~~s.1Llphone~z~Z~~onic acid S03H-C6H2(NH2) <c6H3(NH2)> so - is formed together with the di- tri- and tetra-sulphonic -acid when the sulphone is heated with fuming sulphuric acid a t temperatures above 100'.The crude product is boured 01 to ice and after keep-60 Al3Sl'RACTS OF CIIENICAL PAPERS. i n g for some time the solution is filtered; the tri- and tetra-hulphonic acids being readily soluble in cold water pass into the filtrate whilst the mono- and di-sulphonic acid which are only sparingly soluble remain ou the filter. The residue is dissolved in soda and the mono- sulphonic acid is precipitated from the filtered solution by adding acetic acid ; the disulphonic acid in the filtrate is then precipitated by adding a large excess of hydrochloric or sulphuric acid. Benzi- dinesulphonesulphonic acid crystallises from hot water in which it is only sparingly soluble in small light-yellow needles and is almost insoluble in alcohol.The tetrazo-derivative is a reddish.brown amorphous compound ; i t combines with amines phenols and with their carboxglic and sulphonic acids forming dyes which are of a redder shade and are much more sparingly soluble than those derived from benzidinesulphonedisulphonic acid (see below). The ccr Zcium salt (Cl,H,NTS20,)2Ca + S&H20 crystallises in small yellow needles and is readily soluble in hot water but only moderately so in boiling alcohol and sparingly in cold water. The barium salt (with 3+H,O) crystallises in small golden needles and is more sparingly soluble in water than the calzium salt. Ben zidinesu @ honedisdphon ic acid 1$H,O separates in small light-yellow needles when a boiling aqueous solution is evaporated.It is inodermtely easily soluble in hot water but only sparingly in alcohol and almost insoluble in cold hydrochloric or sulphuric acid. The tetruzo-compound is a light- yellow voluminous substance ; i t combines with naphthols and naphttolsulphonic acids yielding purple to violet dyes and with naphthylamines and naphthylaminesulphonic acid Porming red or bluish-violet colouring matters. It yields beautiful reddish-violet or indigo-blue azo-dyes (sulphoneazurines) wi tli alkyl- and phenyl- naphthylamines. The calcium salt CI2H,N2S3O8Ca + i H 2 0 crystal- lises in yellow needles or plates and is readily soluble in hot but orily sparingly in cold water and insoluble in alcohol. The barium salt (with 4iH,O) crystallises in needles or very small prisms and is insoluble in alcohol and only very sparingly soluble in boiling water.The sodium salt crjstallises from hot concentrated aqueous solu- tions in long yellow needles and is only sparingly soluble in cold water. Orthotolidine yields analogous compounds to those obtained from benzidine under the same conditions. Ol.thotoliJirnesziZphon~c acid is vwy sparingly soluble in water and does not crystallise readily. The tetmzo-derivative is readily soluble in water. The barium salt loses 4 mols. H,O when dried a t 150". The disuZpyhonic acid crystallises from hot concentrated aqueous solutions in small colourless needles and is readily soluble in hot water. The tetrazo-derivative is insoluble in water. The salts are moderately emily soluble in water; the sodium salt crystallises in cuhes (with 4H,O) the ctcbium salt in plates (with 5H20) and the barium salt in needles (with 3H20).Tolidinesdphone is a greenish-yellow amorphous compound the salts OF which are very similar to those of benzidinesulphone (D.R.-P. No. 44,784). F. S. K. >so + yJL(NH,) (S0,H) C,H,(NH,)(SO,H)ORC INIC CHEMISTRP. 61 p-Naphthylhydrazine. By F. HAIJFF (Awnalen 253,24-35).- The derivatives of p-naphthylhgdrazine bear a close resemblance to the corresponding phenylhydrazine-derivatives. The acetyl-deriva- tire Cl,,H7*N2H,Ac. prepared by boiling p-naphthylhydrazine with glacial acetic acid for several hours in a reflux apparatus forms colourless needles soluble in alcohol chloroform and benzene and melts a t 164-165". Renzoylnnphthylhydruzine C,,H,*N~H,BZ is ob- tained on adding benzoic chloride to an ethereal solution of naphthyl- Iiydrazine (3 mols.) ; naphthylhydrazine hydrochloride is precipitated and the filtrate on being evaporated and the residus treated with a hot dilute solution of sodiiim hydroxide to remove unaltered benzoic chloride leaves the hg drazine.When pure it crystallises in needles melts at 154-155" and is soluble in hot alcohol ether benzene and chloroform. I n order to introduce a second benzoyl-group into the preceding compound it is necessary t o act on it with beuzoic chloride at a high temperature. The dibenzoyl-derivative C'10H7.N2HB~2 melts a t 162-163". B-NaphthyZsemicarbazide C1nH7*N?H2*CO*NHz prepared by the action of potassium cyanate on naphthylhydrazine hydrochloride is soluble in hot alcohol and acetic acid ; i t melts at 220" (uncorr.) and resembles the corresponding phenyl-derivative in its chemical pro- perties.It is decomposed by the action of hydrochloric acid in sealed tubes at 140° yielding naphthazine which has previously been described by Witt (Abstr. 1887 153). P-Naphthy Zthiosemicarbazide C,oH7*N2H2*CS*NHz is obtained by boil- i n g an alcoholic solution containing equal parts by weight of naphthyl- hydrazine hydrochloride and ammonium thiocyanate. This substance melts at 201 -202" (uiicorr.) and is soluble in hot aniline and alcohol. It is decomposed by hydrochloric acid in sealed tubes at 130-140" NH yielding napht~~y Zthiocarbizine CIOH7N< & . The carbizine melts at 2.53-2.54" and crystallises in plates. It is solublc in warm alcohol and forms a crystalline hydrochloride and platinochloride.A violet precipitate is formed when bleaching powder is added to the alcoholic solution of the base. Naphthylhydrazine naphthylthiocarbazin~te C,,H7*N2H2*C i3.S H,N,H,*Cl,H cry$tallises in plates and melts with decomposition at 145". It is soluble in warm alcohol. Ethyl-P-naphthylhydrazine is prepared by the action of ethyl iodide (2 mols.) on naphthylhydrazine in alcoholic solution. I t is a pale-yellow oil freely soluble in alcohol ether benzene and chloro- form. I t reduces warm Fehling's solution. The solution in ch1or.o- form is slowly decomposed by mercuric oxide yielding naphthylethyl- am i lie. w. c. w. Derivatives. of p-Naphthylhydrazine. By A. H [LLRINGHAUS (per. 22,2656-26.57).-ln reference to Hanff's work on th:s subject (preceding Abstract) the author states that he has also recently6% ABSTRACTS OF CHEMICAL PAPERS.obtained the acetyl-derivative the semicarbazide and the thiosemi- carbazide. L. T. T. Derivatives of the Two Isomeric Naphthenylamidoximes By E. RICHTER (Ber. 22 2449-2459; compare Abstr. 1887 374 also Ekstrand ibid. 373).-P-Napthenylamidoxime (m. p. 150) is readily soluble in alcohol and ether but only moderately easily in benzene and chloroform and insoluble in light petroleum. The COT- responding a-compound (m. p. 148-149") resembles the /?-deriva- tive in its behaviour with solvents. Benzoy 1-P-naphthenylamidoxime C,oH,*C(NH,):NOBz prepared by heating the amidoxirne with benzoic chloride crystallises from hot alcohol in colourless needles melts at 179' and is only sparingly soluble in cold alcohol ether benzene chloroform and light petroleurn insoluble in water.NO Naphtlteiaylbenzenylazoaime ClOH,*C< - N>CPh is formed when the preceding coinpound is boiled with water dilute acids or diluh alkalis or when i t is treated with concentrated sulphuric acid. I t crystallises from dilute alcohol in colourless plates melts a t 116" aild is readily soluble in alcohol ether benzene chloroform and light petroleum but almost insoluble in water. Acetyl-P-naphtheny lamidoxime CI:,H,2N20 crystallises from alcohol or benzene in yellowish needles melts a t 154" and is only sparingly soluble in ether chloroform a1.d light petroleum and insoluble in water ; when boiled with water or when treated with concentrated sulphuric acid it is converted into the azoxime melting at 85" (compare Ekstrand Zoc.cit.). Ethyl-P-napht hen y larnidoxirnecarboxy late C10H,*C ( NH2) :NOC OOE t separates from alcohol in colourless needles melts a t 121" and is readily soluble in alcohol ether benzene chloroform and acids but very sparingly in light petroleum and insoluble in water and alkalis. NO P-Nap hthen y lcarbon y limidoxime C > C 0 cry s tallises from hot benzene in cclourless needles melts a t 216" and is mode- rately soluble in alcohol ether and chloroform but sparingly in benzene and hot water. The sodium-derivative is crystalline. In an aqueous solution of the ammonium-derivative lead acetate produce? a white and copper sulphate an apple-green precipitate.P-Naphthe?j ylamidethoxime CIOH7.C ( NH2):NOEt crystallises from dilute alcohol in colourless needles melts a t 74-75" and is readily soluble in alcohol ether benzene chloroform light petroleum and hydrochloric acid but very sparingly in water and insoluble in alkalis. Ethylidene-@-naphthenylamidoxime C,oH,*C<NH>CHXe NO pre- pared by dissolving the amidoxime in acetaldehyde crystallises from hot water in colourless needles melting at 121-122". It is readily soluble in alcohol ether benzene and light petroleum very sparingly soluble in cold water and insoluble in acids aud alkalis.ORGANIC CHEBIISTRY. 63 NO Acet oe t heny I- &nap ht heny lazoxime C ,,H7 C<- N>C* C HzAc is f ovmed by boiling the amidoxime with ethyl acetoacetate ; it crystallises from hot water in nacreous plates melts a t 108-109" and is soluble iu alcohol ether benzene and chloroform but insoluble in light petroleum.Acetyl-a-na~hthenylamidoxirrLe crystallises from dilute alcohol in colourless needles melts at 129" and is insoluble in water but readily soluble in alcohol ether benzene and chloroform ; when treated with concentrated sulphuric acid or when boiled wit.h water it is converted into the azoxime (compare Ekstrand Zoc. cit.). Ethyl-a-napht?~enylanaidoxi~mecarbozylatu crystallises in colourless needles melts at 11l0 and is readily soluble in alcohol ether benzene and chloroform but only sparingly in light petroleum and insolnble in water. a- Naphthen.yZcarbonylimidoxirne prepared by boiling the preceding compound wit.h water or alkalis crystallises from dilute alcohol in colourless needles melts at 189" and is readily soluble in alcohol bnt only sparingly in ether benzene and chloroform and insoluble in light petroleum and water.I n aqueous solutions of the ammonium- derivative lead acetate produces a white and copper sulphate a green precipitate. F. S. K. Acetyl- and Ethyl-derivatives of Camphonitrophenol. By P. CAZENEUVE (Bull. SOC. Chiin. C3] 1 467-469 ; compare Abstr. 1889 CsN02 618) .-The acetyl-derivative of camphonitrophenol C8H14<l 1 C*OAc) after saponification and subsequent saturation with slight excess of hydrogen chloride gives with ferric chloride a violet-red coloration CH*N02 which indicates the forniation of the compound C,H,,< I The ethyl-derivative CsHld<E.oEt is made by heating sodium camphonitrophenoxide with excess oE ethyl iodide in sealed tubes at 120" for three hours; after separation of sodium iodide the liquid is evaporated to dryness and the residue crystallised from benzene.The compound forms large colourless flat crystals which melt at 54" and decompose on distillation. C(OH)2 T. G. N. Camphonitrophenol Phosphate. By P. CAZENEUVE (BUZZ. SOC. Chirn. [ 3],1,46!b--47 1) .-The normal phosphate ( C,,t€,,NO,),PO is prepared by boiling camphonitrophenol with phosphoras trichloride for several hours. It exists as an amorphous yellowish insoluble sub- stance which when heated decomposes without melting. Nitrophenol forms an analogous compound ( C6K4NO,),PO with phosphorus pent+ chloride only traces of metachloronitrobenzene being simultaneoiisly produced. This reaction confirms the constitution previously giveu to camphonitrophenol. T.G. N.64 ABSTRXCTS O F CHEJIICAL PAPERS Camphonitrophenol Benzoate and Phthalate. B J P. CAZE- C-NO N EUVE (BUZZ. Soc. Chim. [3] 1,471-4B).-The benzoate C,H,,< I I C-OBz i R prepared by the reaction of equal parts of camphonitrophenol and benzoic chloride at 100' ; it forms small crystals which are insoluble in water but soluble in hot alcohol ether and benzene; these melt a t 131" ; and partially volatilise a t 150" without decomposing. On saponification with alcoholic potash it yields potassium benzoate and the compound C,N,,< I C-NO C(OH)?' Phthalic chloride by a similar reaction forms a compound (N0o.C 10Hl,o)J&H,02 which melts at 275" with slight decomposition.T. G. N. Quercetin-derivatives. By J. HERZIG (LVonatsh. 10 561-567 ; compare Abst)r. 11388 1309) .-In a preyious communication the author has called attention to the fact that pure xanthorhamnin ie not the sole product obtained from Persian-berries by the method of Liebermann and Hijrmann (Abstr. 1879 'L71). It is now shown that besides xanthorhamnin the berries cont.ain a glucoside of rhamnetin or some nnstable molecular compound of the glucosides of rhamnetin and quercetin. This result is in accordance with the fact that Schutzenberger obtained two glucosides ( a - and P-rhamnin) from Persian-berries. His a-rhamnetin (from z-rhamnin) is evidently identical with rhamnetin his P-rhamnetin (from p-rhamnin) with quercetia.G. T. M. Scutellarin one of the Constituents of Scutellaria 19nceo- lwia. By I). TAKAHASHI (Chem. Centr. 1889 ii 100.)-The root of ScuteZZariu Zunceularia one of the labiatse is used medicinally in China and Japan. By extracting the root with ether agitating the ether extract with sodium hydroxide and acidifying the alkaline solu- tion a yellow. flocculent substance scutellnrin is obtained. It forms odourless and tasteless shining flat yellow needles melts at 199-199*5" is insoluble in cold little soluble in hot water very readily soluble in alcohol ether chloroform light petroleum and carbqn bisulphide ; soluble in sodium hydroxide and carbonate solut,ions ,but carbonic anhydride is not expelled from the latter. It dissolves in concentrated sulphuric acid with a yellow colora- tinn and water reprenipitates the substance unchanged. It dis- solves in nitric acid with red coloration and in like manlier in a solu- tion of sulphuric acid and potassium nitrite.Fehling's solution is llot reduced by it even after boiling with hydrochloric acid. J t does not combine with phenylhydrazine ; neither silver nitrate nor lead acetate precipitates it from its alcoholic solution but solu- tions of lead and copper acetates produce a yellow-red precipitate with the dcoholic solution. When treated with bromine in carbon bisulphide solution a substance crystdlising in yellowish needles is formed ; the determiriation of bromine in it however! gare unsatis- factory results. The el2mentary analysis of scutellarin give figuresORGANIC CHEMISTRY.65 which corresponded with the formula CloH,03 ; it contains neither nitrogen nor water of combination. 5 grams of scutellarin produced no effect when administered to a dog in an emulsion of milk and gum arabia The author believes it to be a phenol and possibly an isomeride of juglone. J. W. L. Crystallised Digitalin. Ry ARNAUP (Compt. rend. 109 6i9- 682) .-Digitalin prepared by Nativelle's method from the digitalis of the Vosges formed very thin brilliant white rectangular lamelh which melt at 243" dissolve in absolute alcohol to the extent of 0.650 part in 100 at 14" and also contrary to the statement of Schmiede- berg dissolve in boiling benzene. When subjected to fractioual solution the melting points of the different fractions varied only between 242" and 245".A second quantity prepared by Adrian melted at 245-246" and when dissolved fractionally in alcohol and benzene the melting points varied only between 243 and 245" as with the first sample. Digitalin is a distinct chemical individual and it is not necessary to denote it by any name such as digitoxin. It seems to be the typt. of a large group of compounds. C. H. B. Dihydropyrroline. By F. ANPERLINI (Ber. 22 2512-2515).- Dihydropyrroline hydrochloride is decomposed when heated givingr off vapours which colour pine-wood red ; it is partially decomposed by concentrated hydrochloric acid at 130-140". The uuroch loride. C4NH7,HAuC14 crystallises from cold water in small prisms melts at 152' and is slowly decomposed when boiled with water. The picrate CdNH7,C6H3N307 separates from water in yellow crystals melts at 156" arid is readily soluble in alcohol and water.Benzoy Zdihydropyrroline C4NH6Bz prepared by heating dihydro- pyrroline hydrochloride with benzoic chloride at 110" is an oily liquid boils at 160-161" (2 mm.) and is miscible with alcohol and ether but is insoluble in water. It dissolves freely in con- centrated hydrochloric acid yielding a salt which does not crptallise readily. Benz y Zdihy drop yrroline C4NH6*C H,Ph prepared by treating di - hydropyrroline with benzyl chloride boils at 150". The aurochloride CIIH,,N,HAnCl~ crystallises from water in yellow needles melting. at 111". E. S . K. Derivatives of Alkylpyrrolines. By C. U. ZANETTI (Bey. 22 2515-2519 ; cornrare Ciamician and Zanetti Abstr.1889 727).- 1-Ethylpyrroline boils at 129-130" (762 mm. corr.). The tetra- bromide melts at 83" and is converted into ethyl dibromomaleimide (m..p. 93-94") by cold nitric acid of sp. gr. 1.49. The diacGtyZ- derivative C4NHzEtAc is a crystalline compound melts at 58-59' boils a t about 183" (29 mm.) and is readily soluble in alcohol ether benzene light petroleum and warm water. When the mixture of c-ethylpyrrolinep boiling at 150" (compare Ciamician and Zanetti Zoc. cit.) is treated with acetic anhydride and sodium acet'ate an oil is obtained which can be separated by frac- VOL. LVIII. f66 ABSTRACTS OF CHEXICAL PAPERS. tional distillation into a portion boiling at 210-235" and a portion builing at 240-255". The former is volatile with steam and has the composition and properties of an 1-acetyl-c-ethylpyrrolins C4NH3EtAc.The latter after having been boiled with potash and repeatedly distilled in order to free it from 1-acetyl derivatives solidifies parti- ally when exposed to long continued cold and can thus be separated into its constituents ; the crystalline substance is an acetyl-deriva- tive melting a t 42-44" probably identical with the compound (m. p. 47") obtained by Dennstedt a a d Zimmermann from c-ethyl- pyrroline (compare Abstr. 1886 1043). Both the liquid and the solid compound give a silver-derivative which has the composition l-Propylpyrroliije C4NH4Pr is obtained in small quantities when potassium pyrroline is treated with propyl iodide but isomerides and other compounds are also formed; it) is a colourless oil hoiling a t 145-5-146*5" (755.8 mm.).Nitropyrroline-a-carboxylic Acids. By F. ANDERLINI (Ber. 22 %503-2506).-Methyl nitropyrroline-a-carbox~lafe NO,-C,NH,*COOMe (m. p. 197") is formed together with an isomeride (m.p. 179") and other nitro-compounds when finely divided methyl pyrroline-d- carboxylate is gradually added to ice-cold nitric acid of sp. gr. 1.5 aud the solution poured into cold water; after neutralising with soda and adding a lit'tle sodium carbonate the solution is extracted with ether It crystallises from boiling water in coloudess needles melting a t 197". The corresponding acid N0,.C4NH,COOH ob- tained by hydrolysing the ethereal salt with potash crystallises from water with 1 mol. H,O in light-yellow needles and is readily soluble in alcohol ether and hot water but only sparingly in benzene and cold water.I t loses its water when kept Over snlphuric acid under reduced pressure and the anhydrous crystals melt a t 217". Nethyl nitropyrroline-a-carboxylate (m. p. 179") is obtained together with other nitro-compounds when the alkaline solution from which the isomeride (m. p. 197") has been extracted is acidified and then extracted with ether. It can be isolated by hactionally cry stallising the crude product from water. It separates from dilute alcohol in yellow needles melting at 179". The corresponding acid crystallises from hot water with 1 mol. H,O in light-yellow needles and is readily soluble in alcohol ether and hot water and moderately so in benzene but .only sparingly in cold water.It loses its water when kept over sulphuric acid under reduced pressure the anhydrous compound melting a t 161". The mother-liquors from the preceding compound (m. p. 179") probably contain the third isomeride which has previously been pre- pared by Ciamician and Danesi (Abstr. 1882 875) from dinitro- pyrocolf but this compound could not be obtained in a pure condition. They also contain the methyl salt of a dinitropyrroline- carboxylic acid C4NH2(N02)2*COOMe ; this compound crystallises froin watler dilute alcohol and benzene in light-yellow plates melting a t about 113". F. S. K. C,HioNOAg. F. S. K.ORGXSIC CHEJIISTRY. 67 Molecular Weights of the Imidoanhydri 3es of Pyrroline- carboxylic and Indolecarboxylic Acids. By G. MAGNANLNI (Bw. 22 2j01-25Oq.Molecular weight determiuations by Raoult's method in naphthalene solution show that the molecular formula of pyrocoll is C10H6N202 that of tetramethylpyrocoll ClIH,,N,02 that of diacetylpyrocoll C14HloN20~ and that of the imidoanhydtide of a-indolecarboxylic acid C18H10N202. The depression constant of naphthalene was taken as 82 according to Raoulb. Action of Methyl Iodide on Tetramethyldihydropyridine. By F. ANDERLINI (Ber. 22 250d-f251l).-Pentamethyldihydro- py r i din e h y d riod i il e is obtained w h en t e trame t hy Id i hy d rop y rid in e (b. p. 158") is treated with methyl iodide (compare Cilimician and Anderlini Abstr. 1889 728) The free base boils at 188-190" (45-46" ; 7 mm.). A bnse C12H?,N is formed when pentamethyldihydropyridine is treated with niethyl iodide in the cold and the resulting oily hy- driodide distilled with potash; the base was not isolated.The uu?-ochZoride CI2Hz1N,HAuCl4 crystallises in thin golden needles melting a t 99-99.5". F. S. K. F. S. K. Synthesis of Oxypyridine and Piperidine Bases. By A. Lau~xsunc; (Ber. 22 2583-2590) .-a-Picolylalkins is obtained as a thick brown syrup by the action of formaldehyde on a-picoline and is purified by distillation under 20-30 mm. pressure. It is a colourless syrup boils at 179" nnder 25 mm. pressure dissolves readily in water and alcohol sparingly in ether i t is rather hygroscopic and can only be dried over fused potassium carbonate ; sp. gc". 1.111 a t 0". Theplcitinochloride (C7H9NO),,H,PtCl crystallises well in pristiis very readily soluble in hot water and melts a t 170" with effervesceuce.The aurochioride crpstallises in well- formed crystals rather sparingly soluble iii water. Vi,t ylpyridirw C5NHI.C2HB prepared by distilling the above com- pound under higher pressure o r in preseiice of potash is a colourless mobile liquid very readily soluble in alcohol ether and chloroform &c. but only sparingly in water. It boils with decomposition a t 158-13:! at t.he ordinary pressure but distils without decomposition a t 79-82' under 29 mm. pressure ; sp. gr. = 0.9985 a t 0". The ylutinocldoride (C,H7N)?,H2PtCI6 crystallises in needles or large plates melts a t 174" with decomposition and is rather readily solutle in water. The chuimhloyide cadnzioiodide bismuth iodide and rnemwocll loride cryst,aI- lise well. a-YipecoZyZalTcine C,NHlo.CH2*CH2*OH obtained by the action of sodium and alcohol t)n picolylalkine is a colourless crystalline base Tvhich melts at 31-32' aiid boils at 225-228'.It is very hygro- scopic and is readily soiuble water alcohol and ether. It is a strong base and turns red litmus blue. The yZutinocltZorit?e (C,H,,NO),,H,PtCI crystallises in splendid large transparent crys- tals like gypsum and melts at 158". f 268 ABSTRACTS OF CHEMICAL PAPERS. a-Meth?/ZpipecolineaZX;ine C,NH,Me*CH,2*CH2*OH is formed when a-pipecolylalkine dissolved i n metlipl iodide is Lrmted with methyl iodide and sodium at the ordinary temperature. When the methyl iodide has disappeared the alcohol is evaporated the residue re- peatedly extracted with ether the base converted into the hydro- chloride and warmed slightly with sodium nitrite.The nitrosamine which separates is removed by ether. The hydrochloride is then treated with potash and the tertiary base is extracted with ether and dried with potash. The aurochloride is crystalline ; the plafino- chloride cadmioiodide and periodide were also prepared. Vin ylpipwidine C,NH,,;C,H (?) is obtained from pipecolylalkin by the method previously employed for the preparation of tropidine from tropine (Annalen 217 118). It is a colourless liquid boils a t 146-148" is readily soluble in water and has an odour of tropidine aiid coniine. The aurochloride and p i c m t e crjstallise well and are rather soluble in water. a-Picolyl~2ethylaIkine7 C5NH4*CE3*CHMe*OH is formed in a manner himilar to a-picolylalkine from a-picoline and acetaldehyde and is purified by means of the platinochloride. It is yellowish boils a t 176-181" under 18 mm.pressure and is readily soluble in water alcohol and chloroform sparingly in ether. The plrctinochlorz'de ( CRHl,NO)2,H2PtC16 crystallises from hot water in small plates which melt R t 189" with decomposition ; the auroohEoride crystallises well. a-Pipecolylmetl~ylalkit~e C,NH,,*CH,*CHMe*OH melts at 47" boils at 224-226" and is readily solnble in water alcohol and ether The platinochloride melts at 149". I n its properties the base resemhles conydrine with which it is isomeric. N. H. M. Hydroxymetadiazines (Hydrsxypyrimidines). By E. v. ME YE^^ (J. pr. Chem. [2 ],40 303-304) .-Amidomethyldiphenylmetadiazine (Abstr.1889 578) melts at 1G8" not 172" ; it can also be obtained by acting on a mixture of ethyl cyanide and phenyl cyanide with sodium o r sodium ethoxide. Hydroxymethyldiphenylmeta#diazine (loc. cit.) melts at 250" not 256" ; it can also be obtained by the condensation of benzamidine and ethyl methylbenzoylacetate. By heating it with alkaline potassium permanganate adding dilute hydrochloric acid to the colourlew solu- tion dissolving the precipitate in weak ammonia filtering and again precipitating with hydrochloric acid a hy droe ydiphenylmetadiazinecar- boxylic acid C P h < ~ ~ ~ ~ ~ C C O O H is obtained ; this crystallises from alcohol in beautiful pale-yellow prisms melting at 236" with evolution of carbonic anhydride. When heated in a diphenylamine bath at 250" until evolution of carbonic anhydride ceases it leaves a yellow crystalline residue mostly soluble in potash ; if the preci- pitate obtained by adding hydrochloric acid to this potash solution is digested with weak ammonia and crystallised from alcohol yellowish slender needles CI6Hl2NZO which melt a t 280.5" (uncorr.) are ob- tained. These appear to be identicad with Pinner's diphenylhydroxy- pyrimidine (Abstr. 