24 ABSTRACTS OF CHEMlCAL PAPERS. Organic Chemistry. Volatility of Methane-derivatives. By L. HENRY (Compt. rend., 103, 603-606) .-The volatility of methane-derivatives follows the same order as that of the substituted elements when the latter are arranged in natural families in the order of their atomic weights. The boiling point rises as the molecular weight increases, but the differences between the volatility of the methane-derivatives are much less than those between the boiling points of the electronegative elements which they contain. B. p. Diff. cl, gas ...... - 35") 96" Br, liquid .... + 63 I, solid . . , . . + 250 } O , ~ R S ........ - 181 N, gas. ...... - 193 S, solid ...... + 448) 629 P, solid ...... + 287}480 B. p. Diff. MeC1, gas .... - 23" } 27.5 Me20, gas .....- 23 } 60.0 4- } 50.0 Me3N, gas MeBr, gas .... + 4.5 MeI, liquid ... Me,S, liquid. .. + 37 Me3P, liquid.. . + 41 44 } 39'5 ..... The differences show that electronegative elements in the same natural family are far from being comparable in the free state, whilst ip methane-derivatives they may be regarded as existing under analogous physical conditions. I n each of the groups of methane-derivatives, the rise of the boiling point is not proportional to the increase in the molecular weight ; in fact the greater the increase in the molecular weight resulting from substitution, the less proportionally is the rise of the boiling point. The substitution of sulphur causes proportionally less rise in the boil- ing point than the substitution of oxygen, and the snbstitution of phosphorus less than the substitution of nitrogen, although sulphur and phosphorus are solids, whilst oxygen and nitrogen are gases.The atomic weights being nearly equal, the diminution of volatility resulting from substitution is greater the more strongly marked the electronegatire character of the substituted element, or, in other words, the more distinctly its properties differ from those of hydro- gen. This is well seen in the case of the nitrogen- and boipon-deriva- tives. Me3N, mol. wt. 59, a liquid boiling at 9.3". Me3B, mol. wt. 36, a gas which liquefies at -10" under a pressure of 3 atmos. This phenomenon is doubtless connected with the fact that the heat of combination of carbon with electronegative elements diminishes as the atomic weight of the latter increases.Sugars. By BERTHELOT (Compt. rend., 103, 533-537).--8 soh- tioh of invert sugar which had been kept for nearly 30 years, deposited spheroidal groups of radiating crystals, which when care- C. H. B.ORGANIC CHEMISTRY. 25 fully dried on filter-paper resembled purified glucose. The crystals have the composition C6H,,0e when anhydrous ; their reducing power is equal to that of glucose, and they are completely fermentable, but their rotatory power is only [a]= = + 32.2, or little more than half that of glucose. The crystals are a compound of glucose and levu- lose, in which one constituent behaves like water of crystallisation. The compound is decomposed by solvents ; its rotatory power shows that the ratio of levulose to glucose is 1 : 5.A similar compound prepared by G6lis has the rotatory power of +15O, which corresponds with a ratio of levulose to glucose of 1 : 3. The compound formed as an intermediate product in alcoholic fer- mentation is most probably formed by the union of one molecule of levulose with two of glucose, but it does not seem to have been ob- tained in crystals. In the process of extracting raffinose from cotton-seed cake, crys- tals were obtained which when dried on filter-paper without treatment with any solvent had all the properties of mellitose from the manna of eucalyptus. When the aqueous solution of this substance is treated with yeast, only half the sugar undergoes fermentation, and the liquid contains a non-fermentable sugar with the properties of eucalpe. If the mellitose is treated with boiling alcohol, it splits up into rafflnose, which crystallises after some time, and eucalyne, which remains in solution.An alcoholic solution of ra5nose and eucalyne when allowed to remain, deposits crystals which seem to be formed by the recom- bhation of the rnffinose with the eucalyne. Mellitose, which is widely diffused in the vegetable kingdom, is the result of the association of raffinose, a true saccliarose, with eucdyne, a non-fermentable carbohydrate. This association bears no resemblance to the union of glucoses to form saccharoses, and the constitution of mellitose is analogous to that of hydrates and alco- holates rather than to that of ethereal salts. C. H. B. Sugar formed in the Inversion of Lichens. By P. KLASON (Ber., 19, 2541).