1889 lOOS) which melts at 284".ORGANIC CHEYISTRT.69 N ='CEt Hydrozymethylefhylmet?~ ylmetadiazine CMeGN ,c (bH)>CMe is obtained from acetamidine and ethyl propionylpropionate ; it melts at 167*5" and is isomeric with the hydroxy-base of cyanmetthethine melting at 150" (Abstr. 1885,646). A. G. B. Pyrimidimes. By A. PIXNER (Rer. 22 2609-2626 ;.compare Abstr. 1889 1006) .-The formation of the pyrimidines appears to take place in three stages. Employing benzamidine and ethyl acetoacetate as examples these stages are as follows :- I. NHXPh-XH + COOEt*CH,-COMe = NH CPh*NH*C 0 *CH2*COMe + EtO H. The ethyloxalylacetylbenzamidine already described (Abstr. 1889 1009) is the first-stage product in the formation of phenylhydroxy- pyrimidinecarboxyiic acid and may be easily converted into the latter by the action of soda. The compound obtained at the same time and melting at 263" is phenyIhydroxypyvimidinecarboxytbenzamidine N<g[k@-$>C*CO*N H C Ph N H the benzamidine haviii g reacted with the second carboxyl-group of the acetoxalate. It is converted int,o the above carboxylic acid by the action of soda.As already noted (Zoc. cit.) the free acid melts with decGmposition at 247" ; carbonic anhydride being evolved and phenylhydroxypyrimidine is formed. When benzamidine and ethyl acetomalonate react on one another one carboxyl-group is separated and the same pyrimidine formed as is obtained from ethyl acetoacetate. When ethyl acetosuccinate benzamidine hydrochloride and sodium hydroxide or potassium carbonate are mixed together two compounds are obtained melting respectively at 1 7 8 O and 212". The former (m. p. 1 7 Sv> is ethyl pheny lmet IL y lh y drox yp yrimidirkeacetnt e - I t is easily soluble in alcohol ether and acetone sparingly in water and crystallises in needles. When saponified with soda it yields phen.y lmethglhydrox ypyrimidineacetic m i d which crystallises in needles melts a t 259" and is soluble in alcohol.The needles crystallising at 212" have the formula C11H,oN202 and are probably succinylbenzimide ?H2'Co >N.CPh:NH. This compound forms the principal product CH,.CO if caustic soda is used for liberating the benzamidine from its hydro- chloride in the reaction whilst if potassium carbonate is employed the pyrimidine is the chief product.70 ABSTRACTS OF CHEMICAL PAPERS. With ethyl acetylglutarate benzamidine yields etlbylphen yluz ethyl- h y droxyp yrimidine~r~p~ona t e C P h q N N:C(OH)/ - '' eW2 C H,*C H,. C 0 0 E t which crystallises in needles is soluble in alcohol ether and acetone and melts a t 145". The.free acid forms a white powder almost in- soluble in water and alcohol and melting a t 215".When ethyl diacetosuccinate is mixed with benznmidine ethyl phe~iylmethylhydroxypyrimidineacetate (m . p. 178") and phenyl- met h y 1 ace tony l h y droa yp yrimidine C P he" 6 gy>C. CH,G OM e are formed. The latter is insoluble in acet,one soluble in alcohol ; it crvstallises in needles and melts at 225". The author was uuable to obtain the dipyrimidine C P h ~ N ~ c ~ o H ~ ~ - C ~ c I C H ~ ~ ~ CMe - N - CMe which he had anticipated the second' aceiyl-group appearing alwajs to be separated before the pyrimidine formation set in. A mixture of ethyl succinylsuccinnte and benznmidine yields a sub- stance easily soliible in alcohol and melting at 272" and another almost insoluble in the usual solvents. The fornier. tetra7~i/dl.owhe?.uZ- .I 1 .I ?~ycirox~ketopui?kasdine ~:C(oH)'f?CHz*~Hz crystallises in needles. CPh Pr'*C'CH,-CO The latter owing t o its insolubilit'y could not be thoroughly purified but appears to have the formula C,H,,N4O2 and to be dihydrocli- ~:C(OH)*~.CH,*$*N = CPh It dis- plieny ldih y clrox yantetrazine CPh=N*C*CH,.C*C(OH):N solves in boiling caustic soda yielding a crystalline sodiz~nz-deri.cat.iz;e C,,H,,Na,N,O + 4Hz0. The amidine of acetonecyanhydrin OH.CMe2*C (gH,):NH yields with e thy1 a cetoa cetate hydroxyisoprop y lmrfh ylhy d ~ o x y p yrimiditie OH.C?ile,.C~,:,(,,~~CH N-CMe crystallising in easily soluble needles and meltingat 98". If ethyl benzoylacetate is employed instead of the ace t oacet a t e h y droxy isoprop y @ heny lhy &ox yp y rimidine is formed. This crystallises in small glistening prisms sparingly soluble in water easily so in the usual organic solvents and melts at 198".L. T. T. Phenylhydrazonelevulinic Anhydride. By F. ACH (Annale?? 253 44-57). Two compounds are formed by the action of phos- phorus pentachloride on phenylhydrazonelevulinic anhydride a t 150. One contains 2 atoms of hydrogen less than the anhydride and the second compound is a monochloro-substitution-product of the first. The crude product of the reaction is poured into water containing ice. In the course of 24 hours phenylmethylchloropyridazone is deposited in crystals. The mother-liquor is rendered alkaline and treated with ether to extract the phenylrnethylpyridazone. The residue is redis- solved in 100 parts of boiling water to which a small quantity ofORGANIC CHEMISTRY.71 hydrochloric acid is added. On cooling the chloro-substitution-pro- duct crystallises out and the base is extracted from the mother-liquor as before. It is finally purified by precipitation as the hydrochloride by passing dry hydrogen chloride through its solution in benzene. NPh-N Phen?lEmeth?/~~yridazone CO< CH:CH>CMe is freely soluble iu alcohol ether chloroform benzene and acetone melts at 81-82' and has feeble basic properties ; its salts are decomposed by water. By the action of sodium on the hot alcoholic solution a crystalline base is produced which appears to have the composition C2,H,,N ; this melts at 200" and yields a sparingly soluble platinochloride. The solution in dilute sulphuric acid acquires a violet-blue colour on the addition of chromic or nitrous acid.Phenylmethylchloro/iyridazone C 0 < ~ ~ ~ ~ ~ > C M e crystallises ill flat prisms and melts at 136-137". I t is freely soluble in hot alcohol chloroform benzene and acetone and also dissolves in mineral acids but is reprecipitated unaltered from the acid solutions by water. The nitro-derivative melts at 210-213". The chlorine is displaced by ethoxyl by the action of alcoholic potassium hydroxide. PhenylmethyZathoxypyridazone melts at 14ti0 crystallises in flat prisms or plates and dissolves freely in hot alcohol benzene chloroform acetone and in hot water and is also soluble in strong acids. It is decomposed by heating at 125" in sealed tubes with hydrochloric acid yielding phenyZnzethyLhydroxypyyidazone.The hydroxy-derivative crystallises in needles and melts at 196". It is soluble in hot acetone benzene and chloroform in strong mineral acids and in alkalis. The addition of ferric chloride to the hydrochloric acid solution produces a red-brown coloration which turns to carmine on dilution. At 170" hydrochloric acid converts the hydroxy-componnd into phenyrnethyl- pyrazolecarboaylic acid I I >C*COOH. The acid is soluble in hot. alcohol chloroform benzene ether and in strong mineral acids C MeCH N-NPh melts at 165-166" and decomposes at 200" yielding phenylmethyl- pyrazole >CH probably identical with the phenylmethyl- Me*CH N-NPh pyrazole described by Knorr (Abstr. 1887 601). Phenylmethylpyrazole me1t.s at 34-36" and boils at 254-255" under 753 mm.pressure. It dissolves freely in ether alcohol chloro- form acetone benzene and light petroleum. The platinochloride forms orange-coloured needle-s haped crystals sparingly soluble in water. The pyrazole is convertled into the pyrazoline by the action of sodium on its alcoholic solntion. The pyrazoline melts at 73-75" and distils without decomposition. It is soluble in ether alcohol and benzene and gives the characteristic pyrazoline-colour reaction with ferric chloride or chromic acid. w. c. w. Synthesis of Quinazoline-derivatives. By C. PAAL and 31. BUSCH (Ber. 22 2683-2702) .-The authors have studied the action of orthonitrobenzyl chloride on the sodium-derivatives of form-52 ABSTRACTS OF CEEhlICAL PAPERS. anilide and of scetanilide and of some of their homologues.The met- nnilides did not give satisfactory results but with the fornianilides the following reactions (where R is an aromatic radicle) take place :- N0,-C6H4*CH2C1 + R-NNaaCOH = N0,.CsH4~CHz*NR~COH. On reduction the product yields quinazoline-derivatives Action of Orthonitrobenzyl Chloride on Sodium Formanilide.-Sodiuin formanilide is prepared by adding sodium to a benzene solution of form- anilide and then a proportional quantity of orthonitrobenzyl chloride is added. Orthonitrobenzy Iformanilide NOz.C6H4*CH,*NPh*COH is soluble in the usual organic solvents insoluble in water. It melts at i 7 " and forms yellow monosymmetric plates gixing the measure- ments a b c = 0.5477 1 1.085 and l3 = 69" 7'. This formanilide was also obtained by boiling ort~honitrohenzylaniline (Lellmann and Stickel Abstr.1886 793) with formic acid. When reduced with zinc and acetic or. hydrochlonic acid phenyldihydropuinuzoline C6H4<CH2.hph is formed ; this crystallises in hexagonal plates is N=CH almost insoluble in water and alkalis easily soluble in mineral acids alcohol ether &c. It melts at 95" and distils at a very high tem- perature with partial decomposition. When distilled with zinc-dust i t yields equal quantities of aniline and benzonitrile. Its sulphate ( Cl4H,,N,),,H,SO4 + 2Hz0 crystallises from water in needles loses water at 70" and melts at 79"; when free from water i t melts a t 140-143" ; the hydrochloride + 'LH,O forms glistening needles melting a t 80" ; the anhydrous salt melts at 221" and is easily soluble i n alcohol and ether.The pZatin.ochZoride forms yellow crystals me1 ting a t 208" ; the aurochloride orange scales ; the sfunnochlol-ide ( ',4HlzN,,HSnC13 flat white needles or scales melting a t 130-134". When heated with methyl iodide in closed tubes at loo" the quinazoline yields three derivatives the methiodide periodide Cl4Hl2NZMeI,I forming glistening golden-yellow scales melting at 157" ; the meth- iodide C14H12N2,Mel crystallising in white needles melting a t 170" ; and a third substance crystallising in prisms melting a t l80" which appears to be a second isomeric rnethiodide. When oxidised with potassium permangmate the quinazoline yields phenyllietodihydro- YH which crystdlises in almost colourless quinazoline C&< glistening scales or well-formed rhombic crystals giving the measure- ments a b c = 2.4228 1 3.2742.It melts at 139" and sublimes without decomposition. No hydroxylamine-derivative or phenyl- hydraaide could be obtained but with hydrazine (amidogen) it yields >C<&,; this forms y heny lketoh?y drazodihy dro quinazoline white glistening needles which melt at 204" and in small quantities siiblime without decomposition. The hydrochloride Cl4H,,NZO,HCl crystallises in glistening scales and melts at 213-214" ; it loses its CO*NPh' NH H*NPh N- CeH,OHGAXIC CHEJJISTRY. 73 hydrogen chloride ah a moderate heat. The platinochloride crystal- lises in yellow needles melting above 300". When the keto-base is t,reated in alcoholic solution with sodium phen yltetrahydroq.uinazolir~e c,H,< CH,.&Ph is formed which is soluble in organic solvents cyystallises in white needles melts at 117" and distils at a high tem- perature without decomposition.It is only feebly basic its salts decomposirig on the addition of water. It yields a hydrochloride a crystalline aceto-derit,atice and 8 nitrosamine. An unstable inter- mediate product containing the (CH-OH) group appears to be formed along with the tetrahydro-componnd but it could not be isolated When oxidised with permanganate the tetrahydro-derivative is recon- verted into the keto-compound but both here and in the original formation of the keto-derivative small quantities of a sparingly soluble nitrogenous crystalline compound melting at 219" are formed. Actiosn of Orthonits.obenzy1 Chloride on Sodium Formqmrato1uide.- The reactions here are similar to those with formanilide.Ortho- ?&itl'oI)enzy~ornzopas.a,tolziide N02*C6&*CH2*N (CaH,Me)*COH crys- tallises in pale yellow needles melting a t 79" and is easily soluble in the usual organic solventls. It may also be easily prepared from orthonitrobenzylparatoluidine (Lellniann and Stickel Zoc. &t.). Yura- NH. CH AT- c1U I.( - w II t oZy ldih ydropuinazoline C6H4 < cH?.& C6H,Me 7 is easily soluble iii alcohol ether benzene and chloroform sparingly so in light pet8roleurn. It crystallises in glistening white scales melts at 120" and distils with partial decomposition. Distilled witn zinc-dust. it yields the amine and nitrile like the phenyl-derivative. The hydrochloride with 2 mols.H20 forms flat white needles and melts at 85" the anhydrous salt at 251" ; the platinoch loride forms glistening yellow needles melting a t 216" ; the stannochloride sparingly soluble needles melting a t 165". Methyl iodide forms two derivatives namely the methiodide crystallis- ing in white needles melting a t 186" and green metallic needles which appear to be the methiodide periodide. On oxidation the base yields which crystal- iuaratolylketodihydropuiizazoliiLe C,H,< CO.k*CsH,Me' lises in micaceous needles sparingly soluble in boiling water easily in organic solvents and melting at 146". The hydrochloride forms white needles melting at 213-214" and is dissociated by slight rise in teni- perature ; the pltztinochloride forms golden yellow scales melting above 300".By oxidation pralietediii ydrop,LLinazolylbenzoic acid P is produced as well as the above quinazo- line; the acid forms white crystals sparingly soluble in organic solvents and melting at 320". The silver salt torms a white flocculent precipitate. Yarntoyltetrahydropuinazoline crystallises in white needles melts at 127" and is easily soluble in chloroform and benzene sparingly in ether and alcohol. It forms a red nitrosamine a white unstable hydro- chloride and a yellow unstable platinochloride. Action oj* Orthonitrobenzyl Chloride o n Sodiumformo-orthoto1uide.- The reactions are similar to those with the isomeric para-compouud. N I C H K F H C6H~<co~N.CaN,~COOH74 ABSTRACTS OF CHEMICAL PAPERS. Orthonitrobenzylformo-orthotoluids forms a Sellow oil which melt,s at 'i69 and decomposes on distillation.Orthotolyldi?iydroyuinazoline forms a yellow amorphous mass its platinochloride orange-yellow needles me1 ting at 210" and its stannochloride and hydrochloride could not be obtained in a crystalline form. When reduced in alco- holic solution with sodium the base appears t,o yield the tetrahydro- derivative but this was not obtained in a pure state. L. T. T. Hydrastine. By W. KERSTEIN (Chem. Centr. 1889 ii 91 from Zeit. Naturwiss. Halle 61 425-429).-According to the author's experiments hydrastine obtained from the root of Hydrastis cuncc- densis has the formula C21H2,N06 and forms colourless needles melt- ing at 132". The hydrochloride C21H,lN06,HCl and hydrobromide C H,,NO HBr are white micro-crystallire salts ; the hydriodide is two wnish- y el lo w.In addition to those reactions already described showing the rela- tion which exists between hydrastine and narcotiue the author finds that by oxidation with potassium permanganate in acid solution opianic acid and probably also cotarnine are formed. When dis- tilled in a current of steam niecotiine and trimethylamine are formed in the case of both these alkaloi'ds. On the other hand they do not show any similarity in their behaviour towards acetic anhydride acetic chloride water under pressure or dilute sulphuric acid. From hydrastine ethiodide by the action of potassium hydroxide solution ethylhydrlnstine is obtained ; it forms lemon-yellow crgstals which melt at 127". By the action of iodine hydrastine is split up into opianic acid and hydrastonine ; the latter is distivguished from tarconine methiodide in tha,t no formaldehyde is formed on boiling its icdide 31 hydroxide with barium hydi-oxide. In addition from the root of H?/drastis canndensis the author has separated phytosterin C,,H,O + H,O ; this forms plates melting a t 13:3" the solution of which in acetic anhydride gives a red coloration passing into intense blue with concentrated sulphuric acid.J. W. L. Formation of Optically Active Tropic Acids and Optically Active Atropines. By A. LADENBURG and C. HUNDT (Ber. 22 2 5 ~ ~ 2 5 9 2 ) .-A dilute aqueous alcoholic solution of quinine (1 mol.) was added to a hot aqueous solution of tropic acid (ni. p. 116-1 18- 1 mol.) and the whole evaporated down on a water-bath until crystal- lisation commenced. On cooling a quantity of dull white crystals separated (quinine dextrotropate) and on further evaporation of the mother-liquor an oil separated which gradually solidified to hard cyystals of a glassy lustre (quinine kevotropate). Quinine dextrotropate melts a t 186-187".The free acid cryst allises from ether in hard clear prisms and from water in clear plates melts a t 127-128" and showed a rotatory power of 71.4". Quinine Zcevotyopate was not obtained quite pure ; i t melts a t 178" The free acid which was also not obtained pure melted at 123" and showsd a rotatory power of 65-15'.ORGANIC CEEMTSTRY. 75 When treated with tropine and tropic acid (Aiznalen 206 274) both acids yield the corresponding atropines. Deztro-atropine cqstallises from alcohol in white lustrous needles melts a t 110-lll" and has a rotatory power of + 10".The auro- c h l w i d e forms dull deep-yellow crystals melting a t 146-147". Lcmo-atropiua is a crystalline powder melting a t 111". The auro- chloride crystallises in lustrous needles and melts a t 246". The base resembles hyoscyamine but the two are not identical which is due to the fact that the latter base has two active asymmetrical carbon- atoms whilst the former has only one. N. H 31. Bases contained in the young Shoots of Solanum Tubero- sum. By R. FIRBAS (ilfonafsh. 10 541-56O).-The two products the one crystalline and the other amorphous obtained in the prepara- tion of solanine from the young shoots of the potato are now shown contrary to earlier views not to be chemically identical.The author names the crystalline compound solanine. It has the formula C52H,sN0,s,4&H,0 and when dried a t 100" appears to be anhydrous or t o contain only half a molecule of water of crystullisation. From a solution in 85 per cent. alcohol it crystallises in coloiirless needles which melt a t 244" are almost insoluble in ether and alcohol and are readily dissolved by dilute hydrochloric acid. Xolanidine hydro- chloride 3(C4,H6,N02,Hc1)Hcl + H,O or l&H?O is obtained by boiling solanine with a 2 per cent. solution of hydrochloric acid. It is a slightly yellow powder which is only very sparingly soluble in water and carbonises without melting when heated to 287". Simul- taneously with solanidine hydrochloride. a sugar is formed in accord- ance with the equation C52Ev3N0,8 = C40H6,N02 + BC6H1,0s + 4H20.The amorphous substance obtained simultaneously with solanine and which the author names solaiLeine has when dried a t loo" the formula C53Hs7N013 or C5,H,NOl3. The loss of weight on heating the air-dried compound a t 100" corresponds with the formula C,,H,,KO + 3 i or 4H,O. It is a yellow horny perfectly amorphons substance melting a t 208" is more soluble in an 85 per cent. solution of alcohol than is solanine and on treatment with hydroctloric acid yields solanidine and a sugar in accordance with the equation C52H83N013 + H,O = C4,H6,N0 + 2C6HI2O6. The sugar obtained by the hydrolysis of solanine and solanaine forms a yellow amorphous mass with a caramel-like odour dissolves readily in water and wood-spirit and has a specific rotatory power of [z]D = + 28.6%.With phenylhydrazine hydrochloride and sodium acetate in aqueous solution i t forms a glucosazone melting at 199" and resembling the compounds obtained similarly from dextrose levulose and several other sugars. With nitric acid it gives no recog- nisable trace of mucic or saccharic acids. The general behaviour of the sugar points to the conclusion that it is some other sugar than dextrose or a mixture of sugars. Solunidine has the formula C4,,H61N0 or C4,H&N02 and is obtained from alcoholic solution in amorphous masses interspersed with needles melting a t 191". It dissolves readily in hot alcohol with difficulty in76 ABSTRACTS OF CHEMICAL PAPERS. ether and on treatment with excess of dilute sulphuric acid forms a sulphate 3(C40H6,N02,H~SO~),H,s0 + 8H20 ; this crystallises in scaly plates melting at 247” and is readily soluble in water.Its diacetyl-derivative CmH5,02NAc2 crystallises in needles melting at 203”. G. T. M. Cinnarnylcocaine from Coca Leaves. By C. LTEBERNANN (Ber. 22 2661-2662) .-Measurements of crystals and quantitative decomposition determications are given to show that the cinnamyl- coea’ine which t>he author prepared synthetically from ecgonine is identical with t h a t obtained by Giesel horn the coca leaf. L. T. T. Haematoporphyrin and Bilirubin. By If. v. NENCKI and A. ROTSCHY (Monatsh. 10 568-573 ; compare Abstr. 1858 304 and 971) .-The authors suggest that Raoult’s method may be employed with advantage to determine the molecular weights of unstable substances of organic origin and have investigated the practicability of the method in two cases.Making use of acetic acid and phenol as solvents hzematoporphyrin gave numbers varying bet ween 226 and 331 which correspond with the simple formula C,6H,eN20 (mol. wt. = 286). I n the case of bilirubin ethylene dibromide and phenol were used RS solvents. This compound has the same molecnlar formula and is consequently isomeric with hzematoporphyrin. The range in the numbers obtained in both cases is due to the compounds being only slightly dissolved by the solvents employed. The iso- merism of haematoporphyrin and bilirubrin is confirmed by the fact that on reduction with tin and hydrochloric acid two different urobilins are obtained.G. T. 31.20 ARSTHACTS OF CEEMICAL PAPERS.Organic Chemistry.Tetrabromides of Diallyl. By G. CIAMICIAR and F. ANDERLINI(Bey. 22 2497-!2500).-A small quantity of an oily bromide,C6H1,,Br1 is formed in preparing diallyl tetrabromide (m. p. 63") bytreating the hydrocarbon with bromine ; when the crude product iscrystallised from alcohol the liquid bromide remains in solution. Itboils at 135-140" (about 8 mm.) with slight decomposition and itsmolecular weight determined by Raoult's method in benzene solu-tion was found to be 325 as the average of two experiments.?-Pen tyleneglycol and its An'hydride (Tetrahydromethyl-furfuran). By A. LIPP (Bey. 22 2567-2573).-y-PentylenegIycol(Freer and Perkin Trans. 1887 836) mixes in all proportions withwater alcohol and chloroibrm is rather sparingly soluble in ether inpresence of moisture and is insoluble in light petroleum.At -18" itis quite viscid. It boils at 219-220" (under 713mm. pressure) anddoes not decompose at 236". Sp. gr. = 1.0003 a t 0" (water at 0" = 1).When heated with 35-40 per cent. hydrobromic acid for one hour at loo" the anhydride is formed ; this boils at 77-7.9" ; sp. gr. = 0.8748a t 0" (water a t 0" = 1). It !is not changed when heated with watera t 200-210".y-Penty Zene dihrornide CHBrMe.CH2*CH2*CHzBr is obtained byheating the glycol or the anhydride with 3 to 4 parts of fuming hydro-bromic acid for three hours at 100". I t boils at 200-202'with partialdecomposition is insoluble in water readily soluble in alcohol ether,chloroform and carbon bisulphide.Action of Lead Peroxide on Organic Substances in AlkalineSolution.By M. GLASER and T. MORAWSKI (Jfonatsh. 10 57%-584).-When a mixture of glycerol (2 grams) sodium or potassiumhydroxide (5-10 grams) and lead peroxide ('25 grams) contained inwater (100 c.c.) is gently heated a vigorous evolution of hydrogenoccurs sodium or potassium formato being simultaneously formed,according to the equation C3Hs03 + 3 0 = H2 + SH*COOH.About 97 per cent. of the theoret cal quantity of formic acid isproduced.Under somewhat similar circumstances ethylene glycol also yieIdshydrogen and formic acid (yield about 60 per cent.) G2H6Oz + 2 0 =F. S. K.Ammonia is also withaut action on it at 200".N. 3. &IORQANIC CHEMISTRY. 22H + 2CH,O2.peroxide with polyhydric alcohols in alkaline solution.The,authors intend to study the behaviour of lendG.T. 31.Action of Ammoniacal Cupric Oxide on Carbon Compounds.By C. VINCEPT and DELACHAXAL (Conzpt. rend. 109 615 -616).-Pure sorbite is completely precipitated by ammoniacal cupric oxide,and hence cannot be separated from mmnilol by means of this reagent(compare Guignet Abstr. 1889 1133).Action of Cuprammonium Sulphate on Sorbite. ByC. E. GUIGNET (Coiiipt. rend. 109,645).-Cupr,zmmonium sulphate un-doubtedly precipitates sorbite (preceding abstract) but it precipi-tates mannitol more rapidly and by fractional precipit,ation the authorhas been able repeatedly to separate pure mannitol from liquids whichalso contained sorbite. C.H. l3.C. H. B.Sorbite. By C. VINCEXT and DELACHANAL (Conipt. rend. 109,676-679).-Sorbtte exists in the fruit of all the wsaceSe and espe-cially in pears cherries arid plnms which contain 0.7 to 0 8 per cent.When heated with concentrated hydriodic acid it yields /3-hexyliodide which boils at 16'7" undera pressure of 753 min. ; when heatedwith alcoholic potash i t yields /3-hexylene boiling a t 68.5 under apressure of 735 mm. and acetic and butyric acids when oxidised.90 C.C. of water and 35 grams of red phosphorus were graduallymixcd with 150 grams of iodine in a capacious retort 60 grams ofcrystallised sorbite was added and the mixture gently heated. Anenergetic reaction took place and /3- hexyl iodide was obtained inalmost theoretical quantity no resinous products being formed.Mannitol yields the same /3- hexyl iodide when treated wit,h hydriodicacid.When heated with acetic anhydride and a small quantity of zincchloride sorbite yields a hexacetate C6H,(OAc) which is obtainedas a very thick colourless syrup on washing the crude product withwater dissolving in ether and evaporating the filtered ethereal solu-tions.It follows from these results that the constitution of anhydroussorbite is c6&( OH),.C. H. BTransformation of Cane Sugar .*into Dextrose. By J. BOCK(Che:;i. Cedr. 1889 ii 30 from Oster-ungar. xeit. Zucker. h i d .L w d w . 18 194) .-Cherries which had been preserved by heatingwith a hot concentrated solution of cane-sugar and which hadkept perfectly sound during the winter were allowed to remain forfour or five days in a loosely covered dish when it was found thatthey were coatedwith a white crystalline mass which after separationand recrystallisation proved to be dextrose.Levulose was notfound. The exact circums tames under which this change took placecould not be determined. J. W. L.Raffinose. By BERTHELOT (Conzpt. r e d . 109 548-550).-Theordinary crystals of raflinose are generally regarde.1 as having th28 ABSTRACTS OF UHEMXCAL PAPERS.composition C,,H,,016 + 5H20 but rafliriose from cotton seed sepa-rates from dilute alcohol in the form of a syrup which graduallysolidifies to lamellar crystals which contain 6 mols. H,O and aredifferent from the ordinary crystals.The rotatory power of theirsolution is however the same as that of a solution of the ordinar;)-crystals.The aut,hor confirms Tollens' observat'ion that good beer yeast fer-nients raffinose completely but that weak yeast ferments only aboutone-third even after 48 hours zlthough during the same time it willcompletely ferment eaccharose and glucose. I t seems most probabletlint uiider these conditions raffinose splits up into glucose whichferments and either a saccharose which has a sinall reducing powerlike lactose or a mixture of two glucoses only one of which hasreducing power. C. H. B.By D. LOISEAU(C'ompt. 1-e7atZ. 109 614-615).-111 a sealed paper dated March 5th'1888 the author described the following results Raffinose is com-pletely fermented by low bcer yeast but with high beer yeast onlyabout one-third of the total possible alcohol is formed whilst thesolution has a reducing power equivalent to that of a quantity ofglucose equivalent t o the amount of raEnose which has been fey-mented.It is probable that 2 mols. of raffinose are converted into1 mol. of laevogyrnte glucose which always ferments and twice thequaiitity of a dextrogyrate compoiind which is not fermented by highyeast. Prolonged contact with acids converts this compound intoglucose which is completely fermented by both forms of yeast.This difference in behaviour wit,h raflinose may be used as a meansof distinguishing between high and low yeast (compare Berthelot,preceding abstract). C. H.B.Lactose. By E. W. T. JOKES (Analyst 14 81-83).-Havingobtained some very pure crystallised lactose the author has redeter-mined the specific rotatory power and cupric reduction. For a solu-tion of 5 grams of the crystals C,,H2,0 + H,O in 100 c.c. pi.('-pared hot and of sp. gr. 1018.6 at 15*5" the values obtained are :-Fermentation of Rafhose by Beer Yeast.For C,2H,,01,.60.5"54.6CUO x 0.5723 = C1ZHZZO1I.CuO x 0.6024 = ClzH2z0,1 + H20.The determinations were made by O'Sullivan's method the cuprousoxide being converted iuto cupric oxide by careful ignition andweighed.Lactose is not affected optically or in reducing power by heatingwith citric acid whilst cane sugar is completely inverted. Thecryst,als do not lose their water by 24 11oui*s' heating in a water-oven,bnt if dissolved in water and re-dried the anhydrous sugar is obtainedin a few hours.31. J. SORGANIC CHEMISTRY. 23Methylhydrazine. By G. v. BR~~NING (Annalen 253 5-14).-I n order to prepare methylhydrazine nitrosomethylcarbamide,NO-NMe-CONH is first obtained by adding the theoretical quantity ofsolid sodium nitrite to a solution of methylcarbamide nitrate mixed wif hpowdered ice. Not more tban 50 grams of methylcarbamide nitrateshould be used in each operation. The nitroso-compound forms small,yellow crystalline plates and melts at 123-124" with decomposition.It is soluble in hot water alcohol and ether. The aqueous solutionis decomposed by prolonged boiling. Methylhydrazine is prepared byadding zinc-dust (4 parts) in small quantities to the nitroso-compoundsuspended in water (6 parts) and acetic acid ( 2 i parts) ; the tempe-rature of the mixture must be kept between 5" and 15" and theoperation lasts two to three hours.The product is filtered; thefiltrate acidified with hydrochloric acid concentrated and the thickliquid boiled with 3 pwts of strong hydrochloric acid for 12 hoursin a flask provided with a reflux condenser in order to decompose thecarbamide; the well-cooled liquid is then mixed with an excess ofsodium hydroxide and distilled in a current of steam the distilla-tion being stopped as soon as the distillate ceases to reduce l-'ehling'ssolution. The distillate consists of an aqueous solution of methyl-hydraziiie ammonia and methylamine. The latter compounds areremoved by boiling the solution briskly for eight hours in a flask witha reflux condenser.The methylhydrazine is converted into the acidsulphate which is deposited on the addition of absolute alcohol to theconcentrated solution. The free base is obtained by decomposing aconcentrated solution of the sulphate with sodium hydroxide. Thelast traces of water are removed by treating the base with bariumoxide in sealed tubes at 100". Methylhydrazine NHMe*NH2 is acolourless mobile liquid fuming in damp air. It boils a t 87" (745 mm.),and is miscible in all. proportions with water alcohol and ether. It,strongly red iices Fehling's solution at the ordinary temperature andattacks cork caoutchouc and the skin. The acid s d p h u t e ,N,HJfe,H2SO4 forms long white needles.It melts a t 139.5" anddecomposes a t 182". Unlike the normal sulphate it is insoluble inalcohol. The hydrochloride is precipitated from its alcoholic solutionby ether. The picrate isdeposited from alcohol in yellow needle-shaped crystals and melts a t162" with decomposition. Methylseinicarbazide NH,*CO*N2H,Me,prepared by the action of potassium cyannte on methylhydrazinesulphate. crystallises in prismatic plates and melts at 113". It isfreely soluble in water and alcohol. 1Clethylphenylthiosemicarbazide,NHPh.CS*N,H2Me is formed by the action of phenylthiocarbimide onan aqueous solution of methylhydrazine. This compound is solublein water and alcohol and melts at 143"; the aqueous solution isdecomposed by mineral acids.Dibenzoy Zmethylhydrazine N,HMeBz,,is freely soluble in alcohol and in dilute alkalis ; it melts at 143" andcrystallises in colourless needles. Metlylpicraxide N,H,Me*C,H,(NO,),,is formed when an alcoholic solution of picryl chloride is added to asolution of the base. It crystallises in yellow plates melts a t 171"with decomposit]ion and is freelv soluble in alcohol and ether.OxnZyZd inaethyZhydraci?ze N,H,Me*C,O,*N,H,Me melts at 221" butThe oxalate is soluble in warm alcohol2 4 Al3STHACTS OF CHEMICAL PAPERY.it begins to sublime about 160". It is soluble in alcohol and reducesFehling's solution when gently warmed. The nitroso-derivativecrystallises in plates and melts at 147" with decomposition.Action of Methylhydrazine on Dialdehydes and Diketones.By K.KOHLRAUSCH (A.nii.aZen 253 15-24).-Methylphenylhydr-azine yeacts with berizile a t loo" yielding b e n z i Z e m e t h y l ~ h e ~ ~ ~ ~ Z h ~ d ~ r a x o ~ ~ e COPh.CPIi:K*NMel,h a crystalline substance freely soluble in alcohol,ether and light petroleum. It melts a t 5.5-56" and is completelydecomposed a t 200" ; it is also decomposed by strong hydrochloricacid a t the ordinary temperature. Benzilemethylphenyiosuzone,C,Ph,(N*NMePh) is formed when a mixture of benzile (1 mol.) andmethylphenylhydrazine ('2; niols.) is heated a t 120" ; the crudeproduct is treated with hot dilute sulphuric acid to remove the excessof base and the red crystalline mass which is deposited when themixture cools is purified by recrystallisation from alcohol.The puresubstance forlns yellow needles soluble in ether arid acetone melts a t1 7 ~ - 1 8 ~ " and is decomposed a t 220' ; it is not readily attacked bystrong hydiw hloric acid.Olyoxulrtteti~ylp;pherLyl.,scizolze C,H2(N*NMePh) is deposited as ayellow pi-ecipttat,e when an aqueous solution of glyoxal is added tonil acetic acid solution of niethylpheiiylhydrazine. It melts a t217-218" and is completely decomposed a t 250". This osazone doesuot give a characteristic coloration with ferric chloride.i sfreely soluble in ether.. It melts a t 103-104" and begins to decom-pose a t 2 10'. 1'.2'.3'-MethylplienylacetylilLclole is formed whenmethylpheiiylhydrazone is fused with zinc chloride. The indolemelts a t 136" arid dissolves freelyin glacial acetic acid.It is decom-posed by strong hydrochloric acid a t loo" yielding Degen's1'.2-methylplie1rylindole (Abstr. 1887 149).Acet!jlu,:etonem~t~~~ZplisiLylh~drazirL~ CHi?Ac.CMe:N*NePh is ayeliow oil which can be distilled in a vacuum without decomposition.The compound formed by the action of niethylphenylhydrazine onan excess of acetonylacetone could not be isolated as it undergoesspon tsrieous decomposition losing a molecule of water and changinginto the methylphenylamidodimethylpyrroline described by Knorr(Abstr. 1887 276).a c e t o n y l i c e t o . r L e m ~ t ~ ~ y l ~ ~ ~ e n ~ I l ~ ~ ~ i y d r a % o n e C2H4( CMe:NMePh) isdeposited in the form of an oil which slowly crystallises when anaqueous solution of acet,onylacetone is added to excess of metliyl-phenyl hydrazine dissolved in acetic acid.The crystals melt at143-144!" and dissolve in alcohol ether benzene and light petroleum.The diliydrazone dissolves also in hydrochloric acid ; when this solu-tioii is heated the preceding pyrroline-compound appears to beformed. w. c. w.w. c. w.Be 7 b zoy 1 ace t o ? A e rn e 1 IL y lp h my 1 hg d r az 011 e C H A c * C P h N * N Me P h ,Derivatives of Dichloromaleimide. By G. CIAMICIAN and p.SICBEE (Ber. 22 fL490-2497).-Chlorar1ilidomaleimide (m. p.195-196") is decomposed when heated a.bore its melting- point; it issoluble in ether and hot alcohol but only sparingly in boiling waterORGANIC CEEMISTRP. 25It dissolves in hot dilute sulphuric acid,.yielding a colourless solution,and in alcoholic solutions dimethylanilme produces a reddish-browncoloration.Chloramidomaleinzide C,C102(NH,) :NH is obtained in sinallquantity when dichloromaleirnide is he8 ted under pressure withexcess of alcoholic ammonia. It ci~ystallises from water in goldenneedles melts a t 280" and is soluble in alcohol and ether but insolublein benzene.It dissolves in alkalis with a yellow coloration but thesolution becomes colourless on heating.Dich ZoromuZewnic acid COOH-C,Cl,-CO-NH + H20 prepared byheating dichloromaleiniide (8 grams) with ammonia (80 c.c.) in sealedtubes separates from water in crystalline aggregates melts a t 175"with decomposition and is soluble in ether alcohol and warm water,but insoluble in benzene.The silver salt CaHC1,N0,Ag2 crystallisesin colourless needles and explodes when heated.An orange-red compound CuH,,N,O or C,,H,,N,O2 separates incrystals when dichloromaleimide is heated with phenylhydrazine inalcoholic solution. This substance crystallises from boiling acetoneor glacial acetic acid in orange-red needles melts at 269-271" withdecomposition and is only sparingly soluble i n most ordinary solvents.It dissolves in concentrated sulphuric acid with an intense redcoloration and on adding water an orange-red flocculent substance isprecipitated. P. S. K.BJ- E. BAUMANN and E. F n o m ( B e y . 22,2600-26~9).-P-Trithioaldel~yde (Klinper Abstr. 1879 780) is formedwhen hydrogen sulphide is passed through a mixture of aldehyde(1 part) with alcohol previously saturated with hydrogen chloride(3 parts) ; crystals soon separate and the whole becomes solid.Theproduct is washed with water and crystallised from alcohol fromwhich it separates in Iong needles melting a t 125-126". A smallamount of a-trithioaldehyde melting a t 101-102" is also formed aswell as a few crystals of a substance melting a t 76" possibly Marck-wald's y-derivative (Abstr. 1886 865).a-Trithioaldehyde is obtained as the chief product when eqiral partsof aldehyde water and strong hydrochloric acid are used. It crlstal-lises from acetone ill splendid prisms an inch long. The /%compoundis also formed.p-'l'hiobenzaldehyde and ythiobenzaldehyde are formed when hydro-gen sulphide is passed through a mixture of benzaldeb yde and alcoholichydrogen chloride.The product is boiled with benzene until almostall is dissolved; on cooling the @compound separates in crystalshaving the ComposiLion sc7H6s + c6H6 (not C7H,S 4- CsHc Klinger) ;this gives up all the benzene a t ItjO" and a portion when kept a t theordinary temperature for a long time.y-T~~iobenzuZdehy~e C7H6S crystallises from Senzene in small,pointed needles melting a t 166-167". The crystals contain nobenzene of crystallisation. When the solution in benzene is treatedwith iodine the whole solidifies after some time being converted intothe p-derivative.When a - or P-trithioaldehyds is oxidised with potassium perman-Thioaldehydes26 ABSTRACTS OF CHEXICAL PAPERS.ganate they both give as end-product a trisdphone C6Rl2S3O6,together with products containing less oxygen (compare Guareschi,Abstr.1884 294). This forms slender needles softens at 340",becoming yellow and sublimes a t a higher temperature without melt-ing. It is almost insoluble in water very sparingly soluble in alcohol,ether chloroform and benzene more soluble in hot acetic acid; italso dissolves readily in strong nitric or sulphuric acid but is pre-cipitated by water. Alkalis dissolve it readily and it can be crystal-lised from ammonia and alkaline carbonates. The constitution oftrithioaldehyde sulphone is S02<CHMe.SO:>CHMe. CHMe* S 0 When analcoholic alkaline solution of the substance is treated with methyliodide the compound CgH18S3O6 melting at 302" is formed.I n asimilar manner ethyl- allyl- and benzyl-groups may be added.N. H. M.Thio-derivatives of Ketones. By E. BAUMANN and E. FROMX( B e r . 22 2.592-2599 ; compare Abstr. 1889 852).-ThioacetoneCSMe is formed as a readily volatile oil in the preparation of tri-thioacetone and tetrathioacetone (Zoc. cit.) but was not isolated owingto it's instability and the difficulty of separating it from trithioacetone.It is also produced together with ethyl sulpliide and other sulphur-derivatives when acetone-ethylmercaptole CMe,(SEt) is heatedabove 160". Owing to the very unpleasant odour of the compound,which is stronger tIhan that of any other known substance thesmallest traces of it being sufficient to infect whole districts the studyof the compound was not continued.Trithioacetone is decomposed by strong nitric acid with explosiveviolence.A further examination of the sulphone obtained by oxidising tri-thioacetone with potassium permanganate (loo.cit.) showed that thiscould be separated by crystallisation from alcohol inho two substances.The more sparingly soluble compound triacetnnetrisulphone C9H,,S306,crystallises from glacial acetic acid in slender needles which melt at.302" (uncorr.) and sublime readily. The more readily soluble com-pound CsHl8SsO4 is probably tritlzioacetonedisu~lio~e ; it melts at208".Acetonetrisulphone is not changed by acids and alkalis; it dis-solves in strong acids and is precipitated by water unchanged.Boiling fuming nitric acid has no action on it.Its constitution isprobably CMe2<S02,.CMe:>S02.The compound CgHl,S304 dissolves in bromine pielding an unstablebromine-derivative which readily decomposes with evolution of hy-drogen bromide. When gently heated with fuming nitric acid,the compound is oxidised with formation of much sulphuric acid.Probably the substance has the constitution S<C&e:,so:>CMe2.SO *CMeCMe -SON. H. M.The Introduction of Acid Radicles into Ketone Molecules.By L. CLAISEN (BUZZ. Xoc. Chin&. [S] 1 496-510 ; compare Abstr.ORGANIC CHEMISTRY. 271888 666 671 676 and 1889 5S4 619 850).-B re'sume' of theauthor's already published work on this subject concluding with adiscussion as to the theory of the reactions.Substituted Acrylic and Propiolic Acids.By C. F. MARERYand A. W. S w r H (Ber. 22 2659-2660) .-When a,!%dichloracrylicacid is dissolved in carbon bisulphidc and chlorine passed throughthe solution whilst it is exposed to sunlight tetrachloroproyiolzic acid,C,HCl,-COOH gradually crystallisea out. It forms large rhombicprisms is soluble in carbon bisulphide chloroform and water andmelts a t 76". Its barium salt crystallises in prisms ; its ca1ciu.m saltin needles; its potassium salt in plates. Its silver salt is very un-stable,When ap-dichloracrylic acid is heated with hydrobromic acid inclosed tubes a t 110-120" bromodichloI.opro~ionic acid is formed. It issoluble in water and boiling carbon bisulpliide ci-ystallises in prisms,and melts at 75-76'.When an aqueous solution of bromopropiolic acid is mixed withhypochlorous acid and left.in the dark chlorobro.ulzhydroxyacrzJlic acid,C,(OH)ClBr.COOH is formed. It is easily soluble in boiling wa.ter,is crystalline and melts a t 104-105". I t s silaer salt is soluble innitric acid and is very unstable in aqueous solution.T. G. N.L. T. T.Action of Phosphorus Pentachloride on Chloralide. Tetra-chlorethylidene Trichlorolactate. By R. ANSCH~TZ and A. R.HASLAM (Annalen 253 121-131).-The compound of the composi-tion C,HC1,O3 which the authors obtained by the action of phos-phorus pentachloride on chloralide (Abstr. 1887 9151 proves to bethe tetrachlorethylidene trichlorolactate. It boils a t 276" withoutdecomposition. Nethyl and ethyl alcohol act on this compound atthe ordinary temperature yielding hydrogen chloride and the ethylor methyl salts of trichloracetic and trichlorolactic acids.Normalpropyl and isobutyl alcohols act less energetically than ethyl alcohol.Normalpropyl trichlorolactcrte boils at 115-11 7" under 12 mm. pressure,and at 248-250" under the ordinary atmospheric pressure. Itssp. gr. a t 20° compared with water a t 4" is 1.51628. Isobutyl tri-chZorolactate boils at 111-i12" under 12 mm. pressnre and at236-238" under the normal atmospheric pressure. I t s sp. gr. at 20"is 1.53216. The chloride is slowly decomposed by water yieldingtrichloracetic and trichlorolactic acids. These results indicate thatthe constitution of the chloride is represented by the formulaCC;l,*y (OH)coo- >CC1.CCl,."w. c.w.Derivatives of Ethyl Acetoacetate. By R. SCH~~NBRODT(AwnaZea 253 168-205).-Ethyl monochlor~~cetoacetate is formedby passing chlorine into ethyl cupracetoacetate suspended in chloro-form until the green colour of the compound changes to grey. Byt h e prolonged action of chlorine a dichloro-substit'ution-product isobtained. Analogous resalts are produced when bromine is usedinstead of chlorine ; the sthylic salts of mono- and di-bromacetoaceti28 ABSTRACTS OF CHEMICAL PAPERS.acid have been described by Duisberg (Annalen 213 152 and 143).E t h y l iodacetoacetate prepared by the action of iodine on ethyl cupr-acetoacetate is a yellow oil miscible with ether and alcohol. Thealcoholic solution gives a blood-red coloration with ferric chloride.The compound is unstable.I t decomposes at 25" in a vacuum and itssp. gr. at 1P" is 1.7053 compared with water at the same temperature.It is converted into ethyl monochloracetoacetate by the action ofsilver chloride but with silver cyanide it yields hydrogen cyanide andethyl succinosuccinate. The product of the action of silver nitrite onethyl iodacetoacetnte is a yellvw oil probably ethyl nitroacetoacetate.This substance gives an intense blood-red coloration with ferricchloride and strong snlphuric acid. It does noC yield an amido-com-pound on reduction with tin and hydrochloric acid nor does it form asolid compou'nd with hydroxylamine. It combines with phenylhydr-azine yieldingphenylmethylisonitrosopyrnzolone [ 1 3 4 51 describedby Knorr (AWr. 1887,602).The same compound is formed by theaction of phenylhydrazine on the ethylic salt of monochlor- brom-,or iod-acetate. The reaction may be represented as follows CsFi,C103Bender (Abstr. 1888 53) has shown that in the ethereal solution,phenylhydrazine and ethyl monochloracetoacetate yield the ethylicsalt of p-phenyl azocrotonate. The author confirms the accuracy of thisobservation.Ethyl sodacetoacetate reacts with ethyl iodacetoacetate yieldingethyl diwetosuccinate. Metallic silver eliminates the iodine fromethyl iodacetoacetate and forms the ethyl diacetofumarate describedby Just (Abstr. 1886 141). Ethyl thiacetoacetate first prepared byBuchka (Abshr. 188.5 1200) is formed by boiling sulphur in a solu-tion of ethyl cupracetoacetate in benzene. I n the presence of alcohol,phosphorus acts on ethyl cupracetoacetate forming ethyl acetoacetateand triethyl phosphite.Arsenic trichloride is reduced by the coppercompound arsenic being liberated and ethyl mnochlorncetoacetateformed. Ethyl cupracetoacetate is not attacked by cyanogen. but nitro-gen peroxide acts on it with formation of the nitro-compound whichis produced by the action of silvei. nitrite on ethyl iodoacetoacetate.Attempts to displace a hydrogematom by copper in ethyl mrth-ace toacetate were unsuccessful. w. c. w.+ SNHPh*NHZ = CloHgN302 + 2NHzPh + NHdC1 + C,H,*OH.Ethyl Thiacetoacetate. By I(. BUCHKA and C. SPRAGUE (Bey.,22 2.541-2556 ; compare Ruchka Abstr.1885 1200 ; Delisle,Abstr. 1887 915 ; and Schonbrodt preceding abstract) .-Ethyl thi-acetoacetate is best prepared by Delisle's method; 100 grams ofethyl acetoacetate yield 60-70 grams of pure ethyl thiacetoacetate.Molecular weight determiiiations by Raoult's method in glacial aceticacid solution showd that the molecular formnla was C,,H,,O,S.It melts at about 76" b u t the melting point observed depends to aconsiderable extent on tlie rapidity of heating and on other conditions.The sodium-derivative C,,H,,O,SN& is formed when ethyl thiaceto-acet,ate is treated with sodium in ethereal solution.When ethyl thiacetoacetate is treated with phenylhydrazine,hydrogen sulphide is evolved and phenylmethylpyrazolonsketvORGANIC CHEMISTRY. 29phenyl hydrazon e ( pheny lme thyl p yrazolonenzobenzei~e) melting at156O identical with the compound obtained by K n o x (Abstr.1887,601) is formed together with a yellow substance which is insoluble inall ordinary neutral solvents. The compound obtained by Schon-brodt (Zoc. cit.) by treating ethyl chloro- bronio- or iodo-acetoacetatewith phenylhydrazine is not phenylrnethylisonitrosopyrazolone asstated by him but is identical with the phenylmethylpyrazolone-ketophenylhydrazone referred to above.The yellow compound which is obtained together with phenyl-methg1pyrazoloncketophenylhydrazone (see above) when ethyl thi-acetoacetate is treated with phenylhydrazine is decomposed whenheated but without melting ; it dissolves in alkalis and is reprecipi-tated on adding acids.It seems to have the composition C,,H,N,Sc) ;when heated with phenplhydraeine it is converted into phenyl-methyl pyrazoloneketophenyl hydrazone with evolution of hydrogensulphide small quantities of di-phenylmethylpyrazolone being alsoformed.Para f olylmethy Ipyrazoloneketoparatolylhydrazone,is formed w'hen et'hyl thiacetoacetate is Created wiGth qaratalylhydr-azine ; it crystallises from chlorofrom in orange needles melting a t216-217". When excess of the hydrazine is employed in the abovereaction a compound free from sul i)hur and probably correspondingwith di-phenylmethylpyrazolone is also obtained. If only a small quan-tity of the hydrazine is used a sulphur compound which is onlysoluble in alkalis is formed ; .this substance is converted into tolyl-methylpyrazoloneketotolylhydraaone (im.p. 216-21 7") when heatedwith paratolylhydrazine and when heated with phenylhydmzine ityields a compound. probably tol.ylmethy1pyrazoloneketophenylhydr-azone which crystnllises i n rcd needles melting a t 1.86".E thyl %hiacetoacetate combines with a-naphthylhydrazine yieldingsimilar compounds. I?. S. K.Dithioxamide (Cyanogen DimLphydrate). By J. FORM~NEK(Ber. 22 2655-26569. When a saturated solution of cupric sul-phate is treatod with ammonia untiltthe precipitate first formed is justredissolved potassium cyanide added in quantity just sufficient todischarge the blue colonr and then a rapid stream of hydrogen chloridepassed through the solu+ion the latter becomes first yellow and thenred; and if it is kept well cooled small red crystals of the formulaNH,-CS*CS*NH gradually separate out.L. T. T.Hydroxycitraconic Acid and its Derivatives. By P. MELIKOFFand M. FELDMANN (Annalen 253,87-95 j.-In dilute solutions hypo-uhlorous acid unites with cibraconic acid to form chlorocitramalicacid which has been described by Morawski (this Journ. 1875 142),and by Gottlieb (Annalen 160,101 j. The acid prepared by Gottlieb'sprocess melts a t 139". It is converted into Morawski's hydroxycitra-conic acid by the addition of potessium hydroxide in alcoholic solution30 ABSTRACTS OF CHEMTCAL PAPERS.The precipitate of pot,assium chloride and hydroxycitrctconate i swashed with alcohol and ether. It is khen dissolved i n water thehydroxy-acid liberated by sulphuric acid and extracted with ether.The acid melts a t 162" as stated by Scherks (Abstr.1885,513). Theethyl salt C,EI,O(COOEt) has the sp. gr. of 1.1376 at 0" and 1.1167at 22" compared with water at the same temperatures.Hydroxycitraconic acid dissolves in strong hydrochloric acid a t 0" ;and ether extracts from this solution a monochlorinated hydroxy-acid,CUOH*CH( OH)*CClMe*COOH crystallising in rhombic plates whichis an isomeride of the acid formed by the union of hypochlorons acidand citraconic acid COOH.CMe(OH)*CHCl*COOH. This acidmelts a t 162" and forms unstable salts. The compound which isformed by the addition of hydrobromic acid to hydroxycitraconic acidhas already been described by Scherks (Zoc.cit.). Hydroxycit,raconicacid is a glycidic acid as it is converted into amidocitramalic acidby the action of alcoholic ammonia at 100". The amido-acid formsshort prisms which seem to belong to the monoclinic system; itreddens litmus and decomposes carbonates. 100 C.C. of water at 18"dissolve 31 grams of the acid. It is almost insoluble in hot alcohol.The calcium and barium salts are amorphous. The hjdrochloride,OH.CsH,( NH,) (COOH),,HCI forms transparent prisms soluble inwater and alcohol. It melts a t 100" with decomposition. w. c . w.Acetonediacetic or Hydrochelidonic Acid. By J. VOLHARD(AnnuZen 253,206-236) .-The dilsctone of discetic acid is preparedby maintaining succinic acid in a state of slow ebullition for six hours.When a small quantity of the contents of the retort no longersolidifies on cooling but remains as a greasy mass the operation iscomplete.The crude product is repeatedly extracted with boilingchloroform ; on cooling succinic anhydride is deposited in crystals andthe lactone remains in solution. The chloroform is removed bydistillation the residue dissolved in water and the lactone is ngaiiiextracted from this aqueous solution by chloroforni. The lactoneforms transp3rent rhombic prisms u b c = 0.3649 1 0.9816 freelysoluble in chloroform acetone ether alcohol benzene and ethylacetate. It melts a t 75" and boils between 200 and 205"under 15 mm.pressure. The lactone dissolves in alkalis and in strong hydrochloric orhydrobromic acid yielding acetonediacetic acid CO( CH,*CH,*COOH),,which is identical with the hgdrochelidoiiic acid of Liebenand Haitinger( Monatsh. 