-Bauer showed (Abstir., 1886, 869) that dextrose is formed by inverting lichens.The author previously obtained the same results (Lund’s Pysiogr. Sallskops Minneskr., 1878, 61). Appa- rently no other sugar is formed in the inversion. N. H. M. Action of Dilute Acids on Grape-sugar and Fruit-sugar, By M. CONRAD and &I. GUTHZEIT (Ber., 19, 2569-2574).-According to Tollens and v. Grote (Annnnlen, 175, 181, and 206, 207), dextrose as well as levulose when boiled with sulphuric, or better with hydro- chloric acid, .Fields acetopropionic acid in very small quantity. Quantitative experiments on the decomposition of cane-sugar by hydrochloric acid, made by the authors (Abstr., 1885, 743), pointed to the formation of a small amount of acetopropionic acid from dex- trose.Experiments described in the present paper show that this view (the formation of acetopropionic acid chiefly from levulose) only holds good for the decomposition of cane-sugar with dilute sulphuric acid, and not with hydrochloric acid. Quantities of dextrose and levulose corresponding with 20 grams of26 ABSTRACTS OF OHEMICAL PAPERS. cane-sugar were heated for 17 hours with the same amounts of acid and water as those previously used (Zoc. cit.). 1. Decomposition with dilute sulphuric acid- Aceto- Humic propionic Formio substances. Dextrose. acid. acid. Dextrose.. .... 52.6 0.83 43-70 2.78 1.21 Levulose.. .... 32.6 13.78 - 16.78 6.46 Cane-sugar.. .. 100.0 = 14.61 43.70 19.56 7-87 2. Decomposition with dilute hydrochloric acid- Aceto-. Humic propionic Formic Dextrose., ....52.6 4-76 14-52 15.53 6-51 Levulose.. .... 52.6 10.65 - 16.28 8-78 substances. Dextrose. acid. acid. Cane-sugar, , . . 100.0 = 15.41 14-52 31.81 15.29 Decomposition of Milk-sugar by Dilute Hydrochloric Acid. By M. CONRAD and M. GUrHZElT (Bey., 19, 2575--2576).-The follow- ing results were obtained froni three experiments, in which 21, 21, and 10.5 grams of milk-sugar were heated with 50 C.C. of water and 4.87, 5.0, and 487 grams of hydrochloric acid respectively :- substances, (unchanged). acid. acid. N. H. M. Humic Milk-sugar Acetopropionic Pormic 1 ...... 3.68 5.54 6-29 2.39 2 ...... 3.94 - 5-80 2.24 3 ...... 1-60 L 3.32 1.33 In 2 and 3, the milk-sugar was not determined. N. H. M. Carbohydrates. By 0. WALLACE (Annalea, 234, 364-375).- The rhizome of the water lily, Iris pseudacorw, contains a peculiar Carbohydrate, called " irisin " by the author.Irkin, CaHl0O5 + HzO, closely resembles inulin, but is distinguished from the latter by its more powerfal action on polarised light; [dc]D = -49' 90 for a 2 per cent. solution of irisin, and [ a ] D = - 37" 27' for a soIution of inulin of the same strength. Fehling's Rolution is not reduced by irisin, but the carbohydrate is easily attacked by dilute acids, yielding levulose as the chief product. Irisin is four times as soluble as inulin in water s t 22". Under the microscope, the globules of irisin resemble the minute globules of inulin in size, but they do not exhibit double refraction. w. c. w. Animal Gum. By H. A. LANDWEHR ( P f t i i g ~ ' ~ arc hi^, 39,193- 204) .--The animal carbohydrates may be arranged in parallel groups with those occurring in the vegetable kingdom, and animal gum resembles vegetable gum in yielding oxrzlio acid after treatment with nitric acid.Mwiin was prepared It is obtained readily from m u c hORGANIC CHEMISTRY. 