5 353) and with Marckmald's propiondicarboxylic acid(Abstr.1888 678)The acid forms rhombic plates soluble in hot water and in alcohol.It melts a t 143O and decomposes at a higher temperature. Thenormal salts of the alkali metals are very soluble in water and do notcr-j-st:~llise well. The acid potassium sodium and ammonium saltsare anhydrous. The barium salt crjstallises with 2 and with 2; mols.H,O. The manganese salt C,H,MnO + fLH,O forms pale pink needles.The zinc and cadmium salts crjstallise in six-sided plates containing2 mols. H20. The silver salt C7H8Ag?03 is crjstalline and insoluble iORUANIC CHEMXSTRY. 31water.The dimethyl salt melts at 56' and boils with decompositionat 276-277" (uncorr.). The sp. gr. of the diethyl salt is 1.0862 at 13".Acetic chloride acetic anhydride and phosphoric anhydride convertthe acid into the lactone. The phenylhgdrazide of acetonediacetic acidmelts at 107 -108". The phenylhydrazide of the dimethyl salt meltsa t 88-90' and dissolves in ether benzene and hot alcohol. Thecorresponding diethyl compound melts at 67". The oximeof the acidcrystallises in prisms and melts with decomposition at 129". Theoximes of the dimethyl and diethyl salts form needles and melt at 52"and 38' respectively. w. c. w.Alkyl-derivatives of Methyluracil and Nitrourscil. BJ- R.BEHREKD (Annalen 253,65-68).-Ethyl bromide does not react w i t hfree methyluracil but it acts on potassium methylurscil forming mono-methyluracil and dimethyluracil.I t is probable that monethylmethyl-uracil is first formed. A portion of the monethylmethyluracil reactswith potassium methyluracil formingpotassium monethylmethyluracil.This is attacked by ethyl bromide yielding diethylmethyluracil.In a previous communication the author stated that methyl iodideacts on potassium methyluracil yielding trimethyluracil and thedihydride of methyluracil ; he now finds that the supposed dihydrideis identical with the dimethyluracil described by Hoffmann (nextAbstract). w. c. w.Alkyl-derivatives of Methyluracil. By J. HOFFMANN (Annalen,253 68-77).-Ethyl methyluracil and diethylmethyluracil areformed by the action of ethyl bromide or iodide (3 mols.) on potassiummethyluracil (1 mol.) in sealed tubes at 150; the excess of ethylbromide or iodide is removed from the crude product by distillation,the residue is dissolved in water and the aqueous solution treatedwith chloroform.The chloroform extract is then dried and distilled andthe residue dissolved in boiling alcohol ; on cooling crystals of ethyl-methyluracil are deposited. The mother-liquor contains monethyl- ariddiethyl-methyluracil. The former is deposited as a crystalline crust,but the diethyl-derivative can only be isolated by dropping a crystalof diethylmethyluracil into the mother-liquor when crystallisationtakes place. fithylmethyZuraci1 is deposited from ethyl bromide inprisms and from alcohol in needles.It is freely soluble in chloroformand in ethyl bromide and is much more soluble in hot than in coldalcohol. A crystalline silver salt C,H,E tAgN20z is obtained whensilver nitrate is added in sufficient quantity to produce a permanentturbidity t o a solution of ethylmethyluracil in a 10 per cent. solutionof potassium hydr0xid.e. Diethylnaetl/y Zz~racil crystallises in rhombicplates and melts at 52-53" dissolves freely in chloroform alcohol,ether and water and is decomposed by potassium hydroxide at theordinary temperature with liberation of ethylamine. Methjl bromideacts on potassium methyluracil at 140" forming dimethyluracil and tri-methyluracil. !Z'~*imethylz~raciZ melts at lo>" crystallises in rbombicplates and is freely soluble in chloroform alcohol and water aridsparingly soluble i n ether.Di~niethyluracii is insoluble in ether but ca32 ABSTRACTS OF CHEMICAL PAPERS.be reerystallised from hot alcohol. Methyluracil di-iodide C,H,N,O,I isformed by the action of iodine dissolved in strong hydriodic acid onmethyluracil. It is an unstable compound dissolvinq with decompo-sition in water alcohol and chloroform. The di-iodide furms deepNitrouracil-derivatives. By M. LEHMANN (Annalen 253,77-87).-Meth~lZnifrozcracil C,H,N30 + H20 is formed by theaction of methyl iodide on potassium nitrolnracil in sealed tubes a t140". It crystallises in long needles and is soluble in hot water.100 C.C. of water a t 20" dissolve 0.714 gram and 100 C.C. of alcohola t 17" dissolve 0.115 gram of the substance.It is less soluble inether chlorofsm benzene and methyl iodide than in water. Thepotassium silver and barium salts are crystalline; the silver andbarium salts me almost insoluble in cold water. Methylisobarbitiiricacid C5H6N203 is deposited in crystals when methplnitrouracil isrediiced by tin and hydrochloric acid ; the mother-liquor containsmethylamidoucacil in small quantiky. A neu,tral solution of methyl-amidouracil hydrochloride turns red on the addition of potassiumcyanate ; the d o u r is destroyed by hydrochioric acid and methylhy-droxyxanthine C6H8N403 is deposited a s a yellow crystalline powder.100 C.C. of water a t 16" dissolve .0*16 gram of rnethylhydroxyxan-thine. Methylnitrouracil i s decomposed by baryta-water a t 160-1 70",with liberation of methylamine ; dimethylnitrouracil under similartreatment yields dimethylamine.Dimethylnitrouracil melts at 154.5"and is deposited from hot water in needles eontairling 9 mol. H20.It does not unite with bases to form salts. The constitntion ofmethyl- and dimethyl-nitrouracil can be represented by the formulae,C o < ~ ~ e - ~ ~ NH'cH >C*NO and C O < ~ ~ ~ ~ ~ > C . S O . Methyhitro-methyluracil prepared by the action of methyl iodide on potassiumnitromethyluracil crystallises in needles and melts a t 149". Itunites with bases forming c r p t a lline salts. E t h y7nit rouracil,C,H,N304 + H,O forms silky needles and melts at 194.5 ; it is de-posited from alcohol in anhydrous crystals and is soluble in hotwater ether chloroform benzene and ethyl bromide.The potassiumand silver salts crystalhe in needles.Ethylisobarbituric acid C,H,N,O melts at 250" but begins todecompose at 230". It is soluble m hot but almost insoluble in coldviolet crystals. w. c. w.water. Ethylhdroz yxanthine crystallises in prisms which turn pinkon exposure to the air. Etl~lllrnethy Znitrouracil CO<N~e.CO>C.N02 NFtCHcrystallises from hot water in needles containing 1 mol. H,O. Thecrystals effloresce ; it melts at 109". itl;.thyleth~lnit,.ouracil,CO<NEt.Co >C*SO melts at 73" and crystallises in rhonibohedra,containing 1 mol. H20. The substance becomes anhydrous a t go',and remains liquid a t the ordinary temperature but solidifies on theaddition of water.NMe-CHI t is freely soluble in alcohol and ether.w. c. wORGANIC CHEMISTRY. 33FUCUSO~. By MAQUENNE (Compt. rend. 109 571-573).-DriedFucus vesiculosus was heated in an oil-bath at 160" with 4.5 parts ofsulphuric acid of 20" B and the product after neutralisntion wasdistilled and fractionated. Small quantities of water and acetonewere obtained together with two fractions boiling a t 162-163" and185-187" respectively. The fraction 162-163" consists of pure fur-furaldehyde the fraction 185 - 187" is methyIfurf.~raldehyde aliquid of sp. gr. 1.105 at 15". With ammonia it yields a crystallineproduct closely resembling furfuramide ; its hydrazone is an oilyliquid ; with silver oxide i t yields methylpyromucic acid melting at108-109".When treated with hydriodic acid it resinifies but doesnot carbonise and does not become green ; the product yields iodo-form when mixed with potassium hydroxide. With acetic anhydridein presence of fused sodium acetate it yields methylfurfuracrylicacid melting a t 157" and crystallising from boiling water or alcoholin small white needles which retain aboilt Q mol. H20. If methylfur-furaldehyde is heated with strong hydrochloric acid it becomes green,a reaction which Stenhouse observed with fucusol. The followingreaction serves to detect methylfurfuraldehyde in presence of a largeproportion of furfuraldehyde. One drop of the liquid is dissolved i n5-6 C.C. of alcohol of 90" and 1 C.C. of sulphuric acid of 60" is addedslowly without agitation; a green coloration appears at the junctionof the two liquids.The coloration persists even after agitation ifthe methylfurfuraldehyde is abundant but changes to grey if furfur-aldehyde is in excess. The reaction is similai- to that given by heptine(or its oxidation-products) from perseitol.This methylfurfuraldehyde is identical with that obtained by Hillfrom wood tar.Fucnsol is not a distinct compound as Stenhouse supposed but isa mixture of furfuraldehyde with about. 10 per cent. of methylfurfur-aldehyde. C. H. B.Relation between Sugars and Furfuran-derivatives. ByMAQUENNE (Compt. rend. 109 603-606) .-Methylfnrfnraldehydefrom Fucus (preceding Abstr.) yields acetic acid on oxidation andhence contains a terminal methyl-group and is one of the threeisomerides which contain the methyl-group in the position 2 3 or 4with respect to the aldehyde group.It has the same relation t80 isodul-citol or rliamnope C6HI2O6 m furfuraldehyde has to arabinose C5H,,05.Crystallised isodulcitol distilled with four times its weight of sul-phuric acid of 15 to 20" B yields a small quantity of acetone togetberwith pure methylfurfuraldehyde identicltl with that from Fucus cesi-cutosus or wood tar but no furfuraldehyde is obtained. Fischerand Tafel have shown that isodulcitol is an aldehyde derived fromnormal bexane and according to Herzig it yields acetic acid on oxida-tion and hence contains a terminal methyl-group. Its conversioninto methylfurfuraldehyde would involve the union of the chains2 and 5 by means of an atom of oxygen the methyl-group occupyingthe Position 4.thus :- AVOL. LVIII. L34 ABSTRACTS OF OHEMICAL PAPERS.Since furfuraldehyde is obtained from arabinose by dehydration,it follows that isodulcitol is w-methylarabinose a relation which hasoften been suggested but has never previously been established,The yield of methylfurfuraldehyde from isodulcitol is small but itsuffices to detect the isodulcitol in substances in which its presence isnot recognised by the usual methods and i t has been detected inseveral plants in which it was not known to exist. Since Fucus vesicu-losus yields methylf urfurddehyde (Zoc. cit.) it would seem that isodul-citol exists in marine plants.Selenium and Oxygen-derivatives in the Benzene Series.By C.CHABRII~ (Compt. rend. 109 568-570).-The action of nitricacid on phenyl eelenide (Abstr. 1889 1167) yields nitro-derivatives ;potassium permanganate or chromic acid yields indefinite oxidation-products ; hydrogen peroxide and hydrochloric acid yield compoundsin which oxygen has been introduced into the phenyl-group.The action of selenious chloride SeOCI on benzene in presence ofaluminium chloride yields two compounds according to the proportionsof the reacting bodies. Diphenylselenone SeOPh is an amber-yellowliquid which boils at 230" under a pressure of 65 mm. ; sp. gr. a t19.6 = 1.48. The other product PhSeO*C6HICl crystallises in white,hexagonal prismatic lamellse with a fatty lustre ; it melts at 94" boilsat 230" under a pressure of a few millimetres is insoluble in water,but dissolves in alcohol and is attacked by cold nitric acid.Diphenylselenine when treated with bromine water yields the corn-pound SeO( C6H4Br).? which crystallises from alcohol in modifiedrhombic prisms melting a t 1'20".When mixed with hydrogenperoxide and hydrochloric acid and treated with a current ofair diphenylselenine yields the compound SeO (c6HIc1)2 orPh SeO*C6H,C12 which crystallises from boiling alcohol in small,white prisms melts at 159" and is not attacked by cold nitricacid.The action of the compound Se(OH)&I2 on benzene in presence ofaluminium chloride yields diphenylselenine and selenophenol.Action of Phosphorus Trichloride on Phenol. By R.ANSCH~TZ and W. 0.EMERY (Amer. C'hem. J. 11. 379-38i).-By theaction of phosphorus trichloride on phenol the following three com-pounds were formed (compare Noack Abstr. 1883 735) and wereseparated by distillation under greatly diminished pressure :-Phenylphosphoryl dichloride PCl,-OPh ; sp. gr. 1.35412 at 20" (waterat 4" = I) ; boiling a t 90' under 11 mm. pressure ; diphenyZphosphoryZchloride PCl(OPh) ; sp. gr. 1,24378 a t 20" (water at 4" = 1) ; boil-ing at 172" under 11 mm. pressure ; tripheriyl p h o p h i t e P(OPh) ;sp. gr. 1.18428 at 20" (water at 4" = 1) ; boiling at 220" under 11 mm.pressure.The action of phosphorus pentachloride on the preceding com-pounds was investigated. In the cold no action takes place; at100" crystalline compounds are formed soluble in chloroform andcarbon tetrachloride.Chlorine additive-products were almost cer-tainty formed but they could not be isolated ; they were however,C. H. B.C. H. BORGANIC CHEMISTRY. 35obtained by passing dry chlorine over solutions of the phosphorouscompounds in dry ether. Phenylphosphoryl tetrachloride PCl,*OPh,prepared from chlorine and phenylphosphoryl dicbloride forms smallplates soluble in chloroform and carbon tetrachloride insoluble inether ; it is deliquescent and is decomposed by water normal phenylpbosphate being formed. With sulphurous anhydride i t behaves likethe corresponding phosphenyl compound giving thionyl chloride andthe oxychloride POCl,-OPh boiling a t 121-122" under 11 mm.pressure. Diphenylphosphoryl trichloride PCl,(OPIi) formed fromchlorine and diphenylphosphoryl chloride is a yellow oil solidifyingto minute crystals soluble in chloroform insoluble in ether; it easilytlecomposes when heated and also when treated with water in whichcase phenyl phosphate is formed.Tt.~p~ie~zyll?li~~pla~j~yZ dichluride,PC1,( OPh) prepared from chlorine and phenyl phosphite solidifirsa t a very low temperature ; when treated with water it decomposesinto phenyl phosphate and hydrochloric acid.By the addition of dry bromine to etliereal solutions of the monn-and di-chlorides the compounds PC12Br2*OPh and PClBr,(OPh),were obtained ; these are very unstable substances.Phenylphosphrvl thiochloride PSC12*OPh was obtained by heatingphenylphosphoryl dichloride with sulphur at 190" ; it has a sp.gr. of1.40393 at 20" (water at 4" = I) boils at l19-i20° under 11 mm.pressure and is a highly refractive liquid soluble in ether and chloro-form. DipTien!il~jhosplioryl thiochzoride PSC1( OPh) prepared fromdiphenylphosphoryl chloride and sulphur heated aat 190" ; melts a t63-64" and boils at 194" under 11 mm. pressure. Attempts toobtain the preceding two compounds by heating togeiher phenol andphosphorus thiochloride were unsuccessful hydrogen chloride andnormal phenyl phosphate being formed. Tr+hen yl thiophosphate,PS( OPh) was obtained by heating phenyl phosphite with sulphur at190" ; it forms crystalline needles melting at 49-50" and boiling at245" under 11 mmpressure; sp. gr. = 1.24411 at 20" (water at 4" = I).It is found that these thio-compounds have very nearly the samemelting points and boiling points as the correspondiiig oxy-com-pounds.The existence of the compound PC14*OPh leads to the followingview of the action of phosphorus pentachloride on hydroxj-com-pounds :-R-OH + PC1 = HC1 + RO*PC14 and RO-YCI = POCl + RC1.C. B.B.Apiole. By G. CIAMICIAN and P. SILBER (Bey. 22 2482-2490;compare Abstr. 1888 Ilc;O).-The authors give the name apionole tothe tetrahydroxybenzene which forms the basis of apiole ; the dimethylether of tetrahydroxybenzene is therefore dimethylapionole and'' apiorie " is dimethylmetbyleneapionole,Dimethylapionole C6Hz(0H),(OMe)2 is obtained when apiolic acid(2.5 grams) is heated at 180" for 4 to 6 hours with potash (8 gramP)and alcohol (10 c.c.).l uaqueous solutions ferrous sulphate produces after some time a bluecoloration lead acetate a gelatinous precipitate ai:d silver nitid e aIt melts a t 105-106" and boils at 298".d 36 ABSTRACTS OF CHEMICAL PAPERS.crystalline precipitate which immediately turns black. It dissolvesin concen hated sulphuric acid yielding a yellow solution whichquickly turns red and on warming becomes violet. The diacetyl-derivative C6H2(OMe),( crystallises from alcohol melts a t144' and is soluble in ether warm alcohol and glacial acetic acid,but only sparingly in hot and insoluble in cold water. It dissolvesin warm concentrated sulphuric acid yielding a colourless solution,which turns yellow and then brown on heating more strongly.Tetramethy lapioriole C6H2 ( OMe)4 prepared by treating the di-methyl-derivative with methyl iodide in methyl alcoholic potashsolution crystallises from hot water in colourless needles melts at 81",and is readily soluble in alcohol ether benzene acetone and aceticacid but only sparingly in water.It dissolves in concentrated sul-phuric acid yielding a colourless solution which turns brownish-redon warming and in concentrated nitric acid with a yellow coloration.It is not acted on by hydrochloric acid a t loo" but at higher tem-peratures it is decomposed with evolution of methyl chloride.Apioneacry Eic acid CH2:O2:C6H( OMe) ,*CH C H *C 0 0 H prepared byboiling apiolaldehyde with acetic anhydride and sodium acetate crystal-lisea from hot alcohol in small jellow needles melts at 196" and isreadily soluble in hot glacial acetic acid benzene and alcohol but onlysparingly in ether and hot water and almost insoluble in cold water. Itdissolves i n concentrated sulphuric acid with a yellow coloration thesolution turning brown on warming.The sodium salt crystallises inmicroscopic needles and is readily soluble in water; in an aqueoussolution of the sodium salt lead acetate barium chloride calciumchloride or zinc sulphate produces a colourless nickel nitrate or coppersulphate a green cobalt nitrate a red silver nitrate a light yellow,and ferric chloride a reddish-brown precipitate.Apionecrotonic acid C Hz 0, CGH (OMe),*C H C Me-C 0 OH preparedfrom apiolaldehy de in like manner crystallises from alcohol in lightyellow needles melts at 209" and is almost insoluble in water butsoluble in ether hot alcohol and hot acetic acid.It dissolves in cnn-centrated sulphuric acid with a yellow coloration the solution turningbluish-green on warming. The sodium salt is readily soluble inwater. The calcizim salt (C13H,306)2Ca + 5H20 crystallises from hotwater in broad colourless needles and loses iCs water a t 100". Thesilver salt C13H13@6Ag is colourless and very sparingly soluble inwater. In aqueous solutions of the sodium saIt barium chloFide,magnesium sulphate or zinc sulphate produces a white. crystallineprecipitate arid solutions of copper nickel cobalt and ferric salt8 alsogive a precipitation. When the calcium salt is distilled with lime asmall quantity of a crystalline compound melting a t 83" is obtained.When calcium apiolate is distilled with lime it yields a mixture ofsubstances some of which are volatile with steam ; the non-volatileresidue crystallises from alcohol in needles melts a t 71-72' andseems to hare the composition C,H,O,.The nitro-compound (m.p. 117-118*) previously described (loc.cit.) and obtained by treating apiolic acid with nitric acid of sp. gr.1.4 in glacial acetic acid solution has the composition C,H,N,O notC9H8N20 as previously given arid is probably dinitrapioneORGANIC CHEIIJSTRY. 37The nitro-compound (m. p. 116O) prepared from isapiole byGinsberg (Abstr. 18F8 722) is probably identical with dinit'rapione,and the compound (m.p. 137-138") obtained by the authors fromapiolaldehyde is probably st nitro-derivative of apiolaldehyde.Chlorination and Bromination of Aniline Orthotoluidine ,and Paratoluidine in presence of Excess of a Mineral Acid.By R. HAFNER (Ber. 22 2524+-2541).-When chlorine is passedinto an ice-cold solution of aniline in excess of 97 per cent. sul-phuric acid for about 18 hours almost the whole of the anilineremains unchanged only small quantities of parachloraniline beingformed. Under the same conditions but employing 65 per cent. sul-phuric acid symmetrical trichloraniline (rn. p. 77") traces of a com-pound melting a t 63-64" probably trichlorophenol (m. p. 67-68'),and considerable quantities of resinous products are formed but alarge quantity of aniline remains unchanged.Chlorine acts energetic-ally on aniline in 40 per cent. ice-cold sulphuric acid solution ; theprincipal product is trichloraniline but trichlorophenol resinousproducts and traces of other compounds probably chloraniline anddichloraniline are also formed.When chlorine is passed into an ice-cold solution of aniline inexcess of very concentrated (40 per cent.) hydrochloric acid for about18 hours most of the base is converted into parachloraniline and tri-chloraniline but considerable quantities remain unchanged. Tri-chloraniline is also formed when chlorine (6 mol.) is passed into asolution of aniline (1 mol.) in ice-cold concentrated hydrochloricacid. In 30 per cent. ice-cold hydrochloric acid solution chlorineacts on aniline much more readily ; parachloraniline dichloraniline,symmetrical trichloraniline and other compounds probably chloro-derivatives of phenol are formed and none of the base remainsUnchanged.I n 20 per cent. hydrochloric acid solution under thesame conditions trichloraniline chlorophenols and large quantities ofresinous products 'itre formed.Bromine even when added in large excess has no appreciarbleaction on aniline in 97 per cent. sulphuric acid solution ; after fourmonths' time only small quantities of symmetrical tribromaniline areformed. If a small quantity of iodine is mixed with the bromine,the formation of tribromaniline takes place rather more readily. Tn65 per cent. and i n 40 per cent. ice-cold snlphuric acid solution,aniline is acted on by excess of bromine considerable quantities of tri-bromaniline being formed ; in the latter case small quantities of acompound probably tribromophenol are also formed.When anilineis treated with excess of bromine in 40 per cent. hydrochloric acidsolution a reaction immediately takes place and the whole of thebase is converted into tribromaniline ; in 20 per cent. hydrochloricacid solution small quantities of tri bromophenol are also formed.Aniline hydrobromide is completely converted into tribromanilinewhen treated with excess of bromine in a concentrated ice-cold soh-tion of potassium bromide ; the yield of the pure product is 90 percent. of the theoretical quantity.Wheu chlorine is passed into an ice-cold 97 per cent.sulphuric acidF. S . I(38 ABSTRACTS OF CHEMICAL PAPERS.solution of paratoluidine for about 24 hours metacliloroparatoluirline[Xe C1 NH = 1 3 41 and larger quantities of orthochloropara-toluidine [Me C1 NH = 1 2 41 are obtained but a consider-able quantity of the base remains unchanged. In 40 per cent. hydro-chloric acid solution the whole of the paratoluidine enters intoreaction yielding metachloroparatoluidine metadichloroparatolnidine[Me Cl NH = 1 3 5 41 a crystalline compound probablyorthochloroparatoluidine and oily products probably chlorinated de-rivatives of cyesol.When pal-atoluicfine is treated with excess of bromine in 39 percent. ice-cold hydrochloric acid solution it is almost. completely con-verted in to met adibromoparaholui din e me 1 t ing a t 73 - 74" very smallqiinntities of a bromocresol being also produced.I n 65 per cent.sulphuric acid solution under the same conditions large quantit,ies ofmetadibromoparatoluidine are formed.When orthotoluidine is treated with excess of chlorine in 913 percent. ice-cold sulphuric acid solution it is partially converted into achlorotoluidine ; bromine under the same conditions has no appre-ciable action even after eight days' time.Action of Nascent Nitrous Acid on varims Amines andPhenols. By A. DENINGER (J.pr. Chem. [el 407296-308).-Whensodium nitrite ( 3 mols.) acts on an aqueous acid solution of aniline,ortho- and para-nitrophenol and some resinous su bstarices are pro-duced in quantities dependent on the concentration acidity andtemperature.The qaantity of orthonitrophenol produced is greater,the more rapid the reaction and the higher the temperature above65" ; i t varies from 0 to 50 grams whilst that of paranitrophenol variesfrom 0 to 33 grams per 100 grams of aniline. Air blown through theliquid diminishes the quantity of phenols produced as also does thepresence of oxidising or reducing substances. The nature of the acidhas no apparent effect. To obtain the best yield 10 grams of aniline,20 C.C. of sulphuric acid and 80 C.C. of water are mixed and cooled to15" ; 300 grams of sodium nitrite in 100 C.C. of water are then added,the solution heated in w water-bath and a large quantity of hot dilutesulphuric acid (1 1) immediately added.Alter the reaction theortho-compound is distilled over with steam and thc para-compoundcrystallised from the residue. Nitric oxide alone appears to be evolvedduring the reaction.If orthotoluidine (10 grams) be substitued for aniline in the aboveprocess orthonitrocresol [Me OH NO = 1 2 31 (5to6 grams),melting a t 68-69' is obtained. By using a more dilute solutionand allowing it t o stand for 14 days at 15-2b" paranitrocresol[Me OH NO = 1 '2 51 melting a t 96' is obtained. Withparatoluidine (100 grams) only one nitrocrcsol (138 grams) meltinga t 33-34" is obtainable.By acting on diamidoparadiphenyl and diamidoparadit)olyl respec-tively with sodium nitrite (6 mols.) in the way described above,dinitrodiphenol (m. p.260") and dinitrodicresol (m. p. 270') are pro-duced respectively.The subhate of diamidodicresol (dbstr. 1588 838) obtained byF. S. KORQANIC CHEMISTRY. 39reducing the dinitrocresol is sparingly soluble in water ; by diazo-tising it and decomposing with hot sulphuric acid tetrahydroxyditolylis obtained as a pleasant-smelling oil which is volatile with steam ;its aqueous solution gives a y ellowish-white precipitate with ferricchloride.With naph thylamine the above treatment yields dinitronaphtholand a little nitronaphthol ; when a-naphthylamine is treated with2 mols. more sodium nitrite than is necessary for diazotising anddistilled at once with steam P-nitro-+naphthol (m.p. 128") is ob-tained ; but i€ allowed to stand for 14 days at 10-15" a-nitro-a-naphthol is formed./3-naphthylamine yields a-nitro-@-naphthol(m. p. 103").Sulphanilic and orthotoluidinesulphonic acids yield by this treat-ment garnet-red crystals which lose the sulphonic acid group whentreated with super-heated steam and yield nitrophenol and nitro-cresol respectively. Naphthionic acid yields nitronaphtholsulphonicacid.Salicylic acid and its ethereal salts yield nitrosalicylic acid and itsethereal salts.A new substance is obtained when paraphenolsulphonic acid istreated with sodium nitrite and sulphuric acid ; it is still under in-vestigation. A. Q. R.Some Nitrated Diazoamido-compounds. Ry S. NIEMEN-TOWSKI (Ber. 22 2562-2567).-When metanitraniline is diazotisedin the manner described by Sandmeyer for paranitraniline (Abstr.,1885 981) a resinous precipitate is formed the moment the sodiumnitrite solution is added This can be afterwards separated from themetanitrobenzonitrile by steam distillation.It crystallises from amylalcohol in lustrous golden needles which melt a t 191-1'32"with decomposition. It has the formula C,,H,N504 and is identicalwith Griess' metadiazoamidonitrobenzene (m. p. 195.5 AnnaZen,121 2i2) and with Hallmann's dinitroamidoazobenzene (m. p.175-176" Ber. 9 389). I n order to determine the constitution ofthe compound a qustntit'y of it was prepared by Hallmann's method ;the substance prepared by this method when crystallised from amylalcohol also gave the m. p. 195". When the compound is heatedwith hydrochloric acid (sp.gr. = 1.17) for 10 hours at 185' meta-chloronitrohenzene is formed. Amy1 alcohol decomposes it at 185"with formation of metanitraniline and nitrobenzene. These reactionsand the behaviour of the substance towards aromatic amines andphenols with which it yields dyes show that the compound is diazo-amidonitrobenzene. Hallmnnn's method (Zoc. cit.) is a very con-venient one for the preparation of nitrated diazoamido-corn-ponnds.DiuzoamidonitrotoZuene CI4H,,N,O4 (from metanitroparatoluidine) isprepared by treating metanitroparatoluidine (m. p. 114" 30.4 grams),suspended in alcohol (250 grams) with nitric acid (sp. gr. 1.52,7.5 grams) and with a saturated solution of potassium nitrite(8.5 grams). It crystallises from am371 alcohol in dark reddish-brownbranched needles melts ah 169 dissolves very sparingly in alcohol40 ABSTRACTS OF CHEJIICAL PAPERS.more readily in ether and carbon bisulphide and very easily incold benzene acetone aiid chlorofwm.When heated with alcohola t 1 70° it is decomposed into metanitroparatoluidine and metanitro-toluene.Diazoanzido?zitroto?zcene (from paranitro-orthotoluidine m. p. 107")crystallises from alcohol in long bright pellow needles melts at 212"with decomposition and is readily soluble in acetone benzene andchloroform. N. H. 31.Trinitrohydrazobenzene. By E. FISCHER (Annulen 253.1-5).-The author's process for preparing trinitrohydrazobenzene frompicryl chloride and phenylhydrazine has been criticised by Willgerodtand Ferko (Abstr. 1888 830). In reply the author maintains thatthe process yields good results if the necessary conditions are observed.Symmetrical Nitrophenylhydrazines of the Aromatic Series.By C.W ILLGEEOUT ( J . pr. Cliem. [2] 40 264-270).-SSymmetricalpicrylhydrazines are obtained by cohabating picryl chloride and thehydrochloride of the aromatic hydrazine (in molecular proportion)in alcohol a t the ordinary temperature. Picrylphenylhydrazine,picr!j 1 ort hotoly 1 hydruzin e y icry lparatoly hydrazine and picryl -a-naph-thyEhydrazine have been thus obtained.All these decompose before they melt a t temperatures dependenton their state of division ; tbus picrylphenylhjdrazine in powderdecomposes a t 177" whereas its crystals decompose at 181" (compareAbstr. 1888 829).T1.e author has studied the action of heat on the nitrophenyl-hydrazines in presence of various liquids and finds that the decom-positions which occur may be classified as follows :-(l.)- The liquiddoes not decompose the nitrohydrazineperse; in this case the hydrazinehydrogen reduces the nitro-group to 8 nitroso-group ; such liquidsare water dilute hydrocliloric acid benzene and glacial acetic acid.(8.) The liquid is an oxidising agent ; the nitrobydrazine is oxidisedto a nitroazo-compound.(3.) The liquid decomposes the nitro-hydrazine altogether. (4.) The liquid acts as a reducing agent suchliquids being ethyl and methyl alcohols formic acid and acetone ; thefirst two and acetone convert picrylhydrazine into dinitrosonitroazo-benzene melting a t 219-220" ; formic acid converts it into a mixtureof two substances melting a t 225" and 233".(5.) The liquid is anorganic base ; in this case the nitrohydrazine is first converted intonit ro-nitroso-azo-compounds and these into polyazo-con1 pounds.The paper conclnde,s with a reply to Freund (Abstr. 1889,977) whccriticises the author's and Ferko's former work (Abstr. 1888 829).A. G. B.w. c. w.Phenylhydrazone. By E. FISCHER and F. ACH (Annnlen 253,5 7-65) .-Acetor?Rdi?Litroplienylhydrazone CBHIONIOI is prepared byslowly adding acetonephenjlhydraeone (12 grams) to strong colour-less nitric acid (25 grams) Rurrounded by a freezing mixture ; thissolution is allowed to drop into 100 grams of well-cooled f u z i n gnitric acid and the mixture is poured into ice water ; the product iORQANIC CHEMISTRY.41extracted with small quantities of ether and the residue purified byrecrystallisation from alcohol. It melts a t 127" (uncorr.) is solublein benzene chloroform ether and in hot alcohol and is quicklydecomposed by hot alkaline solutions b u t less readily by acids.Phenylhydrazonelevulinic anhydride is converted into the paranitro-derivative N02*C6H4*N<,~,CH2>CH2. by fuming nitric acid. Thissnbstance crystallises in flat needles of a yellow colour is soluble inhot alcohol benzene and glacial acetic acid and melts a t 118-119".The alcoholic solution is converted into paraphenylenediamineby reduction with zinc-dust and acetic acid. Warm alcoholic potas-sium hydroxide or warm concentrated hydrochloric acid convertsthe anhydride into paranitrophenylhydrazonelevulinic acid,NO2.C6H4.NH.N :C Me*C2H4*C 0 0 H.This acid forms orange-colouredneedles soluble in acetone and hof alcohol; i t also dissolves inalkalis forming intense deep-red solutions. It darkens a t 190' andmelts with decomposition a t 200". The ethyl salt melts at 156-157"with slight decomposition. It crystitllises in needles and dissolvesfreely in hot alcohol benzene and glacial acetic acid.The hydrazones of acetone and of acetaldehyde propaldehyde andoenanthaldehjde are decomposed by gently warming with pyruvicacid ; acetone or aldehyde is liberated and phenylhy drazonepyruvicacid is produced. The ketones and y-ketonic acids behave in thesame way.Paranitropli,enyl?zydrmon ep yruvic acid N0,*C6H4*NH*N:CMe-C 0 OH,is precipitated when pyruvic acid is added to a hot dilute solution ofnitrophenylhydrazonelevulinic acid in hydrochloric acid.The acidis soluble in acetone and in warm alcohol and is decomposed by heat.N ' CMew. c. w.Amidoximes and Azoximes. By F. TIEMANN (Ber. 22 2391-2395 ; compare Abst. 1886 875).-The conversion of nitriles intoamidoximes by the action of hydroxylamine may be considered to bea general reaction a s hitherto it has been found to apply to all cases,except that of nitriles such as pentamethylbenzonitrile which cannotbe or are only with difficulty converted into the' correspondingacid by the usual reagents. As a rule the formation of the amid-oxime takes place much more slowly with nitriles of high molecularweight and rich in carbon and the acid character of the product isless marked.The amidoximes combine readily with hydrogen cyanate phenyl-carbimide and phenylthiocarbimide yielding uramidoximes phenyl-uramidoximes and phenylthinramidoximes.The ethyl-derivativesof the amidoximes also combine with phenylthiocarbimide aud withphenylcarbimide. F. S. K.Phenylallenylamidoxime-derivatives. By H. WOLFF (Rer.,22 2395-240 1 ; compare Abstr. 1886 798) .-Phenylallenylethoxirnenitrite CHPh:CH*C(N*OEt)-O*NO separates in colourless needleswhen a solution of phenylallenylamidethoxime (1 mol.) in dilutesulphuric acid is treated with sodium nitrite (2 mols.) in the cold48 ABSTRACTS OF CHEMICAL PAPERS.It turns yellow after a short time and is very unstable explodingalightly when treated with concentrated sulphuric acid or wbenheated quickly.It melts at 61" is readily soluble in alcohol chloro-form benzene and ether but only sparingly in light petroleum andalmost inPoluble in water. I t can be crystallised from alcohol a ttemperatures below 55" but slight decomposition occurs. It isdecomposed b y acids or alkalis yielding cinnamic acid. The chloride,CHPh:CH.CCl:N*OEt separates as a yellowish oil when the amid-ethoxime is dissolved in excess of hydrochloric acid and the solutiontreated with sodium nitrite. It is soluble in ether alcohol benzene,and chloroform but only sparingly soluble in light petroleum andcarbon bisulphide and almost insoluble in water; it is not decom-posed when warmed for a short time with acids or bases.Phen y 1 dibromoprop eny lethoxime chloride C HBrP h- CHBr C CKN* OE t ,prepared hy warming the chloride with a slight excess of bromine isa solid compound readily soluble in ether benzene and chloroform,but only sparingly in light petroleum and insoluble in water.Pheny la1 len y Ipheny luramidet Iioxime,CHPh:CH*C (NOE t)*NH*CO*NBPh,obtained by treating phenylallenylamidethoxime with phenylcarb-imide crystallises from dilute alcohol in colourless needles melts a t155-156" and is readily soluble in alcohol ether benzene andchloroform but only sparingly in light petroleum hot water andhydrochloric acid and insoluble in potash and cold water.Phenylalleruy lp h enyluramidoxime,CHPh:CH*C (NO H)*NH*CO*NHPh,prepared in like manner from phenylallenylamidoxime crystallisesfrom dilute alcohol in colourless needles melts a t 158-159" and isreadily soluble in ether but only moderately so in benzene andchloroform sparingly in light petroleum and insoluble in coldwater ; i t is only very sparingly soluble in acids and alkalis.Pheny 1 all eny luramidoxim e C H Ph CH*C (PU'OH) *NHX 0 -NH sepa-rates in colourless needles when an aqueous solution of phenylallenyl-amidoxime hydrochloride is treated with potassium cyanate ; it meltsa t 158-159" and is readily soluble in alcohol and ether but onlymoderately in benzene and chloroform and sparingly in light petro-leum and cold water.It forms salts with acids and dissolvesunchanged in alkalis but when treated with concentrated acids oralkalis a t the ordinary temperature it is reconverted into the amid-oxime.The platinoch7oride ( C,,HllN,O,),,H,PtC1 is crjstalline.E t h y l pJ~ei~ylallenylainidoximecarboxylu te,CH Ph C €3- C (N H,) :N.O-CO OE t,is obtained together with the hydrochloride of the amidoxime whenphenylallenylamidoxime (2 mols.) is treated with ethyl chlorocarb-onate ( I mol.) in benzene solution. It is a crystalline unstablecompound melts at 101" and is readily soluble in erher alcohol,chloroform and benzene but only sparingly in light petroleum andinsoluble in waterORGANIC CHEJlISTRY. 43Phen~lallen~lcarbonyli.nzidoxime CHPh:CH*C<gzg> is formedwhen the preceding compound is warmed with alkalis or heatedabove its melting point.It crystallises from dilute alcohol in slenderneedles melts a t 199-2200" and is readily soluble in alcohol ether,benzene and chloroform but only sparingly in light petroleum and isinsoluble in cold water. It has an acid reaction and in neutral solu-tions of the ammonium-derivative silver nitrate produces a white,and copper sulphate a green precipitate. F. S. K.Substituted Amidoximes. By H. M ~ L L E R (Ber. 22 2401-2412 ; compare Abstr. 1€W 875) .-Benzenylphenylcarbonylimid-oxime melting a t 166-1 67" is formed together with benzjlanil-idoxime hydrochloride when benzenylanilidoxime is treated withcarbonyl chloride in benzene solution.Benzenylanilidoxime combines with chloral in the cold forming acolourless flocculent compound NHPh.CPh:NOH,C,C130H whichmelts a t 128-130" is readily soluble in alcohol ether chloroform,and benzene and is decomposed by concentrated acids and boilingwater .Ethylbenzamide COPh-NHEt prepared by gradually addingbenzoic chloride to an ethereal solution of etbylamine in the cold,separates fieom ether in large crystals melts a t 69-70" and is solublein water tenzene chloroform and alcohol but only sparingly inlight petroleum ; i t is moderately easily soluble in hydrochloric acid,but insoluble in soda.Uenzoparutoluidide COPh*NH*C,'R,Me prepared from benzoicchloride and toluidine in like manner crystallises in plates andmelts at 157-1563".Thiobenzoparatoluidide CSPh*NH*C,H,Me is hest prepared bywarming the preceding compound with phosphorus pentasulphide ;it crystallises from dilute alcohol in long yellow needles melts a t128-129' and is readily soluble in alcohol ether chloroform,benzene light petroleum and soda but insoliible in water.Benzenylpuratoluidoxirne NOH:CPh*NH*C6H,Me prepared byheating t hiobenzotoluidine with hJdroxy1amine hydrochloride andsodium carbonate in dilute alcoholic solution ~rpt~nllises from dilutealcohol in long colourless needles melts at 176' and is readilysoluble in ether chloroform benzene acids and alkalis but onlymoderately so in hot water.The hydrochloride C,4HliNz0,HCI,crystallises in colourless needles and is sparingly soluble in water.Be~tzenylparafoluy lcarbontlli?nidozime C6&Me< >NO pre-pared by treating benzenyltol~iidoxime with ethyl chlorocarbonate inchloroform solution crystallises from dilute alcohol in yellowishneedles melts at 163" and is readily soluble in ether chloroform,benzene and light petroleum but insoluble in water acids anda1 kal i 9.Ethenylanilidoxime NOH:CMe*NHPh (m.p.120-121"). is obtainedwhen thiacetanilide is boiled with an alcoholic solution of hydroxyl-ainine hydrochloride and sodium carbonate. The hydyochloride,CP44 ABSTRACTS OF CHEMICAL PAPERS.CsHloNzO HCJ crystallises in colourless needles. The pZatinochZoride,( C8H,oN20),,H,PtC16 crystallises in slender yellow needles. Thehenzoyl-dei-ivative NOBz:CMe*NHPh crystallises from dilute alcoholin colourless needles melts a t 110" and is soluble in benzene chloro-form and ether but insoluble in water and light petroleum.Methenylanilidoxirne NOHlCH-NHPh prepared in like manner,crystallises from a mixture of benzene and light petroleum in colour-less needles melts a t l l G o and is moderately easily soluble in water,alcohol ether chloroform and benzene but almost in soluble in lightpetroleum.The hydrochloriide C7H8N20,HCl crystallises in needles.The pZatinocl~Zoride (C,H,N,O),,H,PtCI crystallises in yellowishneedles. The benzoyl-derivative NOBz:CH*KHPh crystallises incolourless needles melts a t 14&-145" and is moderately easilysoluble in alcohol ether chloroform and benzene but almost in-soluble in water and light petroleum. F. s. K.Action of Acetaldehyde and of Ethyl Acetoacetate onBenzenylamidoxime. By F.TIEMANN (Ber. 22 2412-2417).-prisms when an aqueous solution of acetaldehyde (1 mol.) and benz-enylamidoxime (1 mol.) is kept for some time in a warm place. Itmelts a t 82" and is readily soluble in alcohol ether acetone andbenzene but only sparingly in hot and insoluble in cold water ; it isdecomposed when heated with acids. The hydrochloride CgHloN,O,HCl,prepared by passing hydrogen chloride into an ethereal solution ofthe base is crystalline. The platinochlorida ( C9H,,N,0),,HzPtCI isan orange-yellow compound fioluble in alcohol and decomposed bywater. The base is converted into benzenyletheny lazoxime by potas-sium permanganate in cold dilute sulphuric acid solution.BenzenyZacetoetiienyZazoxirne CPh<Ng>C*CH,Ac - prepared byheating benzenylamidoxime with ethyl acetoacetate crystallises fromboiling water in short yellowisli prisms melts a t 86" and i s readilysoluble in alcohol ether benzene and acetone b u t only sparingly inlight petroleum and boiling water ; it dissolves freely in alkalis butis insoluble in acids. When boiled with alkalis it is decomposed intobenzenylethenylazoxime and acetic acid.The oxime CllHllN302,crystallises from alcohol in colourless needles melts at 80" and issoluble in ether benzene and hot water but almost insoluble in lightpetroleum and cold water. It is a feeble acid and reduces Fehliog'ssolution on warming. The hydrazone C1,H16N40 prepared by heatingthe ketone with phenylhydrazine crystallises from dilute alcohol inyellowish needles melts a t 126" and is insoluble in water and lightpetroleum but readily soluble in alcohol ether benzene and acetone.Paranitrobenzenylamidoxirne and Paramethylorthonitro-benzenylamidoxime.By J. WETSE ( B e y . 22 2418-2432).-Paranitrobeizzeriylamidoxime NO,*C,HI*C(NHz) :NOH is obtained,together with paranitrobeneamide (m.p. 197") when paranitrobenzo-ni trile prepared from paranitraniline by Sandmeyer's method isEthylidenebenxeny Zamidoxime CPheNH>CHMe NO separates in rhom-F. S. KORGANIC CHEMISTRY. 45digested with hydroxylamine hydrochloride and sodium carbonate inaqueous solution. It crystallises in yellow needles melts at 169",distils without decomposition and gives all the reactions of amid-oximes ; it is moderately easily soluble in alcohol and hot water butrather sparingly in benzene ether and chloroform and insoIuble inlight petroleum.The hydrochloride C7H7N303,HC1 crystallises fromwater in colonrless hygroscopic needles melts at 185" with decompo-sition and is soluble in alcohol but is reprecipitated ou adding ether.The ethyl-derivative NO2.C6H4*C(NH2):N*OEt is obtained bytreating the amidoxime with sodium etboxide and digesting theresulting deep-red solution with ethyl iodide ; it is best obtained in apure state by decomposing the hydrochloride with dilute soda. Itforms large yellow prismatic crystals melts at 59-60' and isreadily soluble in alcohol and ether but only moderately so in benzene,and sparingly in light petroleum and hot water.The hydrochlorideseparates from akoholic ether in colourless crystals.Paranitrobenzenylethenylazoxime NO,*C,H,*C<- N>CMe preparedby dissolving the amidoxime in acetic anhydride crystallises incolourless plates melts a t 1U0 and is readily soluble in alcohol,ether and benzene but only very sparingly in hot water. The corre-NO-.T ,,sponding benzen,yl-compound N02*C6H4*O<~~>CPh prepared bywarming the amidoxime wi t8h benzoic chlo~ide crystallises fromalcohol in small colourless needles melts at 198" and sublimes wit'h-out decomposition when heated slowly but explodes when heatedquickly. It is insoluble in light pet,roleum and only moderat.elysoluble in alcohol but readily i n ether benzene and glacial aceticacid.Eth y 1 parnnitro b enzen ytnmidoximecarbox y lnte,NO,*CsH,*C (NH,)XO*COOEt,is €ormed when the amidoxime is treated with ethyl chlorocarbonatein cold chloroform solution.It crystallises from cold dilute alcoholin small needles melts at 169" and is moderately easily soluble inalcohol ether benzene and chloroform but only very sparingly inwater and insoluble in light petroleum.ParunitrobPnzenylcarbonylimidc~xime N02C,H4*C<NH>C0 is ob-tained when the preceding compound is boiled with alkalis or heatedalone; it separates from alcohol in small yellow needles melts a t286" and is insoluble in light petroleum and only very sparinglysoluble in hot water but more readily in alcohol ether and benzene.It is a very stable compound and dissolves freely in alkalis; in aneutral solution copper sulphate produces 8 green precipitate.NOCarbon y ldi-purani t r o b enzen y 1 amidoaim e,prepared by *treating the amidoxime with carbonyl chloride inbenzene solution at the ordinary temperature crystallises in small,jellowish needles melts at 236" and is very readily soluble in alcohol46 ABSTRACTS OF CHEMICAL PAPERS.and moderately so in hot water but more sparingly in benzene andether and insoluble in light petroleum ; it is converted into pnranitro-benzenvlcarbonvlamidoxime when warmed with alkalis.d YE t h y 1 idm9para nit ro benz e mjla in idozi me N 02*C6 H,<g; > C HMe,separates in dark yellow crystals when an aqueous solution of theamidoxims is treated with a slight excess of acetaldehyde and keptfor some days ; it crystallises in needles melts at 153" and is readilysoluble in alcohol ether benzene and chloroform but only sparinglyin hot water and insoluble in light petroleum.It is not acted on bydilute acids or alkalis in the cold but oxidising agents convert itquantitatively into the a.zoxime. It is decomposed into its con-stituents when warmed with dilute hydrochloric acid. A yellow,flocculent compound separahes from the solutiou when etbylidene-paranitrobenzenylamidoxime is treated with warm dilute soda. Thissubstance melts a t 252" is very stable and is insoluble or onlyverysparingly soluble in most ordinary solvents. It dissolves uncliaiigedin concentrated sulphuric acid and is not acted on by reducing oroxidising agents or when heated at 150" with concentrated hydro-chloric acid; it is decomposed by fuming nitric acid yielding aneutral compound which melts at about 180" and seems to be Rdinitroethenylazoxime.Chloreth~lidelwparanit robelzzen~ilamidoairne,NO NO,*C 6H4*C<NH > C H*C H2C1,is formed when the amidoxime is boiled with dichlorethyl ether inaqueous solutions. It crystsllises from dilute alcohol in yellow plates,melts at 176" and is very readily soluble in alcohol but only mode-rately easily in benzene ether and water and insoluble in lightpetroleum.It re3embles the preceding compound in its chemicalbehaviour and yields a complex condensation-product when warmedwith alkalis.EtA yiparaizitrobenzen ylozinie nitrite N02*C6H,*C( NOE tr).O*NO pre-pared by treating the amidoxime with sodium nitrite in cold dilutesulphuric acid solut'ion is a yell0 w very unstable flocculeiit com-pound melting a t 55" with explosive violence ; it is soluble in alcoholand ether but insoluble in water.It decomposes slowly a t theordinary temperature with evolution of oxides of nitrogen andexplodes when heated with water or when treated with concentratedsulphuric acid. > C*CH2Ac,is formed when the amidoxime is digested with ethyl acetoacetate.I t crystallises from d-ilute alcohol in golden plates melts a t 140" andis readily soluble in alcohol and ether but only moderately so inbenzene very sparingly in water and insoluble in light petroleum.When heated with alkalis it is quickly decomposed into acetic acidand nitrobenzenylethenylazoxime.Paramidobenien ylamidoxime NH?*C6H,*C(NH2):XOH prepared byreducing the nitr+compound with stanuoos cbloride and hydrochloricNO Paranitro benzeny lacetoet heny lazoxirne N D2*C H,*CORGANIC CHEMISTRY.47acid and decomposing the resulting salt with sodium carbonate crys-tallises in yellow plates turnx brown at lGO" and melts at 174" withdecomposition. It is very readily soluble in alcohol but only mode-rately easily in benzene and ether sparingly i n hot water and in-soluble in light petroleum ; it gives the reactions of amidoximes anddissolves freely in alkalis.Paramethylorthonitrobenzonitrile [ CN NO2 Me = 1 2 41 pre-pared from metanitroparatoluidine by Sandmeyer's method crgstal-lises from water in long yellowish needles melts at 99" distils withoutdecomposition and is readily soluble in alcohol ether benzene andchloroform but only sparingly in hot water and almost insoluble inlight petroleum.Paramet hy lort honitrobenzeny lamidoxiime N02*C6H3&1e*C (NH?) :NOH,is obtained by digesting rnethylnitrobenzonitrile with hydroxylaminein alcoholic solution and is best prepared in a pure state by decom-posing the copper-derivative with hydrogen sulphide.It crystallisesin long yellow needles melts at 161" and shows the properties of anamidoxime ; it is moderately easily soluble in alcohol and hot water,but only sparingly in benzene ether and chloroform and is insolublein light petroleum. The hydrochloride CBHSNYOS,HC1 is a colonrless,crystalline compound soluble in alcohol but reprecipitated on addingether.Paramethylorthonitrobenzamide [CONH NO2 Me = 1 2 41 isformed in the preparation of the preceding compound.It crystallisesfrom water in long yellow needles melts at 152" and is readilysoluble in alcohol ether and benzene but almost insoluble in lightpetroleum ; it is converted into the corresponding acid when boiledwith alkalis.Para rneth y 1 orthamidoben,zeny lamidoxime,is produced in small quantities when methylnitrobenzenylamidoximeis reduced with stannous chloride and hydrochloric acid. It is abrown flocculent compound melts at about 166O and gives the reac-tions of aniidoximes. The hydrochloride is a colourless crystalline,hygroscopic compound soluble in alcohol but reprecipitated on addingether.F. S. K.Para- and Ortho-homobenzenylamidoxime and their De-By L. H. SCHUBART (Bey. 22 2433-2440; comparz rivatives.Abs tr. 1886 79 7) .-Parahomo benz eny letheny lazoxime,prepared by boiling the amidoxime with acetic anhydride crystallisesin colourless prisms melts at 80° and is readily soluble in alcohol,ether chloroform and benzene but insoluble in acids and alkalis.Parahomobenzenylethoxime chloride C6H4Me*CCl:NOEt obtained bytreating the amidethoxime with hydrochloric acid and sodium nitrite,is a ,yellow oil boils at about goo" a.nd is soluble i n aloollol andether. The corresponding bromide prepared in like manner is 48 ABSTRACTS OF CHEMICAL PAPERS.heavy brown oil; it decomposes at 155" and is readily soluble inether chloroform and benzene.Parahomobenzenylp-openylazoxime-w-carboxylic acid,C6H4Me*C<- "0 y>C*C2H4-COOH.Ais formed when the benzenylamidoxime is melted with succinic an-hydride.It crystallises from boiling water in colourless needles,melts at 138*5" and is soluble in alcohol ether chloroform andbenzene.Parahomobenzenyluramidoxime C,H,Me*C(NOH)*NH*CO.NH pre-pared by treating the hydrochloride of the atnidoxime with potassiumcyanate in aqueous solution crystallises in colourless needles meltsa t 170" and is readily soluble in alcohol ether and benzene but onlysparingly in water. The thiowuinidozime,C,H,Me*C (NOH) *NH*CS.NHPh,prepared by treating the amidsxime with phenylthiocarbirnide crys-tallises from hot water in colourless needles melts ot lYO" and isreadily soluble in alcohol and ether but more spariiigIy in chloroformand benzene.Para<horno b enzen y lpheny luvani idoxime,C6H4Me*C( NOH)*NH*CO*NHPh,prepared from phenylcarbimide in like manner separates from dilutealcohol in colourless crystals melts a t 155" and is readily soluble inrtlcohol ether and hot water.Ethyl pamhornobenzenylnnzidoximecarboJ.ylate,C6H4&fe-C (NH,):NO*COOEt,is obtained by treating the amidoxime with ethyl chlorocarbonate i nchloroform solution ; it crystallises from dilute alcohol i n colourlessneedles melts a t ISO" and is readily soluble in alcohol ether chloro-form and benzene but only sparingly in light petroleum and water.PnrahomobenzenyEcarBonyZirnidoxime C6H4Me*CWNH>C0 NO crystal-lises from hot water in colourless needles melts at 220" and is solublein ether alcohol and alkalis.Diparahomobenzenylnzoxime C6H4Me*C< >C*C6H4Me is formedwhen the amidoxime is heated with glacial acetic acid. It crystallisesfrom dilute alcohol in long colourless needles melts a t 135" and isinsoluble in water but readily soluble in ether benzene chloroform,and light petroleum.C6H4Me*CeK NO I-_i > CHM e,melts a t 127.5".and is readily soluble in alcohol ether and benzene,but only sparingly in hot water.NOEtlr ylidenepara.12omobenz eny lainidonime,Parahomobenzenylacetoetheny lctzoxinze C6H4Me*C<L YO N>C.CH2Ac,-pared by treating the amidoxime with etbpl acetoacetate crystalliseORGANIC CHEMISTRY.49from boiling water in colourless needles melts at 97" and is readilysoluble in alcohol ether and benzene.Orthohomobenzeny Zaniicloxime CsH,&Ie*C (NH,) :NOH obtainedfrom homobenzonitrile (b. p. 195") crystallises from hot water inyellowish needles melts at 149.5" is readily soluble in alcohol ether,and benzene and shows the characteristic reactions of amidoximes.The ethyl-derivative C,,H,,N,O forms colourless prismatic crystals,melts at 140° and is readily soluble in ether alcohol and benzene.The benzoyl-derivative C,5Hl,Nz0 crystallises from dilute alcohol inneedles melting at 145".Orthohornobenzenylbenzeny luzoxime C 6 H ~ e * C < ~ ~ > c P h preparedby dissolving the benzoyl-derivative (see above) in cold concentratedsulphuric acid crystallises in long colourless needles melts at 80°,and is insoluble in acids alkalis and cold water but readily solublein alcohol ether benzene and chloroform.F. S. I(.Action of Carbon Bisulphide on the Potassium Compoundof Parahomobenzenylamidoxime. By L. H. SCHUBART (Ber. 22,2441-2442) .