27 by precipiktion with acetic acid from an extract of submaxillary glands, made with a 1 per cent. sodium carbonate solution. The pre- oipitate was washed with weak acetic acid, and then dissolved in weak hydrochloric acid by the aid of heat. On neutralising with soda, a white flocculent preciFitate is obtained, which is increased in amount on the addition of sodium sulphate and boiling. The precipitate is collected and freed from salt by dialysis; i t consists of an ordinary proteid.The filtrate contains no nitrogen, biit contains animal gum. From tendon mucin, the same carbohydrate is obtained, in spite of what Loebisch (Abstr., 1886, 166) says to the contrary; it may also be obtained from synovia, collo'id cysts, and from the mucin of the snail's mnntle. nilucin and animal gum both yield lsvulic acid when treated with hydrochloric acid. By long boiling with water, chondrin splits into gelatin, animal gum, and possibly a third substance not yet further investigated. Pure chondrin is soluble in hot water, and its solutions gelatinise when cold, if not too dilute ; this power of gelatinising is lost after prolonged boiling. A dilute solution gives the following reactions :-Dilute mineral acids cause a precipitate soluble in excess ; acetic acid gives a precipitate insoluble in excess ; acetic acid and potassium ferrocyanide give a precipitate, soluble in excess of the latter reagent.Sodium chloride solution gives no cloud, but hinders the precipitation by acetic acid. Metaphos- phoric acid gives a cloudiness disappearing on warmth. Alum gives a cloudiness, disappearing on adding excess. Lead acetate gives a preci- pitate, soluble in excess. Basic lead acetate gives a precipitate, partially soluble in excess. Lead acetate and ammonia give a flocculent preci- pitate, insoluble in excess. Tannin and acetic acid give a precipitate, insoluble in excess. Copper sulphate and sodium hydroxide colour the liquid violet, which becomes red on boiling. Boiling the solution for fire or six hours with 1 per cent.mlphuric acid gives it the power of reducing copper salts, this being due to the formation of a reducing sugar from animal gum. Animal gum may be separated from chondrin in the same way as from mucin. Metalbumin and paralbumin may also be used as sources of animal gum. It is also found in small quantities, but constantlly in the red blood corpuscles, brain, kidney, spleen, liver, and pancreas. Prote'ids pi-opor do not yield it. Another source of animal gum is chondrin. W. D. H. Derivatives of Thioformaldehyde. By A. WOHL (Rw., 19, 23444347) .-Thiometaforrnaldehyde, (CH,S),, is obtained when an aqueous or alcoholic solution --of hexamethyleneamine saturated with hydrogen sulphide is heated on a water-bath. It separates as a, white, amorphous substance, which is washed with water and hydro4 chloric acid, and extracted with boiling glacial acetic acid and alcohol.It is insoluble in all the usual solvents, and has a peculiar odour ; it melts at 175-176", and decomposes at a high temperature. It dissolves unchanged in strong sulphuric acid. Methy Zthi~formuldine, S2(CH2)sNMe, is prepared by diluting 50 C.O. of a 20 per cent.. solution of formaldehyde with an equal volume of wa&er, 8nd saturating with hydrogen sulphide; 200 C.C. of wafer are28 ABSTRACTS OF CHEMICAL PAPkXS. then added, the whole filtered and stirred with 20 C.C. of a 30 per cent. solution of methylamine. In 24 hours crystals separate. More hydrogen sulphide i s then passed through the solution until it is no longer turbid ; the crystals are collected, washed with water, and dis- solved in ether.I t crystallises in needles melting at 65", and is insoluble in water, soluble in dilute mineral acids, alcohol and glacial acetic acid. It distils with steam, boils at about 185", being at the same time converted into a compound melting at 130-140". The hydrochloride forms needles readily soluble in water ; it melts at 188" with decomposition. Dimeth ylthioformuldinium iodide, SL(CH,),NMe,1, is formed by treating the compound with methyl iodide. In two to three days the liquid solidifies to a mass of slender, lustrous needles. It melts at 161- 163O, and dissolves readily i n water, sparingly in alcohol. The platino- chloride, [ Sz( CH2)3NMe]zMezPtC16, is a bright yellow, crystalline sub- stance.The iodide dissolves in hot aqueous potash and separates unchanged on cooling. When boiled with silver oxide, it yields an ammonium base, which, however, could not be isolated. Chloro-derivatives of Acetals. By 0. MAGNAMINI (Gazxetta, 16, 330-3333) .