-A compound CSH,N,S2 is formed when parahomo-henzenylamidoxime (1 mol.) is dissolved in alcoholic potash and thesolution boiled for about three hours with carbon bisulphide (1 mol.).It crystallises from alcohol in yellow needles melts at 165" and issoluble in ether chloroform benzene and alkalis.The compound C,H6N2S2 can be obtained from benzenylamidoximein like manner. It crystallises from alcohol in yellow prisms andmelts at 160".F. S. K.Xylenylzmidoxime and its Derivatives. By E. OYPENH EIMER(Ber. 22 'L442-2449).-Xylylonitrile [CN Mez = I 2 41 pre-pared from xnet3axylidine by Sandineyer's method separates fromcold dilute alcohol in long colourless crystals melts a t 23-24' isvolatile with steam and is readily soluble in alcohol and ether(compare Oasiorowski and Mere Abstr. 1885 772).Xylenylumidoxime CsH,Mcz.C( NH,):NOH is obtained when thepreceding compound is heated with hydroxylamine for 5 to 6 hoursat 80-85". It crystallises in colourless needles melts at 178" and isreadily soluble in alcohol ether chloroform and hot water but onlysparingly in cold water; it gives all the characteristic reactions ofaruidoxirnes.The ethyl-derivative CI,H,,J,O crystallises in colourlessiieedles melts at 172" and is readily soluble in alcohol ether,chloroform benzene and hot water but only sparingly in cold water.The benzoyl-derivative CI6H,,N,O separates from dilute alcohol incolourless crystals melts at 158" and is only sparingly soluble inwaher and light petroleum but readily in alcohol ether and chloro-f x m .Xy 1 en y Zb enzen y Zuzoxime CsH,Me2*C< N>C Ph prepared by heat-ing the beuzoyl-derivative described above crystallises in yellowishscales melts at 98" sublimes readily and is volatile with steam ; it isreadily soluble in alcohol ether chloroform and benzene.NOVOL. LVIIT. 50 ABSTRACTS OF CHEMICAL PAPERS.Acety Zxy Zeny lamitloxime C6H3Me2-C(NHz) :NOAc obtained bytreating the amidoxime with acetic chloride in ethereal solution,crystallises from cold alcohol in colourless needles melts at 189",and is readily soluble in alcohol and chloroform but only sparinglyin ether.The corresponding ethenyluzoxinte C,,H,,N,O is preparedby heating the amidoxime with acetic anhydride and distilling theproduct with steam; it separates from alcohol or ether in crystalsand melts at 89".Xylenylazoximepropeql-w-carboxylic acid,C 6 H 3 M e 2 0 C ~ ~ ~ ~ C ~ C 2 H 1 * C O O H ,prepared by fusing the amidoxime with succinic anhydride crys-tallises in long colourless needles melts at 112" and is readilysoluble in alcohol ether benzene and chloroform ; it forms crystal-line salts with bases.SEth?/Z xyZenyZamidoxirr,ecarboxyZate C6H3Me*C(NHz):NO*COOEt isobtained by treating the amidoxime with ethyl chlorocarbonate inchloroform solution.I t crystallises from dilute alcohol in colourlesaneedles melts at 142" and is readily soluble in alcohol ether andchloroform but only sparingly in light petroleum; it has feeblebasic properties.Xy Zeny 1 carbon y lamidoxime C6H3Mez* CfNH > C 0 prepared byheating the preceding compound crystallises from hot water inneedles melts at 182" and is readily soluble in alcohol and ether; ithas acid properties.The compound CeH,2Nz0,CCI,*COH is formed by the direct combin-ation of its constituents ; it separates from a mixture of benzene andlight petroleum i n crystals melts at 112" and dissolves unchanged inalcohol and ether but is decomposed by water and by dilute acids.Xylenyluramidoxime CsH,Me2*C(NOH).NH.CO*NHz separates incoiuiwless crysta,ls when the hydrochloride of the amidoxime istreated with potassium cyanate in ethereal solution.It melts at155" is readily soluble in ether alcohol benzene and light petroleum,but onlg sparingly in water; it combines with acids and also butless readily with bases.C6H3Mez.C(NOH)*NH*C0.NHPh,crystallises from alcohol in light yellow scales melts at 138" and issoluble in alcohol ether benzene chloroform hot water and acids.XyZenyZphenyZthiuramidoxime C6H3Mez*C(NOH)*NH-CS*NHPh,separates from dilute alcohol in light yellow crystals meIts at 150",and is soluble in alcohol ether benzene acids and boiling water,but almost insoluble in alkalis.F. S. K.NOThe phenyl-derivative,Action of Sulphuric Acid and Selenic Acid on AromaticCompounds. By ISTRATI (Bull. Xoc. Chim. [3] 1 480-481).-Finding that the prolonged action of sulphuric acid on benzene pro-duced a sulphonic acid sulphobeneide and a francein the authorheated selenic acid sp. gr. 1.4 (200 grams) with pure benzene (50 c.c.ORGANIC CHEMISTRY. 51for 32 hours at 80" ; neither selenobenziile nor a francei'n was produced,but after neutralisation of the acid by barium carbonate a smallquantity of a crystalline organic compound which the author believesto be phenyl selenide (comp. Abstr. 1889,41) was extracted from thebarium salt by hot water. Pentachlorobenzene similarly treated gavea corresponding result.New Data relating to France'ins.By ISTRATI (BUZZ. Xoc. Chiin.[3] 1 481487 ; compare Abstr. 1888 591).-When snlphuric acidis heated with halogen-derivatives of benzene it causes the migration ofhalogen-atoms and this determines the formation from the initial corn-pound of france'ins whose chlorine values differ. Thus from 1 2 4-trichlorobenzene three franceins resulting from the oxidation of di-,tri- and tetra-chlorobenzenesulphonic acids are produced and theseare accompanied by a small quantity of 1 2 4 5-tetrachloro-henzene. From 1 2 4 5-tetrachlorobenzene a francein is ob-tained which is separable into five france'ins of varying solubilitiesand compositions. Numerous analSses are given. T. G. N.Francei'n from 1 2 4 Trichlorobenzene.By ISTRATI ( B d .~ O C . Cltinz. [3] 1 4.88-492) .-From comparative experiments whichhe has made as to the formation of france'ins from 1 2 4-tri-chlorobenzene the author finds that the yield of francein is de-pendent on the temperature and varies inversely as the amount ofsulphonic acid remaining in the mixture a t the close of the operatmion.Action of Heat on a Mixture of Sulphuric Acid and Sul-phonic Derivatives. By ISTR~ATI (BUZZ. SOC. Ckim. [3] 1 49%-496).-From experimental observations the author concludes thatwhen a mixture of excess of snlphuric acid and a sulphonic acid ora sulphonate is heated regeneration of hydrocarbons with formationof water and of pyrosulphuric acid respectively occur while sulpho-benxide is formed as a condensation-product and a decompositionof the sulphonic acid into sulphurous anhydride hydrocarbon andoxygen determines the formation of a franceiin by the oxidation ofunaltered sulphonic acid.T. G.N.T. G. N.T. G. N.a-Ketoaldehydes. By H. MGLLER and H. v. PECHMANN (BPT. 22,2556-2 56 1 ).-Benzoy lf ormaldehy de C OPh . CO H(Abstr. 18e8 146) is prepared by dissolving nitrosoacetophenone(30 grams) in a 35 per cent. solution of sodium hydrogen sulphite(120 grams) contained in a litre flask. When cold the whole solidifiesto a yellowish crystalline mass and is then stirred with alcohol andglacial acetic acid (1 c.c.) and after some time filtered by suction. Theproduct (30 or 40 grams at a time) is boiled with 11 parts of 17 percent.sulphnric acid in a flask fitted with an upright condenser until onequarter of the liquid is boiled off. On cooling crystals of phenylglyoxalhydrate separate and are purified by crystallisation from boiling water.It dissolves in about 35 parts of water at 20". When heated withnitric acid (sp. gr. lath) benzoglformic acid is formed. When anaqueous solution is treated with phenylhydrazine dissolved in dil ntu( phen ylglyosal),e 52 ABSTRACTS OF CHEMICAL PAPERS.acid thea-hydrazone NHPh*N:CPh*COH separates as a brown cryetal-line precipitate which may be obtained from alcohol in yellow plates,melts a t 142-143",and is readily soluble in most solvents. The osazone,C,,H18N is obtained by heating phenylglyoxal with phenylhydrazineacetate (2 mols.) or more conveniently from nitrosoacetophenoneand an excess of phenylhydrazine ; it is identical with Laubmann'scompound from benzoyl carbinol and phenylhydrazine (Abstr.1888,366). When the aldehyde is dissolved in aqueous soda and b:ded fora few minutes sodium lnandelate is formed. It is probable that i nthe formation of mandelic acid from benzoylcarbinol (Rreuer andZincke Abstr. 1880 645) and from acetophenone dibromide (Englerand Wohrle Abstr. 188'7 948) benzoylformaldehyde is formed asintermediate product (compare Zinoke Annalen 216 31 5).When phenylglyoxal is treated with ammonia a compound of theformula C,,Hl,N30 or C,H,,N,O is obtained. This crystallises fromdilute alcohol in yellowish-white lustrous plates melting a t192-193" and can be distilled; i t is soluble in alkalis and is notchanged by sulphuric acid.Phenylglyoxal reacts with hydroxylamine yielding the cnnipoundC16H,3N403. The latter melts a t 219' dissolves in alkalis and is pre-cipitated by acids as a white powder which becomes yellow whenexposed to light.A7itrosomethyZ paratol!/Z fietone C6H4Me.C0.CH:NOH prepared byGaiseti's method crystallises from benzene in colourless needlesmelting a t 100'.ParatohjZgZyoxaZ hydrate C6R,Me*CO.CH(OH) is prepared fromthe a,bove compound in a manner similar to phenylglyoxal.It crys-tallises from water in white matted needles softens at 95" melts a t1OO-l0'Lo and is readily soIuble in alcohol ether and benzene butless soluble in water and light petroleum.When shaken with benzenecontaining thiophen and salphuric acid the latter becomes green.The aldehyde behaves towards alkalis like the phenyl-compound isoxidised by nitric acid (sp. gr. 1.4) to toluylformic acid and by per-mariganate to paratoluylic acid (m. p. 180'). The osazone C21H20N1,obtained by heating a solution of the aldehyde with an excess ofphenylhydrazine acetate for 30 minutes on a water-bath crystallisesin yellow needles melting a t 145".Naphthyl methyl ketone C,,H,,O melts a t 51-52' boils at.300-301" and when oxidised yields /3-naphthoic acid. It is notidentical with the compound obtained by Claus and Feiss (Abstr.,1887 271) but possibly is with Pampel and Schmidt's (Abstr. 1887,252) compound. N. H. M.Isomeric Dinitroparatoluic Acids.By B. ROZA~SKI (Bey.,92 2675-268'2) .-By nitrating orthonitroparatoluic acid (Abstr.,1888 l088) two dinitro-derivdires were ohtnined and their consti-tution establisbed from the corresponding dinitrotoluenes.2 5-DinitroparufrnZiiic acid (COOH NO Me NO = 1 2 4 5 )is very sparingly soluble in cold water easily in alcohol andacetone crystallises in needles and melts a t 158". The sodiu,nz salt(with 3H,O) forms glistening je:low scales ; the bui*ium salORGANIC UHEJIIS'I'RT. 53(with 2&H20) sIrlaI1 yellowish-white needles ; the calciimt salt (with2H20) reddish-brown scales ; the ammonium salt lemon-yellow scales ;the siher salt a white amorphous powder; the copper salt a light-green powder ; the mercuric lead and i r o n salts white precipitates.2 3-Dinitroparatoluic acid [COOH NO NO Me = 1 2 3 41forms yellowish prisms soluble in alcohol and melts at 249".It a i dits salts are less soluble in most solvents than the 1 2 4 5 acid.The bariwn saZt (with 4H,O) forms pale-yellow needles; the calciumsalt (with H,O) pale-yellow scales. The other salts are similar tothose of the isomeric acid. L. T. T.Acetometanitrobenzoic Anhydride. By W. H. GREENE (Airier.,Chenz. J. 11 414-415).-When dry silver metaniirobenzoate istreated with excess of cold acetic chloride and the product pouredinto water metanitrobenzoic acid is regenerated ; Liebermann'sstatement (this Journal 1877 ii 617) that metanitrobenzoylaceticacid (acetometanitrobenzoic anhydride) is formed is incorrect.Acetometanitrobenzoic anhydride is however obtained by treatingsodium or silver metanitrobenzoate with acetic chloride and extract-ing the product with ether.It forms colourless needles which melt a t45". It is insoluble in water but the presence of either water o ralcohol in the ether used for extraction CiLuSes complete decomposi-tion of the anhydride,Action of Phosphorus Trichloride on Salicylic Acid. By R.ANSCHUTZ and W. 0. EMERY (Airier. CRein. J. 11 387-392).-Whensalicylic acid is heated with excess of phosphorus trichloride a tiO-8rj0 and the product distilled first at the ordinary pressure to getrid of tlie excess of phosphorus trichloride and then under reducedprfssure snlicyloplzosphorus chloride C7H403PCl. solidifies in the re-ceiver.This melts st 36-37" boils a t 127" under 11 mm. pressure,decomposes under ordinary pressure a t about 245" and is soluble i nether chloroform and benzene. With phosphorus pentachloride orwith chlorine i t gives an additive-compound C7H403PC13 of sp. gr.= 1.5587 a t 20" (water at 4" = l) boiling at 168" under 11 nim.pressure ; this compound can also be obtained by the action of phos-phoieus pentachloride on salicylic acid. With bromine a similar com-pound CiH1O3PCIBr2 is obtained of sp. gr. 1.8852 a t 20" (water a t4' = l) and boiling at 18.5-188" under 11 mm. pressure. Tliefollowing are given as the most probable formulae for salicylophos-p horus monochloride and its chlorine additive-prodxct respectively :-C. F.13.C. I?. B.Constitution of Isoeuxanthone. By C. ARBENZ (Chem. Centr.,18H9 ii 73; from A r c h . Sci. p h y s . mat. Gen6z.e [3] 21 3'75).-Phenylsalicylic acid is converted by nitric acid into the dinitro-derivative NO,.CsH1(O.CsH,.NO,).COOH which may be split upinto paranitrophenol and pararlitrosalicylic acid proving that bot 11nitro-groups are in the para-position. Sulphuric acid converts th51 ABSTRACTS OF CHEMICA\L PAPERS.dinitro-derivative into dinitrodiphenyleneketona oxide which maybe reduced to the diamido-derivative isoenxanthone. J. W. L.Oxidation of Orthocarboxycinnarnic Acid. By E. EHRLICH(Illonatsh. 10 574-577 ; compare Abstr. 1888 842).-The authorhas previously shown (Abstr. 1888 1306) that in alkaline solution,&naphthol when oxidised with a limited quantity of permanganate,gives rise to orthocarboxycinnamic acid COOH*CH:CH.CsH,*COOH ;whilst the employment of an excess of the oxidising agent leads tothe formation of orthocarboxyphenylglyoxylic acid,CO OH*C0.CsH4.C 0 OH.Thq former acid however is not to be regarded as an intermediate~wnduct for when a 2 per cent.solution of permangaiiate is slowly runi 1 1 tj) a solution of orthocarboxycinnamic acid (10 grams) and potash( I 0 grams) in water (1 litre) decolorisation ceases when about 80 percent. of the permanganate theoretically required to convert it intoorthocarboxyphenylglyoxylic acid has been added and the solutioncontains only orthobenzaldehydecarboxylic acid COH*C6Ho*COOH(yield 50 per cent.) which melts a t 98-99' reduces an ammoniacalsolution of silver.and furnishes a compound with phenylhydrazine,melting a t 107-108". The author has not succeeded in his endeavourto obtain orthobenzaldehydecarboxylic acid by the direct oxidation of/3-naphthol. G. 3'. M.Isomeric Derivatives of Ethylbeneene. By L. SEMPOTOWSKI(Ber. 22 2862-2G74).-When ethylbenzene is heated to boiling anequal volume of sulphuric acid added and then after cooling the massis treated with a small quantity of ice-cold water only para-ethyl-7,eueenesulphonic acid is formed ; this crystallises in long colourless,deliquescent needles is sliyhtly soluble in water and has a rough,bitter taste. The barium saZt (with H,O) forms colourless silky needles;the calcium salt silvery scales ; the coyper salt (with 4+H,O) light-bliie,glistening scales decomposing a t 170'; the cadmium salt (with 7H,O),large transparent quadratic plates ; the potassium salt (with +H,O),micaceous scales decomposing at 150".All these salts are soluble inwater. The sic@haniide C6H4Et.S02NH,[Et SO,NH = 1 41,crystallises from alcohol in flat micaceous prisms easily soluble inether sparingly so in water and melting at 109". The constitutionvas proved by the fusion of the potassium salt with potash whenparahydroxybenzoic acid was formed. With a shorter fusion para-etltyZpheno2 C6H4Et.0H was obtained ; this forms long needles whichmelt at 45-46' boil a t 21:-3-214" and are sparingly soluble in water.*It is very soluble in alcohol and ether and its aqueous solution givesa violet-grey coloration with ferric chloride and a jellowisli-whiteprecipitate with bromine-water.The metnsuZphoizic acid CsH,Et(S03H)*OH[Et S03H OH =1 3 41 is formed both at high and low temperatures. It.is a* Probably identical with the a-ethylphenol of Beilstein and Kuhlberg rind ofFittig and Kiesow.-AbstmrtorORQASIC CHEMtS'l'RY. 55reddish oil of phenol-like odour and miscible with water. The b a r i msalt forms colourless hexagonal plates decomposing a t 120" ; thepotassium salt silky needles ; the calcium saEt colourless needles. Onfusion with potash the acid yields protocatechuic acid proving thecorrectness of the constitution given.Netaparadihydroxyethylbenxene C6H,Et(OH) [Et OH OH =1 3 41 is a liquid boiling at 295" and soluble in water.Itsaqueous solution is coloured green by ferric chloride and this colourpasses on the addition of soda through blue to claret colour.Orthobyomethy lbenzenemetasulphonic acid [Et Br SOsH =1 2 3 or 51 was obtained by the sulphonation of bromethylbenzene.Its barium salt (with 3HzO) iorms colourless plates sparingly solublein cold water; its potassium salt (with $H,O) colourless scales ; andthe sulphamide glistening prisms melting at 104-105".Parabromethylbenzeneorthosulphonic acid similarly formed yields acrystalline barium salt (with 4H20) easily soluble i n water. The potas-sium salt forms easily soluble scales the sukhonamide large micaceousscales melting at 123-124".Barium orthoethylbenzenesulphonute (with H20) formed by debrom-inating the bromine-derivat'ive forms soluble scales ; the cadmiumsalt long soluble needles ; the potassium salt very soluble glisteningscales.Barium o~thoethylphenolrnetasulplLonate forms microscopic scales.Barium nteta-ethyll~en~zenesulplzor~nte (with 2H20) obtained by debromin-d i n g the bromine-derivative forms crystals easily soluble in water ;the potassium salt easily soluble scales ; the sulphonarnicle glisteningscales melting at 85-86" When fused with potash this acid yieldsmeto-ethylphenol which forms a colourless oil liquid at -20" andboiling at 202-204".Barium meta-ethylphenolsulphonate forms easily soluble crystals.L.T. T.Disulphones and Trisulphones. By E. FROMM (Annnlen 235,135-167) .-Baurnann and Escalcs (Abstr.1887 123) obtainedethylidenediethylsulphone by oxidising a-dithioethylpropionic acid.It is more conveniently prepared by acting on a mixhure of acetalde-hyde and ethyl mercaptan with zinc chloride. The resulting ethylmcrcaptal of acetaldehyde (b. p. 186") is oxidised by agitation with asolution of potassium permanganate containing sulphuric acid.E thylidenediethylsulphoiie melts at 75" and boils at 3.20" withdecomposition. The bromide melts at 115". Attempts to obtainsubstitution-products by the action of alkalis sodium ethoxide mer-captan or aniline on the bromide were unsuccessful (Abstr. 1888,357). Ethylidenediethylsulphone chloride CMeCl( S02Et) and sodiumphenylsulphini te are formed by the action of benzenesulphoniochloride on ethylidenediethylsulphone and sodium ethoxide.Thechloride can be prepared by exposing to direct sunlight for severaldays an aqueous solution of ethylidenediethylsulphone saturated withchlorine. It is deposited from an aqueous solution in needles whichmelt at 102-103". The iodide is prepared by boiling the disul-phone with an excess of iodine the crude product being treate56 ABSTRACTS OF CHESlICAT PAPERS.with a cold ~olution of sodium hydroxide then washed with coIdwater and finally recrystallised from boiling water. The iodidecrystallises in needles and melts at 128-129" ; a t a higher tempera-ture it gives off iodine.Diethylsulphonedimet hylmethane has been described by Baumann(Abstr. 1887 123). It can be prepared by the action of methyliodide on an alkaline aqueous solution of ethylidenediethylsulphone.Diethylsulphoneth ylrnethylmefhane is formed by boiling a mixture ofsodium ethoxide ethyl iodide and ethylidenediethylsulphone in aflask with a reflux condenser. It forms quadratic crystals and meltsat 76".The ethjl mercaptal of propaldehyde is lighter than water andboils between 196" and 200'.On oxidation with permanganate ityields propylidenediethylsulphone CH,*CH,.CH( SO,Ett) ; t'his crys-tallises in silky needles and melts a t 77-78". The ethyl mercaptalof isobiitaldehyde boils between 200 and 210"; i t is lighterthan water. lsobut~lidenedie~hylsulphone melts a t 94" and crystal-lises in needles; it is almost insoluble in cold water. The ethylmercapkal of benzaldehyde PhCH( SEt) is lighter than water,and boils with decomposition a t 250-253".Benz~lidenedieth~7sul-phone melts at 133-134"; it is insoluble in cold water but issoluble in cold solutions of the alkalis. €37 the action of sodiumethoxide and methyl iodide i t is converted into diethjlsulphone-methylmethane.Diethylsulrphonemethnne prepared by the oxidation of the ethylmercaptal of formaldehyde (from methylene chloride and sodinmethyl mercaptide) is identicai with the disulphone Raumann ob-tained from ethyl orthothioformate (dbstr. 1887 124). It isconverted into diethylsulphonedimethylmethane (sulphonal) by theaction of methyl iodide in the presence of an alkali; this melts a t12.5-126". D~ethillsul?,honedi~thyli,?ethniie is more difficult to prepare.It melts at 86-88'.An aqueous solution of diethylsulphonemethanereadily absorbs chlorine formiug the dichloride CCl,(SO,Et),. Itcrystallises in needles and melts a t 98-99'. The correspondingdiethylsulphonedibromomethane has already been described by Bau-mann (loc. cit.) .Diethyhdphonedi-iochmethane melts a t 176-177" b u t begins to turnbrown at 170". It crystallises in needles and is sparingly solnble inhot water.DiphenylsuZpphonemethane CH,(SO,Ph) prepared by oxidising thephenyl rnercaptal of formaldehyde crystallises in needles and me1 ts a t118-119". It is soluble in benzene and hot alcohol Diphenylsul-phonedimethylmethane melts at 128" and is soluble in hot alcohol.The corresponding diethyl-derivative melts at 130-131" and issparingly soluble in hot alcohol.When diethylsulphonedibromomethane (1 mol.) is boiled withphenyl mercaptan (I mol.) and an aqueous solution of sodium hydroxide(rather more than 3 mols.) phenyl bisulphide and diethylsulphone-thiophenylmethano are formed.The former is deposited from the solu-tion on cooling whilst the latter separates out on acidifying the filtrate ;i t is washed with cold water and recrystallised from absolute alcoholORGANIC CHEIJTSTR Y. 57Diethylsulphonethiophenylmethane PhSCH( S02Et) crystallises inplates and melts at 86". It is sparingly soluble in hot water and .morereadily soluble in a solution of sodium hydroxide. On oxidation byperman ganat e diet h y Isu 1 phonep h eny lsu Zpiokonern ethane,PhSO,*CH( SO,E t) 2,is produced.This trisulphone melts a t 1ti5". It is less soluble inalcohol than in water and is precipitated from its aqueous solution bystrong acids. The aqueous solution turns litmus red and decomposescarbonates. w. c. w.Phenylated Indoles. By W. H. TNCE (Annrzkn 253 35-44).-3'- Pheriylindole yields a crystalline picrate soluble in benzene ether,acetone and alcohol and melts at 105". The nitrosamine C14H,,N,0,forms minute yellow needles and melts a t 60-61"; it is freelysoluble in benzene acetone ether and chloroform but is insoluble inRolutioris of caustic alkalis. Phenylacetaldehydemethylphenylhydr-azone is formed by the interaction of phenylacetaldehyde and methyl-phenylhydrazine. The alcoliol ic solution of t h i s compound isdecomposed by an alcoholic solution of hydrogen chloride withdeposition of ammonium chloride.The liquid is neutralised withammonia and evaporated leaving a residue of impure 1'-3'-methyZ-phenylindole; t h i s is purified by solution in etherand distillation in avacuum. The pure indole dissolves i n benzene alcohol and ether ; itsalcoholic solution gives a blue colour to a pine chip moistened w i t hhjdrochloric acid. The picrate forms dark brown needles and meltsa t YO". Fischer and Schmidt (Abstr. 1888 958) pointed out that zincchloride a t 170" converts 3'-phenylindole into 2'-phenylindole. In thesame way zinc chloride a t 220" transforms 1'-3'-methylphenylindoleinto the 1'-2'-methylphenylindole described by Degen (Abstr.1887,149).3'-PhenyZ-13-nap72thindoZe is obtained by the action of alcoholichydrogen chloride on the hydrazone produced by the inter-action of phenylacetaldehyde a n d /3-naphthylhydrazine ; it crystal-lizes in glistening needles and melts with decomposition a t 211" issoluble in benzene alcohol ether acetone and hot light petroleum,and stains a pine chip green. The picrate forms reddish-brownneedles melts a t 219-120" and is holuble in benzene acetone,chloroform alcohol and ether. The 3'-phenyl-/3-naph t hindole is con-verted into 2'-phenyl-@-naphthindole by treatment with zinc chlorideat 130". 2'-Phenyl-P-naphthindole can be more conreniently prc-pared by the action of zinc chloride on acetophenone-p-naphthgl-hydrazone obtained by the condensation of acetopbenone andj?-naphthylhydrazine.The hydrazone melts a t 150" but it begins toturn brown a t 117". /3-?zLtphthindoZe melts a t 129-1S0° and is freelysoluble in alcohol ether and benzene. It forms a crystalline picrate(m. p. 165-166") which is soluble in benzene and ether.Benzidine- and Benzidinesulphone-sulphonic Acids. ByP. GRIESS and C. DUISBLRG (Rer. 22 2459-2474).-l?enzidiwe-sulphonic acid NH,.C6H4*C6H3( NH,) .SO,H is formed in small quanti-w. c. w58 ABSTRACTS OF CHEMICAL PAPERS.ties in the preparation of the disulphonic acid (compare Griess Abstr.,1881 428) and it can also be obtained in larger quantity by heatingbenzidine sulphate for 1& to 2 hours a t 1 70" with sulphuric acid mono-hydrate (about 6 parts).It is best prepared by heating benzidinesulphate at 170" for about 24 hours (D.R.-P. No. 44,779). It formsanhydrous crystals and is very sparingly soluble in boiling water andpractically insoluble in alcohol and ether; it is decomposed whenheated yielding a small quant'ity of benzidine. The hydrochloride,C12H,,N2S0,,HCl separates from hot dilute hydrochloric acid ingreyish nodular anhydrous crystals and is decomposed by boilingwater. The barium salt (C,2HlIN2S03)2Ba + 5H20 is moderatelyeasilg soluble in hot water and separates on cooling in small needlesor plates. The tetrazo-compound is obtained when an excess ofhydrochloric acid and a slight excess of sodium nitrite are added toan ice-cold alkaline solution of the sulphonic acid. It is readilysoluble in water and combines with phenols hydroxysulphonic acids,and aromatic hydroxycarboxy lic acids in alkaline solution and witharnines and amidosulphonic acids in sodium acetate solution formingyellow red and purple dyes.The compounds obtained with thehydroxycarbosylic acids phenols and amines respectirely aresparingly soluble ; the other dyes are readily soluble in water. Theyall dye unmordanted cotton wool in am alkaline bath and generallythe shade produced is more distinctly purple than that obtained withtetrazodiphenyl dyes but not so much so as that produced withtetrazodipheny ldisulphonic acid colouring matters.Benzidinemetadisulphonic acid (compare Griess Zoc. cit.) is bestprepared by heating benzidine sulphate (1 part) with sulphuric acid(2 parts) at 210" for 36 to 48 hours ; the yield of the pure compoundis 90 per cent.The azo-compounds derived from the tetrazo-derivativedo not dye vegetable fibres as readily as those obtained from thetetrazomonosulphonic acid but they have a more decided blueshade.Benzidine is not acted on by fuming sulphuric acid a t temperaturesbelow 100-120" but the azo-compounds obtained from tetrazo-diphenyl and naphthylamines react with fuming sulphuric acid inthe cold the hydrogen in the benzidine being substituted.Benzidinetrisulp7zoiLic acid C6H,(NH,)(S03H)2~C6H3(NH2)*S03H +2H20 is obtained together with the tetrasulphonic acid whenbenzidine sulphnte is heated for a long time at 180-190" with sul-phuric acid monohydrate or when a solution of benzidine in a littlehulphuric acid monohgdrate is heated at 160-1T0° poured intofuming sulphuric acid and heated again until a small portion givesonly a slight precipitate when treated with water.The product ispoured into water the solution filtered to separate small quantities ofthe disulphonic acid and neutralised with barium carbonate. Thebarium salt of the trisulphonic acid is readily soluble in cold water,and can be easily separated from the salt of the tetrasulphonic acid,which is only sparingly soluble. Benzidinetrisulphonic acid is pre-cipitated in soft colourless plates on adding concentrated hydro-chloric acid to a moderately concentrated solution of the barium salt.It is readily soluble in cold water but only sparingly i i i alcohol anORGANIC CHEMISTRY.59is reprecipihated from the alcoholic solution on adding ether; it iscompletely decomposed when heated.ci-ystallises in small colourless prisms and is precipitated from itscoilcentrated aqueous solution on adding alcohol.The ba.rium salt,(C,,H9N2S30,)2Ba3 + 12H~0,/2enzidiizetetrasulp~o~,ic acid,CsH?(NH,) (SO,H)z.CsHz(NH,) (SOB),,is precipitated in small colourless needles on adding hydrochloric acidt o a concentrated aqueous solution of the barium salt; it is very readilysoluble in cold water and is also soluble in alcohol. The barium salt,Cl?H8S10,,Ba + €?H,O cryst,allises in colourless needles or prisms,aiid is very sparingly soluble in hot water and insoluble in alcohol.Benzidin esulp hone ?6H3(NH2)>SO? is best prepared by graduallyadding benzidine sulphate (1 part) to a 20 per cent.sulphnric acidsolution of sulphnric anhydride. and heating the mixture on the water-bath until i t is free from unchanged benzidine ; the product is pouredon to ice and the benzidinesulphone sulphate is separated by filtrntiouand decomposed with soda. It crystallises in very small yellow,anhydrous needles melts above 350° and is almost insoluble in boil-ing water and insoluble in alcohol ether and benzene. The salts aredecomposed by water. The hydrochloride C12HloN2S02,2HC1 crystal-lises from hot dilute hydrochloric acid in which it is moderatelyeasily soluble in almost colourless plates.crptallises in grey or colourless needles or plates and is onlysparingly soluble in hot dilute sulphuric acid.The platinochZoridecrystallises in small dark yellow plates and is insoluble in water.,4 h ydroxybenzidine C12HllN2.0H is formed when the sulphone isheated a t 180" with caustic soda; it is a grey compound verysparingly soluble i n water but readily i n soda. The sulphate andl~ydrochloride are sparingly soluble in water.When benzidinesulphoiie hydrochloride is treated with sodiumnit'rite in aqueous Eolution and the resulting brown amorphous,tetrazo-compound reduced with stannous chloride and hydrochloricacid the hydrazine is obtained in small yellow needles sparinglysoluble in water. The latter is decomposed when boiled with coppersulphate solution yielding a diphenylenesulphonic acid melting a t2:'8" and identical with the compound obtained by Stenhouse(Annalen 156 332) from diphenylene sulphide.The azo-dyes obtained from benzidinesulphone differ from those ofbenzidine and benzidinesulp honic acids in possessing a marked blueshade.C,H3(NH,)The s u b h a t e ,CVZHIJ?~SO~,H2SOd + 1iH20,Beizzidi~~s.1Llphone~z~Z~~onic acid S03H-C6H2(NH2) <c6H3(NH2)> so -is formed together with the di- tri- and tetra-sulphonic -acid whenthe sulphone is heated with fuming sulphuric acid a t temperaturesabove 100'.The crude product is boured 01 to ice and after keep60 Al3Sl'RACTS OF CIIENICAL PAPERS.i n g for some time the solution is filtered; the tri- and tetra-hulphonicacids being readily soluble in cold water pass into the filtrate whilstthe mono- and di-sulphonic acid which are only sparingly soluble,remain ou the filter.The residue is dissolved in soda and the mono-sulphonic acid is precipitated from the filtered solution by addingacetic acid ; the disulphonic acid in the filtrate is then precipitatedby adding a large excess of hydrochloric or sulphuric acid. Benzi-dinesulphonesulphonic acid crystallises from hot water in which it isonly sparingly soluble in small light-yellow needles and is almostinsoluble in alcohol. The tetrazo-derivative is a reddish.brown,amorphous compound ; i t combines with amines phenols and withtheir carboxglic and sulphonic acids forming dyes which are of aredder shade and are much more sparingly soluble than those derivedfrom benzidinesulphonedisulphonic acid (see below).The ccr Zciumsalt (Cl,H,NTS20,)2Ca + S&H20 crystallises in small yellow needles,and is readily soluble in hot water but only moderately so inboiling alcohol and sparingly in cold water. The barium salt (with3+H,O) crystallises in small golden needles and is more sparinglysoluble in water than the calzium salt.Ben zidinesu @ honedisdphon ic acid,1$H,O separates in small light-yellow needles when a boilingaqueous solution is evaporated. It is inodermtely easily soluble inhot water but only sparingly in alcohol and almost insoluble in coldhydrochloric or sulphuric acid. The tetruzo-compound is a light-yellow voluminous substance ; i t combines with naphthols andnaphttolsulphonic acids yielding purple to violet dyes and withnaphthylamines and naphthylaminesulphonic acid Porming red orbluish-violet colouring matters.It yields beautiful reddish-violet orindigo-blue azo-dyes (sulphoneazurines) wi tli alkyl- and phenyl-naphthylamines. The calcium salt CI2H,N2S3O8Ca + i H 2 0 crystal-lises in yellow needles or plates and is readily soluble in hot butorily sparingly in cold water and insoluble in alcohol. The bariumsalt (with 4iH,O) crystallises in needles or very small prisms and isinsoluble in alcohol and only very sparingly soluble in boiling water.The sodium salt crjstallises from hot concentrated aqueous solu-tions in long yellow needles and is only sparingly soluble in coldwater.Orthotolidine yields analogous compounds to those obtained frombenzidine under the same conditions.Ol.thotoliJirnesziZphon~c acid isvwy sparingly soluble in water and does not crystallise readily. Thetetmzo-derivative is readily soluble in water. The barium salt loses4 mols. H,O when dried a t 150". The disuZpyhonic acid crystallisesfrom hot concentrated aqueous solutions in small colourless needles,and is readily soluble in hot water. The tetrazo-derivative is insolublein water. The salts are moderately emily soluble in water; thesodium salt crystallises in cuhes (with 4H,O) the ctcbium salt in plates(with 5H20) and the barium salt in needles (with 3H20).Tolidinesdphone is a greenish-yellow amorphous compound thesalts OF which are very similar to those of benzidinesulphone (D.R.-P.,No.44,784). F. S. K.>so + yJL(NH,) (S0,H)C,H,(NH,)(SO,HORC INIC CHEMISTRP. 61p-Naphthylhydrazine. By F. HAIJFF (Awnalen 253,24-35).-The derivatives of p-naphthylhgdrazine bear a close resemblance tothe corresponding phenylhydrazine-derivatives. The acetyl-deriva-tire Cl,,H7*N2H,Ac. prepared by boiling p-naphthylhydrazine withglacial acetic acid for several hours in a reflux apparatus formscolourless needles soluble in alcohol chloroform and benzene andmelts a t 164-165". Renzoylnnphthylhydruzine C,,H,*N~H,BZ is ob-tained on adding benzoic chloride to an ethereal solution of naphthyl-Iiydrazine (3 mols.) ; naphthylhydrazine hydrochloride is precipitated,and the filtrate on being evaporated and the residus treated with ahot dilute solution of sodiiim hydroxide to remove unaltered benzoicchloride leaves the hg drazine.When pure it crystallises in needles,melts at 154-155" and is soluble in hot alcohol ether benzene andchloroform. I n order to introduce a second benzoyl-group into thepreceding compound it is necessary t o act on it with beuzoic chlorideat a high temperature. The dibenzoyl-derivative C'10H7.N2HB~2 meltsa t 162-163".B-NaphthyZsemicarbazide C1nH7*N?H2*CO*NHz prepared by theaction of potassium cyanate on naphthylhydrazine hydrochloride issoluble in hot alcohol and acetic acid ; i t melts at 220" (uncorr.) andresembles the corresponding phenyl-derivative in its chemical pro-perties. It is decomposed by the action of hydrochloric acid insealed tubes at 140° yielding naphthazine which has previously beendescribed by Witt (Abstr.1887 153).P-Naphthy Zthiosemicarbazide C,oH7*N2H2*CS*NHz is obtained by boil-i n g an alcoholic solution containing equal parts by weight of naphthyl-hydrazine hydrochloride and ammonium thiocyanate. This substancemelts at 201 -202" (uiicorr.) and is soluble in hot aniline and alcohol.It is decomposed by hydrochloric acid in sealed tubes at 130-140",NHyielding napht~~y Zthiocarbizine CIOH7N< & . The carbizine meltsat 2.53-2.54" and crystallises in plates. It is solublc in warmalcohol and forms a crystalline hydrochloride and platinochloride.A violet precipitate is formed when bleaching powder is added to thealcoholic solution of the base.Naphthylhydrazine naphthylthiocarbazin~te,C,,H7*N2H2*C i3.S H,N,H,*Cl,H,,cry$tallises in plates and melts with decomposition at 145".It issoluble in warm alcohol.Ethyl-P-naphthylhydrazine is prepared by the action of ethyliodide (2 mols.) on naphthylhydrazine in alcoholic solution. I t is apale-yellow oil freely soluble in alcohol ether benzene and chloro-form. I t reduces warm Fehling's solution. The solution in ch1or.o-form is slowly decomposed by mercuric oxide yielding naphthylethyl-am i lie. w. c. w.Derivatives. of p-Naphthylhydrazine. By A. H [LLRINGHAUS(per. 22,2656-26.57).-ln reference to Hanff's work on th:s subject(preceding Abstract) the author states that he has also recentl6% ABSTRACTS OF CHEMICAL PAPERS.obtained the acetyl-derivative the semicarbazide and the thiosemi-carbazide. L.T. T.Derivatives of the Two Isomeric NaphthenylamidoximesBy E. RICHTER (Ber. 22 2449-2459; compare Abstr. 1887,374 also Ekstrand ibid. 373).-P-Napthenylamidoxime (m. p. 150)is readily soluble in alcohol and ether but only moderately easily inbenzene and chloroform and insoluble in light petroleum. The COT-responding a-compound (m. p. 148-149") resembles the /?-deriva-tive in its behaviour with solvents.Benzoy 1-P-naphthenylamidoxime C,oH,*C(NH,):NOBz prepared byheating the amidoxirne with benzoic chloride crystallises from hotalcohol in colourless needles melts at 179' and is only sparinglysoluble in cold alcohol ether benzene chloroform and light petroleurn,insoluble in water.NO Naphtlteiaylbenzenylazoaime ClOH,*C< - N>CPh is formed whenthe preceding coinpound is boiled with water dilute acids or diluh:alkalis or when i t is treated with concentrated sulphuric acid.I tcrystallises from dilute alcohol in colourless plates melts a t 116" aildis readily soluble in alcohol ether benzene chloroform and lightpetroleum but almost insoluble in water.Acetyl-P-naphtheny lamidoxime CI:,H,2N20 crystallises from alcoholor benzene in yellowish needles melts a t 154" and is only sparinglysoluble in ether chloroform a1.d light petroleum and insoluble inwater ; when boiled with water or when treated with concentratedsulphuric acid it is converted into the azoxime melting at 85"(compare Ekstrand Zoc. cit.).Ethyl-P-napht hen y larnidoxirnecarboxy late C10H,*C ( NH2) :NOC OOE t,separates from alcohol in colourless needles melts a t 121" and is readilysoluble in alcohol ether benzene chloroform and acids but verysparingly in light petroleum and insoluble in water and alkalis.NO P-Nap hthen y lcarbon y limidoxime C > C 0 cry s tallisesfrom hot benzene in cclourless needles melts a t 216" and is mode-rately soluble in alcohol ether and chloroform but sparingly inbenzene and hot water.The sodium-derivative is crystalline. In anaqueous solution of the ammonium-derivative lead acetate produce? awhite and copper sulphate an apple-green precipitate.P-Naphthe?j ylamidethoxime CIOH7.C ( NH2):NOEt crystallises fromdilute alcohol in colourless needles melts a t 74-75" and is readilysoluble in alcohol ether benzene chloroform light petroleum andhydrochloric acid but very sparingly in water and insoluble inalkalis.Ethylidene-@-naphthenylamidoxime C,oH,*C<NH>CHXe NO pre-pared by dissolving the amidoxime in acetaldehyde crystallises fromhot water in colourless needles melting at 121-122".It is readilysoluble in alcohol ether benzene and light petroleum very sparinglysoluble in cold water and insoluble in acids aud alkalisORGANIC CHEBIISTRY. 63NO Acet oe t heny I- &nap ht heny lazoxime C ,,H7 C<- N>C* C HzAc is f ovmedby boiling the amidoxime with ethyl acetoacetate ; it crystallises fromhot water in nacreous plates melts a t 108-109" and is soluble iualcohol ether benzene and chloroform but insoluble in lightpetroleum.Acetyl-a-na~hthenylamidoxirrLe crystallises from dilute alcohol incolourless needles melts at 129" and is insoluble in water but readilysoluble in alcohol ether benzene and chloroform ; when treated withconcentrated sulphuric acid or when boiled wit.h water it is convertedinto the azoxime (compare Ekstrand Zoc.cit.).Ethyl-a-napht?~enylanaidoxi~mecarbozylatu crystallises in colourlessneedles melts at 11l0 and is readily soluble in alcohol ether benzene,and chloroform but only sparingly in light petroleum and insolnblein water.a- Naphthen.yZcarbonylimidoxirne prepared by boiling the precedingcompound wit.h water or alkalis crystallises from dilute alcohol incolourless needles melts at 189" and is readily soluble in alcohol bntonly sparingly in ether benzene and chloroform and insoluble inlight petroleum and water.I n aqueous solutions of the ammonium-derivative lead acetate produces a white and copper sulphate a greenprecipitate. F. S. K.Acetyl- and Ethyl-derivatives of Camphonitrophenol. By P.CAZENEUVE (Bull. SOC. Chiin. C3] 1 467-469 ; compare Abstr. 1889,CsN02 618) .-The acetyl-derivative of camphonitrophenol C8H14<l 1 C*OAc)after saponification and subsequent saturation with slight excess ofhydrogen chloride gives with ferric chloride a violet-red coloration,CH*N02 which indicates the forniation of the compound C,H,,< IThe ethyl-derivative CsHld<E.oEt is made by heating sodiumcamphonitrophenoxide with excess oE ethyl iodide in sealed tubesat 120" for three hours; after separation of sodium iodide the liquidis evaporated to dryness and the residue crystallised from benzene.The compound forms large colourless flat crystals which melt at54" and decompose on distillation.C(OH)2T. G.N.Camphonitrophenol Phosphate. By P. CAZENEUVE (BUZZ. SOC.Chirn. [ 3],1,46!b--47 1) .-The normal phosphate ( C,,t€,,NO,),PO isprepared by boiling camphonitrophenol with phosphoras trichloride forseveral hours. It exists as an amorphous yellowish insoluble sub-stance which when heated decomposes without melting. Nitrophenolforms an analogous compound ( C6K4NO,),PO with phosphorus pent+chloride only traces of metachloronitrobenzene being simultaneoiislyproduced. This reaction confirms the constitution previously giveuto camphonitrophenol.T. G. N64 ABSTRXCTS O F CHEJIICAL PAPERSCamphonitrophenol Benzoate and Phthalate. B J P. CAZE-C-NO,N EUVE (BUZZ. Soc. Chim. [3] 1,471-4B).-The benzoate C,H,,< I I C-OBzi R prepared by the reaction of equal parts of camphonitrophenol andbenzoic chloride at 100' ; it forms small crystals which are insolublein water but soluble in hot alcohol ether and benzene; these melta t 131" ; and partially volatilise a t 150" without decomposing. Onsaponification with alcoholic potash it yields potassium benzoate andthe compound C,N,,< IC-NO,C(OH)?'Phthalic chloride by a similar reaction forms a compound,(N0o.C 10Hl,o)J&H,02,which melts at 275" with slight decomposition. T. G. N.Quercetin-derivatives.By J. HERZIG (LVonatsh. 10 561-567 ;compare Abst)r. 11388 1309) .-In a preyious communication theauthor has called attention to the fact that pure xanthorhamnin ienot the sole product obtained from Persian-berries by the method ofLiebermann and Hijrmann (Abstr. 1879 'L71). It is now shownthat besides xanthorhamnin the berries cont.ain a glucoside ofrhamnetin or some nnstable molecular compound of the glucosides ofrhamnetin and quercetin. This result is in accordance with the factthat Schutzenberger obtained two glucosides ( a - and P-rhamnin)from Persian-berries. His a-rhamnetin (from z-rhamnin) is evidentlyidentical with rhamnetin his P-rhamnetin (from p-rhamnin) withquercetia. G. T. M.Scutellarin one of the Constituents of Scutellaria 19nceo-lwia.By I). TAKAHASHI (Chem. Centr. 1889 ii 100.)-The rootof ScuteZZariu Zunceularia one of the labiatse is used medicinally inChina and Japan. By extracting the root with ether agitating theether extract with sodium hydroxide and acidifying the alkaline solu-tion a yellow. flocculent substance scutellnrin is obtained. It formsodourless and tasteless shining flat yellow needles melts at199-199*5" is insoluble in cold little soluble in hot water veryreadily soluble in alcohol ether chloroform light petroleum andcarbqn bisulphide ; soluble in sodium hydroxide and carbonatesolut,ions ,but carbonic anhydride is not expelled from the latter.It dissolves in concentrated sulphuric acid with a yellow colora-tinn and water reprenipitates the substance unchanged.It dis-solves in nitric acid with red coloration and in like manlier in a solu-tion of sulphuric acid and potassium nitrite. Fehling's solutionis llot reduced by it even after boiling with hydrochloric acid.J t does not combine with phenylhydrazine ; neither silver nitratenor lead acetate precipitates it from its alcoholic solution but solu-tions of lead and copper acetates produce a yellow-red precipitatewith the dcoholic solution. When treated with bromine in carbonbisulphide solution a substance crystdlising in yellowish needles isformed ; the determiriation of bromine in it however! gare unsatis-factory results. The el2mentary analysis of scutellarin give figureORGANIC CHEMISTRY. 65which corresponded with the formula CloH,03 ; it contains neithernitrogen nor water of combination.5 grams of scutellarin producedno effect when administered to a dog in an emulsion of milk andgum arabia The author believes it to be a phenol and possiblyan isomeride of juglone. J. W. L.Crystallised Digitalin. Ry ARNAUP (Compt. rend. 109 6i9-682) .-Digitalin prepared by Nativelle's method from the digitalis ofthe Vosges formed very thin brilliant white rectangular lamelh,which melt at 243" dissolve in absolute alcohol to the extent of 0.650part in 100 at 14" and also contrary to the statement of Schmiede-berg dissolve in boiling benzene. When subjected to fractioual solution,the melting points of the different fractions varied only between242" and 245".A second quantity prepared by Adrian melted at 245-246" andwhen dissolved fractionally in alcohol and benzene the meltingpoints varied only between 243 and 245" as with the first sample.Digitalin is a distinct chemical individual and it is not necessaryto denote it by any name such as digitoxin.It seems to be the typt.of a large group of compounds. C. H. B.Dihydropyrroline. By F. ANPERLINI (Ber. 22 2512-2515).-Dihydropyrroline hydrochloride is decomposed when heated givingroff vapours which colour pine-wood red ; it is partially decomposedby concentrated hydrochloric acid at 130-140". The uuroch loride.C4NH7,HAuC14 crystallises from cold water in small prisms melts at152' and is slowly decomposed when boiled with water. The picrate,CdNH7,C6H3N307 separates from water in yellow crystals melts at156" arid is readily soluble in alcohol and water.Benzoy Zdihydropyrroline C4NH6Bz prepared by heating dihydro-pyrroline hydrochloride with benzoic chloride at 110" is an oilyliquid boils at 160-161" (2 mm.) and is miscible with alcoholand ether but is insoluble in water.It dissolves freely in con-centrated hydrochloric acid yielding a salt which does not crptallisereadily.Benz y Zdihy drop yrroline C4NH6*C H,Ph prepared by treating di -hydropyrroline with benzyl chloride boils at 150". The aurochloride,CIIH,,N,HAnCl~ crystallises from water in yellow needles melting. at111". E. S . K.Derivatives of Alkylpyrrolines. By C. U. ZANETTI (Bey. 22,2515-2519 ; cornrare Ciamician and Zanetti Abstr.1889 727).-1-Ethylpyrroline boils at 129-130" (762 mm. corr.). The tetra-bromide melts at 83" and is converted into ethyl dibromomaleimide(m..p. 93-94") by cold nitric acid of sp. gr. 1.49. The diacGtyZ-derivative C4NHzEtAc is a crystalline compound melts at 58-59',boils a t about 183" (29 mm.) and is readily soluble in alcohol ether,benzene light petroleum and warm water.When the mixture of c-ethylpyrrolinep boiling at 150" (compareCiamician and Zanetti Zoc. cit.) is treated with acetic anhydrideand sodium acet'ate an oil is obtained which can be separated by frac-VOL. LVIII. 66 ABSTRACTS OF CHEXICAL PAPERS.tional distillation into a portion boiling at 210-235" and a portionbuiling at 240-255". The former is volatile with steam and has thecomposition and properties of an 1-acetyl-c-ethylpyrrolins C4NH3EtAc.The latter after having been boiled with potash and repeatedlydistilled in order to free it from 1-acetyl derivatives solidifies parti-ally when exposed to long continued cold and can thus be separatedinto its constituents ; the crystalline substance is an acetyl-deriva-tive melting a t 42-44" probably identical with the compound(m.p. 47") obtained by Dennstedt a a d Zimmermann from c-ethyl-pyrroline (compare Abstr. 1886 1043). Both the liquid and thesolid compound give a silver-derivative which has the compositionl-Propylpyrroliije C4NH4Pr is obtained in small quantities whenpotassium pyrroline is treated with propyl iodide but isomerides andother compounds are also formed; it) is a colourless oil hoiling a t145-5-146*5" (755.8 mm.).Nitropyrroline-a-carboxylic Acids.By F. ANDERLINI (Ber.,22 %503-2506).-Methyl nitropyrroline-a-carbox~lafe,NO,-C,NH,*COOMe,(m. p. 197") is formed together with an isomeride (m.p. 179") andother nitro-compounds when finely divided methyl pyrroline-d-carboxylate is gradually added to ice-cold nitric acid of sp. gr. 1.5aud the solution poured into cold water; after neutralising withsoda and adding a lit'tle sodium carbonate the solution is extractedwith ether It crystallises from boiling water in coloudess needlesmelting a t 197". The corresponding acid N0,.C4NH,COOH ob-tained by hydrolysing the ethereal salt with potash crystallises fromwater with 1 mol. H,O in light-yellow needles and is readily solublein alcohol ether and hot water but only sparingly in benzene andcold water.I t loses its water when kept Over snlphuric acid underreduced pressure and the anhydrous crystals melt a t 217".Nethyl nitropyrroline-a-carboxylate (m. p. 179") is obtained togetherwith other nitro-compounds when the alkaline solution from whichthe isomeride (m. p. 197") has been extracted is acidified and thenextracted with ether. It can be isolated by hactionally cry stallisingthe crude product from water. It separates from dilute alcohol inyellow needles melting at 179". The corresponding acid crystallisesfrom hot water with 1 mol. H,O in light-yellow needles and is readilysoluble in alcohol ether and hot water and moderately so in benzene,but .only sparingly in cold water.It loses its water when keptover sulphuric acid under reduced pressure the anhydrous compoundmelting a t 161".The mother-liquors from the preceding compound (m. p. 179")probably contain the third isomeride which has previously been pre-pared by Ciamician and Danesi (Abstr. 1882 875) from dinitro-pyrocolf but this compound could not be obtained in a purecondition. They also contain the methyl salt of a dinitropyrroline-carboxylic acid C4NH2(N02)2*COOMe ; this compound crystallisesfroin watler dilute alcohol and benzene in light-yellow plates meltinga t about 113". F. S. K.C,HioNOAg.F. S. KORGXSIC CHEJIISTRY. 67Molecular Weights of the Imidoanhydri 3es of Pyrroline-carboxylic and Indolecarboxylic Acids. By G.MAGNANLNI (Bw.,22 2j01-25Oq. Molecular weight determiuations by Raoult'smethod in naphthalene solution show that the molecular formula ofpyrocoll is C10H6N202 that of tetramethylpyrocoll ClIH,,N,02 thatof diacetylpyrocoll C14HloN20~ and that of the imidoanhydtide ofa-indolecarboxylic acid C18H10N202. The depression constant ofnaphthalene was taken as 82 according to Raoulb.Action of Methyl Iodide on Tetramethyldihydropyridine.By F. ANDERLINI (Ber. 22 250d-f251l).-Pentamethyldihydro-py r i din e h y d riod i il e is obtained w h en t e trame t hy Id i hy d rop y rid in e(b. p. 158") is treated with methyl iodide (compare Cilimician andAnderlini Abstr. 