-Trichlorometh y let hylacetal, CC13*C €3 (OMe) OEt, is ob- tained by heating tetrachlorether with methyl alcohol in sealed tubes. The reaction is as follows: CCI,*CHCI*OEt + MeOJ3 = HCl + CCl,GH(OMe)*OEt. It is a colourless liquid of camphor-like odour ; it boils at 193.4; sp. gr. = '1.32. Trichlorodimethylacetal, UCI3*CH(CMe)?, obtained from tetrachlor- ethyl methyl ether, is a liquid of similar characters. It boils at 183.2" ; sp. gr. = 1.28. The tetrachlorethyl methyZ ether, CC13*CHC1*OMe, prepared by the action of phosphoric chloride on chloral methylate, is a colourless liquid boiling at 178"; sp.gr. at 0" = 1.84. I t does not appear to have been previously isolated. Diisonitrosoacetone. By H. v. PECHMANN and R. WEHSARG (Ber., 19, 2465-2467).-V. Meyer and Zublin have shown that when accto- acetic acid is treated with nitrous acid, carbonic anhydride is evolved, and isonitrosoacetone formed. The authors find that when, in like manner, acetonedicarboxylic acid is treated with water and sodium nitrite, a rapid evolution of carbonic anhydride takes place, and diiso- nitrosoacetone, CO (CH-NOH),, is produced. This forms glistening prismatic crystals, meltiug with decomposition at 143-144". It is easily soluble in alcohol and ether, sparingly in cold water, chlorofoim, and benzene.Its aqueous solution when heated decomposes into hydrocyanic acid, car- bonic anhydride, and water. Acids cause a similar decomposition, but hydroxylamine is also among the products. It is more stable in nlka- line solutions, and forms alkali saEts, which crystallise in orange-yellow needles. Its salts, especially the red crystalline silver salt, explode when heated. When warmed with phenol and Rulphuric acid, the nitroso-compound gives a red coloration, with ferric chloride a brown. The authors are further investigating the subject. N. H. M. V. H. V. I t is very unstable, and detonates when heated. L. T. T.ORGANIC CHEMISTRY. 29 Hetines. By L. CON OM IDES (Ber., 19, 2524--2527).-When a very dilute solution of diethylketine, CloH,,N2, is treated with the theoretical amount of potassium permanganate, a ketinedicarboxylic acid is obtained, identical with that prepared by Wleugel by reducing ethyl isonitrosoethylacetate (Abstr., 1882, 949).If the oxidation takes place in a warm solution, other and more unstable acids are formed. When 5 grams of ethyl imidoisonitrosobutyrate are care- fully warmed with powdered zinc chloride at 60-70" for a long time, and the product saponified with alcoholic potash, a small quantity of an acid melting at l90-195", identical with Wleugel's acid (Zoc. c i t . ) , is formed. The above reactions, together with the fact that the ketine- acid does not yield an anhydride, point to the following constitutional formulae for methylketiiie and the ketine-dicarboxylic acid :- CMe*CH CMe* C (C 0 OH) NeCH: CMeyN and NeC(COOH): CMeyN* N. H.M. Pure Bntyric Acid. By A. BANNOW (Ber., 19, 2552-2554).- Pure butyric acid is best prepayed by converting the commercial acid into the ethyl salt, which is then fractionally distilled. The fraction boiling at 120-121" is reconverted into acid. N. H. M. Xoc., 1886, 287-297).--Tiglic (methylcrotonic) acid, Derivatives of Tiglic Acid. By P. MELIKOFF (J. RUSS. C h m ~ CHBle: CNeCOOH, was prepared either by the saponification of the oil of Roman chamo- mile (Kopp, Abstr., 1879, 454), or by heating a-methyl-p-hydroxy- butyric acid (Rohrbeck, Abstr., 1878, 136). The acid was treated under water with an aqueous solution of hypochlorous acid, the pro- duct of the reaction extracted with ether, and the solvent; distilled off.The residue, after remaining for some time over sulphuric acid, solidified to a crystalline mass, which was found to consist of two isomeric chlorhydroxyvaleric acids, C5H9C103. A concentrated aqueous solu- tion of this mixture was neutralised with zinc carbonate : a crystalline zinc salt was precipitated, and the mother-liquor on being evaporated left another salt in the form of an amorphous humoid substance, The two acids obtained by decomposing these salts with sulphuric acid are both easily soluble in water, alcohol and ether ; the one forming a crgstalline sparingly soluble zinc salt, melts at 75", and crjstallises from ether in thin prisms; the other isomeride melts at 111*5", and is obtained from its ethereal solution in the form of large, translucent prisms.When a mixture of these acids, or each of them separately, is treated with alcoholic potash, the potassium salt of an anhydro-acid, CHMe <--,- >CMe*COOH, is formed. The free acid forms silky, crystal- line needles having the odour of butyric acid, easily soluble in water, alcohol, and ether, melting at 62". The energy with which i t enters into direct combination is in the main the same as that shown by p-rnethylglycidic acid : a-methj lglj cidic acid in this respect exhibiting30 ABSTRACTS OF CHEMICAL PAPERS. much greater energy. This circumstance, established by experiments on the hydration of the potassium salt by heating with water, is in accordance with the results obtained by the author in a former work on glycidic and a- and p-methylglycidic acids (Abstr., 1885, 650).The energy of direct combination is diminished with increasing molecular- weight in acid8 of analogous constitution ; at the same time among isomeric acids the greatest energy is exhibited by the one containing tertiarily united carbon in its molecule. a-p-Dimethylglycidic acid contains one CH,-group more than a- and P-methylglycidic acids, but, on the other hand, one of its carbon-atoms combined with oxygen is in tertiary union. By the action of hydrochloric acid on a-P-dimethylglycidic acid, a-methy E-P-clLZor-a-hydroaybzLtyric acid, OH*CHMe*CMeCI*COOH, is formed ; it melts at 75", and is identical with one of the chlorhydroxg- valeric acids above described, the other isomeride being therefore a-methtyl-a-clLZoro-~-~~~droxyLUt~r~c acid, CHMeCl*CMe(OH)-COOH.An aqueous solution of a-/3-dimethylgl@dic acid, when heated during 6-10 hours at 99", is converted into a-P-dimethyZqlycidic acid, OHCHMe*CMe(OH)*COOH, melting at lo?", readily dissolving in water, alcohol, .and ether. A. T. Constitution of Chlorhydroxybutyric and Dichlorobutyric Acid. . By E. MELIKOFF (J. Buss. Chem. SOC., 1886, 227-303).- Chlorhydroxybutgric acid (formed by the combination of crotonic with hypochlorous acid, Abstr., 1884, 1302, and 1885, 650), when heated with concentrated sulphuric acid, yields monochlorocrotonic acid, crys- .fallising in long, thin prisms, melting at 98", sparingly soluble in cold, more readily in hot water, easily soluble in alcohol and ether. This acid yields normal crotonic acid (m. p. 72") ou reduction by zinc and sulphuric acid.The chlorocrotonic acid above mentioned is an a-chlorinated product, the isomeric &derivative being obtained, amongst other methods, by the action of phosphorus pentachloride on ethyl acetoacetate; hence, the chlorhydroxybutyric acid in question must be a-chloro-P-hydroayB?~tyric acid. This acid was heated with hydrochloric acid, and a-/%diChloTObUt?/riC acid was obtained; it crystallises in long prisms and melts at 69". An alcoholic solution of the latter compound, when treated with alcoholic potmh, gives a-monochlorocrotonic acid. a-p-Dichlorobutyric acid is formed in like manner when a-monochlorocrotonic acid is heated with hydrochloric acid. A. T. Hydroxystearic Acids of Different Origin. By A. C. and M. SAYTZEFF (J.RUM. Chem. Xoc., 1886, 328--348).-A hydroxp- stearic acid was prepared by one of the authors some time ago in his work on the oxidation of oleic acid (Abstr., 1886, 140). Another acid of this composition was discovered by Fr6my (AnnuZen, 19, 296 ; 20, 50; 33, lo), who obtained it by the action of concentrated sulphuric acid on oleic acid, and described it under t,he name of hydro- rnargaritic acid. Although the main points of the reaction had been satisfactorily explained by FrBmy's work, yet subsequent work on this question has mostly led to unsatisfactory results. SnbaneieffORGANIC CHEMISTRY. 31 (Qbst?., 1886, 442) ha4 at last succeeded in throwing some new light on the processes involved, but the authors do not in all cases obtain results in agreement with his.Oleic acid was obtained by the saponification of oil of almonds, and purified in the ordinary way by conversion into its lead salt. The action of sulphuric acid was regulated in such a manner as to prevent the temperature rising above 35". The mixture was then allowed to remain 20 hours a t a temperature below O", and decomposed by water. In order to increase the yield of hydroxystearic acid, the fatty layer, separated by the action of water and solidifying a t the ordinary temperature to a crystalline mass, was treated with alcoholic potash, whereby the anhydrides of this acid