1889 728) The free base boils at 188-190"(45-46" ; 7 mm.).A bnse C12H?,N is formed when pentamethyldihydropyridine istreated with niethyl iodide in the cold and the resulting oily hy-driodide distilled with potash; the base was not isolated. Theuu?-ochZoride CI2Hz1N,HAuCl4 crystallises in thin golden needlesmelting a t 99-99.5".F.S. K.F. S. K.Synthesis of Oxypyridine and Piperidine Bases. By A.Lau~xsunc; (Ber. 22 2583-2590) .-a-Picolylalkins,is obtained as a thick brown syrup by the action of formaldehydeon a-picoline and is purified by distillation under 20-30 mm.pressure. It is a colourless syrup boils at 179" nnder 25 mm.pressure dissolves readily in water and alcohol sparingly in ether :i t is rather hygroscopic and can only be dried over fused potassiumcarbonate ; sp. gc". 1.111 a t 0". Theplcitinochloride (C7H9NO),,H,PtCl,,crystallises well in pristiis very readily soluble in hot water and meltsa t 170" with effervesceuce.The aurochioride crpstallises in well-formed crystals rather sparingly soluble iii water.Vi,t ylpyridirw C5NHI.C2HB prepared by distilling the above com-pound under higher pressure o r in preseiice of potash is a colourless,mobile liquid very readily soluble in alcohol ether and chloroform &c.,but only sparingly in water. It boils with decomposition a t 158-13:!at t.he ordinary pressure but distils without decomposition a t 79-82'under 29 mm. pressure ; sp. gr. = 0.9985 a t 0". The ylutinocldoride,(C,H7N)?,H2PtCI6 crystallises in needles or large plates melts a t 174"with decomposition and is rather readily solutle in water.Thechuimhloyide cadnzioiodide bismuth iodide and rnemwocll loride cryst,aI-lise well.a-YipecoZyZalTcine C,NHlo.CH2*CH2*OH obtained by the action ofsodium and alcohol t)n picolylalkine is a colourless crystalline baseTvhich melts at 31-32' aiid boils at 225-228'. It is very hygro-scopic and is readily soiuble water alcohol and ether. It is astrong base and turns red litmus blue. The yZutinocltZorit?e,(C,H,,NO),,H,PtCI crystallises in splendid large transparent crys-tals like gypsum and melts at 158".f 68 ABSTRACTS OF CHEMICAL PAPERS.a-Meth?/ZpipecolineaZX;ine C,NH,Me*CH,2*CH2*OH is formed whena-pipecolylalkine dissolved i n metlipl iodide is Lrmted with methyliodide and sodium at the ordinary temperature. When the methyliodide has disappeared the alcohol is evaporated the residue re-peatedly extracted with ether the base converted into the hydro-chloride and warmed slightly with sodium nitrite.The nitrosaminewhich separates is removed by ether. The hydrochloride is thentreated with potash and the tertiary base is extracted with ether anddried with potash. The aurochloride is crystalline ; the plafino-chloride cadmioiodide and periodide were also prepared.Vin ylpipwidine C,NH,,;C,H (?) is obtained from pipecolylalkinby the method previously employed for the preparation of tropidinefrom tropine (Annalen 217 118). It is a colourless liquid boils a t146-148" is readily soluble in water and has an odour of tropidineaiid coniine. The aurochloride and p i c m t e crjstallise well and arerather soluble in water.a-Picolyl~2ethylaIkine7 C5NH4*CE3*CHMe*OH is formed in a mannerhimilar to a-picolylalkine from a-picoline and acetaldehyde and ispurified by means of the platinochloride.It is yellowish boils a t176-181" under 18 mm. pressure and is readily soluble in water,alcohol and chloroform sparingly in ether. The plrctinochlorz'de,( CRHl,NO)2,H2PtC16 crystallises from hot water in small plates whichmelt R t 189" with decomposition ; the auroohEoride crystallises well.a-Pipecolylmetl~ylalkit~e C,NH,,*CH,*CHMe*OH melts at 47" boilsat 224-226" and is readily solnble in water alcohol and ether,The platinochloride melts at 149". I n its properties the base resemhlesconydrine with which it is isomeric.N. H. M.Hydroxymetadiazines (Hydrsxypyrimidines). By E. v. ME YE^^(J. pr. Chem. [2 ],40 303-304) .-Amidomethyldiphenylmetadiazine(Abstr. 1889 578) melts at 1G8" not 172" ; it can also be obtainedby acting on a mixture of ethyl cyanide and phenyl cyanide withsodium o r sodium ethoxide.Hydroxymethyldiphenylmeta#diazine (loc. cit.) melts at 250" not256" ; it can also be obtained by the condensation of benzamidine andethyl methylbenzoylacetate. By heating it with alkaline potassiumpermanganate adding dilute hydrochloric acid to the colourlew solu-tion dissolving the precipitate in weak ammonia filtering and againprecipitating with hydrochloric acid a hy droe ydiphenylmetadiazinecar-boxylic acid C P h < ~ ~ ~ ~ ~ C C O O H is obtained ; this crystallisesfrom alcohol in beautiful pale-yellow prisms melting at 236" withevolution of carbonic anhydride.When heated in a diphenylaminebath at 250" until evolution of carbonic anhydride ceases it leavesa yellow crystalline residue mostly soluble in potash ; if the preci-pitate obtained by adding hydrochloric acid to this potash solutionis digested with weak ammonia and crystallised from alcohol yellowishslender needles CI6Hl2NZO which melt a t 280.5" (uncorr.) are ob-tained. These appear to be identicad with Pinner's diphenylhydroxy-pyrimidine (Abstr. 1889 lOOS) which melts at 284"ORGANIC CHEYISTRT. 69N ='CEt Hydrozymethylefhylmet?~ ylmetadiazine CMeGN ,c (bH)>CMe isobtained from acetamidine and ethyl propionylpropionate ; it meltsat 167*5" and is isomeric with the hydroxy-base of cyanmetthethinemelting at 150" (Abstr.1885,646). A. G. B.Pyrimidimes. By A. PIXNER (Rer. 22 2609-2626 ;. compareAbstr. 1889 1006) .-The formation of the pyrimidines appears totake place in three stages. Employing benzamidine and ethylacetoacetate as examples these stages are as follows :-I. NHXPh-XH + COOEt*CH,-COMe =NH CPh*NH*C 0 *CH2*COMe + EtO H.The ethyloxalylacetylbenzamidine already described (Abstr. 1889,1009) is the first-stage product in the formation of phenylhydroxy-pyrimidinecarboxyiic acid and may be easily converted into the latterby the action of soda. The compound obtained at the same timeand melting at 263" is phenyIhydroxypyvimidinecarboxytbenzamidine,N<g[k@-$>C*CO*N H C Ph N H the benzamidine haviii g reactedwith the second carboxyl-group of the acetoxalate.It is converted int,othe above carboxylic acid by the action of soda. As already noted(Zoc. cit.) the free acid melts with decGmposition at 247" ; carbonicanhydride being evolved and phenylhydroxypyrimidine is formed.When benzamidine and ethyl acetomalonate react on one another,one carboxyl-group is separated and the same pyrimidine formed asis obtained from ethyl acetoacetate.When ethyl acetosuccinate benzamidine hydrochloride and sodiumhydroxide or potassium carbonate are mixed together two compoundsare obtained melting respectively at 1 7 8 O and 212". The former (m. p.1 7 Sv> is ethyl pheny lmet IL y lh y drox yp yrimidirkeacetnt e,-I t is easily soluble in alcohol ether and acetone sparingly in water,and crystallises in needles.When saponified with soda it yieldsphen.y lmethglhydrox ypyrimidineacetic m i d which crystallises in needles,melts a t 259" and is soluble in alcohol. The needles crystallising at212" have the formula C11H,oN202 and are probably succinylbenzimide,?H2'Co >N.CPh:NH. This compound forms the principal productCH,.COif caustic soda is used for liberating the benzamidine from its hydro-chloride in the reaction whilst if potassium carbonate is employed,the pyrimidine is the chief product70 ABSTRACTS OF CHEMICAL PAPERS.With ethyl acetylglutarate benzamidine yields etlbylphen yluz ethyl-h y droxyp yrimidine~r~p~ona t e C P h q N N:C(OH)/ - '' eW2 C H,*C H,. C 0 0 E t ,which crystallises in needles is soluble in alcohol ether and acetone,and melts a t 145".The.free acid forms a white powder almost in-soluble in water and alcohol and melting a t 215".When ethyl diacetosuccinate is mixed with benznmidine ethylphe~iylmethylhydroxypyrimidineacetate (m . p. 178") and phenyl-met h y 1 ace tony l h y droa yp yrimidine C P he" 6 gy>C. CH,G OM e,are formed. The latter is insoluble in acet,one soluble in alcohol ;it crvstallises in needles and melts at 225". The author was uuable toobtain the dipyrimidine C P h ~ N ~ c ~ o H ~ ~ - C ~ c I C H ~ ~ ~ CMe - N - CMewhich he had anticipated the second' aceiyl-group appearing alwajsto be separated before the pyrimidine formation set in.A mixture of ethyl succinylsuccinnte and benznmidine yields a sub-stance easily soliible in alcohol and melting at 272" and anotheralmost insoluble in the usual solvents.The fornier. tetra7~i/dl.owhe?.uZ- . I 1 .I?~ycirox~ketopui?kasdine ~:C(oH)'f?CHz*~Hz crystallises in needles.CPh Pr'*C'CH,-COThe latter owing t o its insolubilit'y could not be thoroughly purified,but appears to have the formula C,H,,N4O2 and to be dihydrocli-~:C(OH)*~.CH,*$*N = CPh It dis-plieny ldih y clrox yantetrazine,CPh=N*C*CH,.C*C(OH):Nsolves in boiling caustic soda yielding a crystalline sodiz~nz-deri.cat.iz;e,C,,H,,Na,N,O + 4Hz0.The amidine of acetonecyanhydrin OH.CMe2*C (gH,):NH yieldswith e thy1 a cetoa cetate hydroxyisoprop y lmrfh ylhy d ~ o x y p yrimiditie,OH.C?ile,.C~,:,(,,~~CH N-CMe crystallising in easily soluble needlesand meltingat 98".If ethyl benzoylacetate is employed instead ofthe ace t oacet a t e h y droxy isoprop y @ heny lhy &ox yp y rimidine,is formed. This crystallises in small glistening prisms sparinglysoluble in water easily so in the usual organic solvents and meltsat 198". L. T. T.Phenylhydrazonelevulinic Anhydride. By F. ACH (Annale??,253 44-57). Two compounds are formed by the action of phos-phorus pentachloride on phenylhydrazonelevulinic anhydride a t 150.One contains 2 atoms of hydrogen less than the anhydride and thesecond compound is a monochloro-substitution-product of the first.The crude product of the reaction is poured into water containing ice.In the course of 24 hours phenylmethylchloropyridazone is depositedin crystals.The mother-liquor is rendered alkaline and treated withether to extract the phenylrnethylpyridazone. The residue is redis-solved in 100 parts of boiling water to which a small quantity oORGANIC CHEMISTRY. 71hydrochloric acid is added. On cooling the chloro-substitution-pro-duct crystallises out and the base is extracted from the mother-liquoras before. It is finally purified by precipitation as the hydrochlorideby passing dry hydrogen chloride through its solution in benzene.NPh-N Phen?lEmeth?/~~yridazone CO< CH:CH>CMe is freely soluble iualcohol ether chloroform benzene and acetone melts at 81-82',and has feeble basic properties ; its salts are decomposed by water.By the action of sodium on the hot alcoholic solution a crystallinebase is produced which appears to have the composition C2,H,,N ; thismelts at 200" and yields a sparingly soluble platinochloride. Thesolution in dilute sulphuric acid acquires a violet-blue colour on theaddition of chromic or nitrous acid.Phenylmethylchloro/iyridazone C 0 < ~ ~ ~ ~ ~ > C M e crystallises illflat prisms and melts at 136-137".I t is freely soluble in hotalcohol chloroform benzene and acetone and also dissolves inmineral acids but is reprecipitated unaltered from the acid solutionsby water. The nitro-derivative melts at 210-213". The chlorine isdisplaced by ethoxyl by the action of alcoholic potassium hydroxide.PhenylmethyZathoxypyridazone melts at 14ti0 crystallises in flatprisms or plates and dissolves freely in hot alcohol benzene chloroform,acetone and in hot water and is also soluble in strong acids.It isdecomposed by heating at 125" in sealed tubes with hydrochloric acid,yielding phenyZnzethyLhydroxypyyidazone. The hydroxy-derivativecrystallises in needles and melts at 196". It is soluble in hot acetone,benzene and chloroform in strong mineral acids and in alkalis. Theaddition of ferric chloride to the hydrochloric acid solution producesa red-brown coloration which turns to carmine on dilution. At 170",hydrochloric acid converts the hydroxy-componnd into phenyrnethyl-pyrazolecarboaylic acid I I >C*COOH. The acid is soluble inhot. alcohol chloroform benzene ether and in strong mineral acids,C MeCHN-NPhmelts at 165-166" and decomposes at 200" yielding phenylmethyl-pyrazole >CH probably identical with the phenylmethyl-Me*CHN-NPhpyrazole described by Knorr (Abstr.1887 601).Phenylmethylpyrazole me1t.s at 34-36" and boils at 254-255"under 753 mm. pressure. It dissolves freely in ether alcohol chloro-form acetone benzene and light petroleum. The platinochlorideforms orange-coloured needle-s haped crystals sparingly soluble inwater. The pyrazole is convertled into the pyrazoline by the actionof sodium on its alcoholic solntion. The pyrazoline melts at 73-75"and distils without decomposition. It is soluble in ether alcohol andbenzene and gives the characteristic pyrazoline-colour reaction withferric chloride or chromic acid.w. c. w.Synthesis of Quinazoline-derivatives. By C. PAAL and 31.BUSCH (Ber. 22 2683-2702) .-The authors have studied the actionof orthonitrobenzyl chloride on the sodium-derivatives of form52 ABSTRACTS OF CEEhlICAL PAPERS.anilide and of scetanilide and of some of their homologues. The met-nnilides did not give satisfactory results but with the fornianilides thefollowing reactions (where R is an aromatic radicle) take place :-N0,-C6H4*CH2C1 + R-NNaaCOH = N0,.CsH4~CHz*NR~COH.On reduction the product yields quinazoline-derivatives,Action of Orthonitrobenzyl Chloride on Sodium Formanilide.-Sodiuinformanilide is prepared by adding sodium to a benzene solution of form-anilide and then a proportional quantity of orthonitrobenzyl chlorideis added.Orthonitrobenzy Iformanilide NOz.C6H4*CH,*NPh*COH issoluble in the usual organic solvents insoluble in water. It melts ati 7 " and forms yellow monosymmetric plates gixing the measure-ments a b c = 0.5477 1 1.085 and l3 = 69" 7'. This formanilidewas also obtained by boiling ort~honitrohenzylaniline (Lellmann andStickel Abstr. 1886 793) with formic acid. When reduced withzinc and acetic or. hydrochlonic acid phenyldihydropuinuzoline,C6H4<CH2.hph is formed ; this crystallises in hexagonal plates isN=CHalmost insoluble in water and alkalis easily soluble in mineral acids,alcohol ether &c. It melts at 95" and distils at a very high tem-perature with partial decomposition. When distilled with zinc-dust,i t yields equal quantities of aniline and benzonitrile.Its sulphate,( Cl4H,,N,),,H,SO4 + 2Hz0 crystallises from water in needles loseswater at 70" and melts at 79"; when free from water i t melts a t140-143" ; the hydrochloride + 'LH,O forms glistening needlesmelting a t 80" ; the anhydrous salt melts at 221" and is easily solublei n alcohol and ether. The pZatin.ochZoride forms yellow crystalsme1 ting a t 208" ; the aurochloride orange scales ; the sfunnochlol-ide,( ',4HlzN,,HSnC13 flat white needles or scales melting a t 130-134".When heated with methyl iodide in closed tubes at loo" the quinazolineyields three derivatives the methiodide periodide Cl4Hl2NZMeI,I,forming glistening golden-yellow scales melting at 157" ; the meth-iodide C14H12N2,Mel crystallising in white needles melting a t 170" ;and a third substance crystallising in prisms melting a t l80" whichappears to be a second isomeric rnethiodide. When oxidised withpotassium permangmate the quinazoline yields phenyllietodihydro-YH which crystdlises in almost colourless quinazoline C&<glistening scales or well-formed rhombic crystals giving the measure-ments a b c = 2.4228 1 3.2742.It melts at 139" and sublimeswithout decomposition. No hydroxylamine-derivative or phenyl-hydraaide could be obtained but with hydrazine (amidogen) it yields>C<&,; this forms y heny lketoh?y drazodihy dro quinazoline,white glistening needles which melt at 204" and in small quantities,siiblime without decomposition. The hydrochloride Cl4H,,NZO,HCl,crystallises in glistening scales and melts at 213-214" ; it loses itsCO*NPh'NH H*NPhN- CeHOHGAXIC CHEJJISTRY.73hydrogen chloride ah a moderate heat. The platinochloride crystal-lises in yellow needles melting above 300". When the keto-base ist,reated in alcoholic solution with sodium phen yltetrahydroq.uinazolir~e,c,H,< CH,.&Ph is formed which is soluble in organic solvents,cyystallises in white needles melts at 117" and distils at a high tem-perature without decomposition. It is only feebly basic its saltsdecomposirig on the addition of water. It yields a hydrochloride acrystalline aceto-derit,atice and 8 nitrosamine. An unstable inter-mediate product containing the (CH-OH) group appears to be formedalong with the tetrahydro-componnd but it could not be isolated,When oxidised with permanganate the tetrahydro-derivative is recon-verted into the keto-compound but both here and in the originalformation of the keto-derivative small quantities of a sparingly solublenitrogenous crystalline compound melting at 219" are formed.Actiosn of Orthonits.obenzy1 Chloride on Sodium Formqmrato1uide.-The reactions here are similar to those with formanilide.Ortho-?&itl'oI)enzy~ornzopas.a,tolziide N02*C6&*CH2*N (CaH,Me)*COH crys-tallises in pale yellow needles melting a t 79" and is easily soluble inthe usual organic solventls. It may also be easily prepared fromorthonitrobenzylparatoluidine (Lellniann and Stickel Zoc. &t.). Yura-NH. CH,AT- c1U I.( - w II t oZy ldih ydropuinazoline C6H4 < cH?.& C6H,Me 7 is easily soluble iiialcohol ether benzene and chloroform sparingly so in light pet8roleurn.It crystallises in glistening white scales melts at 120" and distils withpartial decomposition.Distilled witn zinc-dust. it yields the amine andnitrile like the phenyl-derivative. The hydrochloride with 2 mols.H20 forms flat white needles and melts at 85" the anhydrous salt at251" ; the platinoch loride forms glistening yellow needles melting a t216" ; the stannochloride sparingly soluble needles melting a t 165".Methyl iodide forms two derivatives namely the methiodide crystallis-ing in white needles melting a t 186" and green metallic needles whichappear to be the methiodide periodide. On oxidation the base yieldswhich crystal- iuaratolylketodihydropuiizazoliiLe C,H,< CO.k*CsH,Me'lises in micaceous needles sparingly soluble in boiling water easily inorganic solvents and melting at 146".The hydrochloride forms whiteneedles melting at 213-214" and is dissociated by slight rise in teni-perature ; the pltztinochloride forms golden yellow scales meltingabove 300". By oxidation pralietediii ydrop,LLinazolylbenzoic acid,P is produced as well as the above quinazo-line; the acid forms white crystals sparingly soluble in organic solvents,and melting at 320". The silver salt torms a white flocculent precipitate.Yarntoyltetrahydropuinazoline crystallises in white needles melts at127" and is easily soluble in chloroform and benzene sparingly inether and alcohol.It forms a red nitrosamine a white unstable hydro-chloride and a yellow unstable platinochloride.Action oj* Orthonitrobenzyl Chloride o n Sodiumformo-orthoto1uide.-The reactions are similar to those with the isomeric para-compouud.N I C HK F HC6H~<co~N.CaN,~COO74 ABSTRACTS OF CHEMICAL PAPERS.Orthonitrobenzylformo-orthotoluids forms a Sellow oil which melt,s at'i69 and decomposes on distillation. Orthotolyldi?iydroyuinazolineforms a yellow amorphous mass its platinochloride orange-yellowneedles me1 ting at 210" and its stannochloride and hydrochloridecould not be obtained in a crystalline form. When reduced in alco-holic solution with sodium the base appears t,o yield the tetrahydro-derivative but this was not obtained in a pure state.L. T. T.Hydrastine. By W. KERSTEIN (Chem. Centr. 1889 ii 91 fromZeit. Naturwiss. Halle 61 425-429).-According to the author'sexperiments hydrastine obtained from the root of Hydrastis cuncc-densis has the formula C21H2,N06 and forms colourless needles melt-ing at 132". The hydrochloride C21H,lN06,HCl and hydrobromide,C H,,NO HBr are white micro-crystallire salts ; the hydriodide istwo wnish- y el lo w.In addition to those reactions already described showing the rela-tion which exists between hydrastine and narcotiue the author findsthat by oxidation with potassium permanganate in acid solution,opianic acid and probably also cotarnine are formed. When dis-tilled in a current of steam niecotiine and trimethylamine areformed in the case of both these alkaloi'ds. On the other hand,they do not show any similarity in their behaviour towards aceticanhydride acetic chloride water under pressure or dilute sulphuricacid.From hydrastine ethiodide by the action of potassium hydroxidesolution ethylhydrlnstine is obtained ; it forms lemon-yellow crgstalswhich melt at 127". By the action of iodine hydrastine is split upinto opianic acid and hydrastonine ; the latter is distivguishedfrom tarconine methiodide in tha,t no formaldehyde is formed onboiling its icdide 31 hydroxide with barium hydi-oxide.In addition from the root of H?/drastis canndensis the author hasseparated phytosterin C,,H,O + H,O ; this forms plates melting a t13:3" the solution of which in acetic anhydride gives a red coloration,passing into intense blue with concentrated sulphuric acid.J. W. L.Formation of Optically Active Tropic Acids and OpticallyActive Atropines. By A. LADENBURG and C. HUNDT (Ber. 22,2 5 ~ ~ 2 5 9 2 ) .-A dilute aqueous alcoholic solution of quinine (1 mol.)was added to a hot aqueous solution of tropic acid (ni. p. 116-1 18-,1 mol.) and the whole evaporated down on a water-bath until crystal-lisation commenced. On cooling a quantity of dull white crystalsseparated (quinine dextrotropate) and on further evaporation of themother-liquor an oil separated which gradually solidified to hardcyystals of a glassy lustre (quinine kevotropate).Quinine dextrotropate melts a t 186-187". The free acid cryst allisesfrom ether in hard clear prisms and from water in clear plates,melts a t 127-128" and showed a rotatory power of 71.4".Quinine Zcevotyopate was not obtained quite pure ; i t melts a t 178"The free acid which was also not obtained pure melted at 123" andshowsd a rotatory power of 65-15'ORGANIC CEEMTSTRY. 75When treated with tropine and tropic acid (Aiznalen 206 274),both acids yield the corresponding atropines.Deztro-atropine cqstallises from alcohol in white lustrous needles,melts a t 110-lll" and has a rotatory power of + 10". The auro-c h l w i d e forms dull deep-yellow crystals melting a t 146-147".Lcmo-atropiua is a crystalline powder melting a t 111". The auro-chloride crystallises in lustrous needles and melts a t 246". The baseresembles hyoscyamine but the two are not identical which is due tothe fact that the latter base has two active asymmetrical carbon-atoms whilst the former has only one. N. H 31.Bases contained in the young Shoots of Solanum Tubero-sum. By R. FIRBAS (ilfonafsh. 10 541-56O).-The two products,the one crystalline and the other amorphous obtained in the prepara-tion of solanine from the young shoots of the potato are now shown,contrary to earlier views not to be chemically identical. The authornames the crystalline compound solanine. It has the formulaC52H,sN0,s,4&H,0 and when dried a t 100" appears to be anhydrous,or t o contain only half a molecule of water of crystullisation. Froma solution in 85 per cent. alcohol it crystallises in coloiirless needles,which melt a t 244" are almost insoluble in ether and alcohol and arereadily dissolved by dilute hydrochloric acid. Xolanidine hydro-chloride 3(C4,H6,N02,Hc1)Hcl + H,O or l&H?O is obtained byboiling solanine with a 2 per cent. solution of hydrochloric acid. Itis a slightly yellow powder which is only very sparingly soluble inwater and carbonises without melting when heated to 287". Simul-taneously with solanidine hydrochloride. a sugar is formed in accord-ance with the equation C52Ev3N0,8 = C40H6,N02 + BC6H1,0s +4H20.The amorphous substance obtained simultaneously with solanine,and which the author names solaiLeine has when dried a t loo" theformula C53Hs7N013 or C5,H,NOl3. The loss of weight on heating theair-dried compound a t 100" corresponds with the formula C,,H,,KO + 3 i or 4H,O. It is a yellow horny perfectly amorphons substance,melting a t 208" is more soluble in an 85 per cent. solution of alcoholthan is solanine and on treatment with hydroctloric acid yieldssolanidine and a sugar in accordance with the equation C52H83N013 +H,O = C4,H6,N0 + 2C6HI2O6.The sugar obtained by the hydrolysis of solanine and solanaineforms a yellow amorphous mass with a caramel-like odour dissolvesreadily in water and wood-spirit and has a specific rotatory power of[z]D = + 28.6%. With phenylhydrazine hydrochloride and sodiumacetate in aqueous solution i t forms a glucosazone melting at 199",and resembling the compounds obtained similarly from dextrose,levulose and several other sugars. With nitric acid it gives no recog-nisable trace of mucic or saccharic acids. The general behaviour ofthe sugar points to the conclusion that it is some other sugar thandextrose or a mixture of sugars.Solunidine has the formula C4,,H61N0 or C4,H&N02 and is obtainedfrom alcoholic solution in amorphous masses interspersed with needlesmelting a t 191". It dissolves readily in hot alcohol with difficulty i76 ABSTRACTS OF CHEMICAL PAPERS.ether and on treatment with excess of dilute sulphuric acid forms asulphate 3(C40H6,N02,H~SO~),H,s0 + 8H20 ; this crystallises inscaly plates melting at 247” and is readily soluble in water. Itsdiacetyl-derivative CmH5,02NAc2 crystallises in needles melting at203”. G. T. M.Cinnarnylcocaine from Coca Leaves. By C. LTEBERNANN(Ber. 22 2661-2662) .-Measurements of crystals and quantitativedecomposition determications are given to show that the cinnamyl-coea’ine which t>he author prepared synthetically from ecgonine isidentical with t h a t obtained by Giesel horn the coca leaf.L. T. T.Haematoporphyrin and Bilirubin. By If. v. NENCKI andA. ROTSCHY (Monatsh. 10 568-573 ; compare Abstr. 1858 304 and971) .-The authors suggest that Raoult’s method may be employedwith advantage to determine the molecular weights of unstablesubstances of organic origin and have investigated the practicabilityof the method in two cases. Making use of acetic acid and phenol assolvents hzematoporphyrin gave numbers varying bet ween 226 and331 which correspond with the simple formula C,6H,eN20 (mol.wt. = 286). I n the case of bilirubin ethylene dibromide and phenolwere used RS solvents. This compound has the same molecnlarformula and is consequently isomeric with hzematoporphyrin. Therange in the numbers obtained in both cases is due to the compoundsbeing only slightly dissolved by the solvents employed. The iso-merism of haematoporphyrin and bilirubrin is confirmed by the factthat on reduction with tin and hydrochloric acid two differenturobilins are obtained. G. T. 31