are decomposed. The saponified product was then converted into the acid by boiling with sulphuric acid. When the products of the action of sulphuric acid on oleic acid are left for some time even at low temperatures, the quantity of hydroxystearic acid is diminished, whilst the quantity of its anhydrides increases.Hydroxpstearic acid was extracted from the above-mentioned crystalline mass by repeated recry stallisation from ether and alcohol. So obtained, hydroxystearic acid, CH,. ( C H,) 13-CH,.CH( 0 H) CH2*C 0 OH, melts at 83-85", and resolidifies a t 68-65". At 20" alcohol (99p Ti-.) dixsolres 8.78 per cent., ether 2.3 per cent. of the acid. Tlydroxy- stearic acid does not absorb bromine. The free acid and the hydroxy- stearates of sodium, calcium, barium, copper, zinc, and silver, were analysed, and the formula of the acid shown to be C18H,0,. With hydriodic acid, hydroxystearic acid yields iodostenric acid. CH,*(CH,)13 CH,*CHI*CH2*COOH ; the latter can be converted into ordinary stearic acid by reducing its alcoholic solution with zinc and hydrochloric acid.When hydroxystearic acid is heated at 100" in sealed tubes with fuming hydrochloric acid, a syrupy liquid is formed, soluble in ether, insoluble in alcohol m d water, and having the composition of oleic acid. It does not show acid properties, nor give additive products with bromine or iodine (in Hubl's solution); it is therefore considered to be a complete anhydride of hydroxystearic acid, formed by elimination of 2 mols. of water from 2 mols. of the acid (analogous to glycolide or lactide). The anhydride is decomposed into hydroxystearic acid by treatment with alcoholic potash a t tem- peratures above 150". Heated with dilute sulphuric acid (in sealed tubes at looo), hydroxystearic acid yields the same anhjdride, but when concentrated salphnric acid is iised a t ordinary temperature, two other products of non-saturated character are formed, one corn bining with 17 per cent., the other with 33 per cent., of iodine, when heated with it on the water-bath.These substances bear a great resemblance to FrBmy 's metoleic acid, and will be further investigated. It wag shown that the hydroxystearic acid prepared by $he action32 ABSTRACTS OF CHEMICAL PAPERS. of moist silver oxide on iodostearic acid was identical with that described above. Finally, the authors have studied the action of alcoholic potash on iodostearic acid. After heating the mixture in a reflux apparatus, and expelling the alcohol by distillation, the product of the reaction was decomposed by sulphuric acid.An acid was obtained, solidifying ak ordinary temperatures to a crystalline mass, and consequently not identical with oleic acid. It was purified by converting it into the sodium salt, recrystnllising this salt from alcohol, precipitating with zinc sulphate, recrystallising from boiling alcohol, and decompodng the zinc salt by sulphuric acid. Thus purified, the substance crys- tallises from ether in translucent, rhombic tables, easily soluble in alcohol, sparingly in ether, and melts at 40-45". The composition of this acid was found to be the same as that of oleic and elaidic acids. It is a non-saturated compound, taking up two atoms of bromine 01' iodine. When oxidised by potassium permanganate i n alkaline solution, it yields dihydroxystearic acid, melting a t 78".The authors intend to continue the investigation of this solid oZeic acid. Another acid, melting a t 20-25", simultaneously formed by the action of potash on iodost,earic acid, was found to be a mixture of ordinary and solid oleic acids. The constitution of solid oleic acid is CH,*( CH2) Is*CH2*CH : CH*COOTJ, ordinary oleic acid being repre- sented by CH3*(CH2)13*CH : CH*CH,-COOH. A. T. Action of Trimethylene Bromide on Ethyl Acetoacetate, Benxoylacetate, and Acetonedicarboxylate. By W. H. PKRKIN, Jun. (Ber., 19, 2.557-2561 ; comp. Abstr., 1886, 689).-When the acid C7Hl0O3 (from trimethylene bromide and ethyl sodacetoacetate) is boiled with aaker, carbonic anhydride is evolved, and Lipp's acetobutyl alcohol (Abstr., 1886, 218) is formed. When the acid is distilled, the anhydride of acetobutyl alcohol, CH2<cCH2.C,2-->0, CH : CHMe is obtained; it is a mobile oil.The same compound is also formed when acetobu tyl is heated. Strong hydrobromic acid dissolves the ethyl salt C9Hla03, and decomposes it into bromobntyl methyl ketone ( Lipp, Zoc. cit.) and carbonic anhydride. Benzoyltetramethylene- carboxylic acid is decomposed by hydrobromic acid in a similar manner, with formation of the compound COPh*CH2*CHz*CH2*CHzBr ; this cyystallises in plates melting a t 61". The instability towards hydrobromic acid of the products obtained by the action of tri- methylene bromide on etbyl acetoacetate and benzoylacetate respec- tively, distinguishes them sharply from tetramethylenedicarboxylic acid.Trimethylene bromide acts on the sodium compound- CO(CHNa*COOEt)2 (from ethyl acetonedicarboxglate and sodium ethoxide), yieiding the compound C O O E t * C H ~ ~ ~ , ~ ~ C > O . The latter is a colour- less oil boiling at 238-240-(under 150 mm. pressure). The mon- et/t,yl salt melts at 114"; the free acid at 185--190" with decom-ORGANIC CHEMISTRY. 33 position. When the monethyl salt is distilled, a subtance is obheined apparently identical with the product of the reaetion between tri- methylene bromide and ethyl acetoacetate. The dicarboxylic acid is decomposed by boiling water into acetobutyl alcohol and carbonic anhydride. N. H. M. Ethyl Acetotrimethyleneearboxylatk By W, H. PERBIN, Jun., and P.C. FREER (Ber., 19, 2561--2569).-The fact that trimethyleno bromide reacts with ethyl malonate, yielding a tetramethykne- derivative, and with ethyl acetoacetate with formation of an ether, sugges6ed the possibility that the product of the reaction between ethylene bromide and ethyl acetoacetate (Trans, 1885, 801) is not a trimethylene-derivative bdt an ether. The aesults of determinations of the magnetic circular polarisation, and the optical properties point, however, to the trimethylene formula first ascribed to the compound, E t h yZic brometh y Zucetoacetate, CH2Br+H2-CHAc*C00Et, is obtained by dissolving ethyl acetyltrimethylenecarboxylate, well cooled., in hydrobromic acid, sp. gr. 1.85 (3 parts) ; after being left for 10 minutes at the ordinary temperature, it is poured into ice water..It is a yellowish oil, having an odour of camphor ; when exposed to air it becomes brown, and gives off hydrobromic aeid.. When reduced by means of zinc-dust and acetic acid, it is converted into ethyl aceto- acetate. Acetopropy I aZcohoZ, COMe*CHz-CH2-CH2-OH, is prepared by boiling 20 grams of the above homo-compound for two hours with 5 grams of hydrochloric acid and 20 grams of water. The reaction is analo- gous to that by means of which Lipp obtained acetobutyl alcohol from ethyl bromopropylaeetoacetate (Abstr., 1886, 216). It i s a colourless oil, very soluble in water; the solution very readily reduces ammoniaeal silver solution but not Yehling's solution. It is very unstable. A phenylhydrazine-compound was prepared. When the alcohol is heated, it is converted with evolution of water into a mobile oil, having an ekhereal odour ; it is probably an anhydride, CMe- cHqCH2* CH2>0 (comp.A'bstT., 1886, 219). y-PeNty Zeme glycol, OH-CHMe*CH2-CR2.CH2-OH, is obtained by reducing acetopropyl alcohol with sodium amalgam. I t is a very thick, colourless oil, extremely soluble in water. It boils a t 210- 220" with partial decomposition. When heated above its boiling Doint. or with 50 to 60 Der cent. of sulDhuric acid at 100'. it is con- I ' CHM - verted into the anhydride, CH2< CH,. &,>O, boiling at 78- 83". - - Pentylene glycol dissolves in hydrobromic acid (sp. gr, 1-85) with considerable development of heat ; when the solution is heated at W", the momobromohydrin of the glycol, C5HI13&, is formed, This is a colourless oil, which boils (under 150 man.pressure) at 144-145". N. H. M. Derivatives of Diaxosuccinic Acid. By T. C m r m and F. KOCH (Ber., 19, 2460--2462).--This is a continuation of the authors' previous work on this subject (Abstr., 1885, 885). Aspartic acid wsls VUL. LIr. d34 ABSTRACTS OF CF-IElIICAL PAPERS. obtained by the reduction of ethyl diazosuccinate with zinc-dust and acetic acid, thus proving the correctness of the formula formerly ascribed to diazosuccinic acid. NHz* CO* CN,*CHz*CO ONe (from the action of ammonia on methyl dia zosuccinnte), crystallises in long, golden-yellow prisms soluble in ether and alcohol, and melting at 84". When ethyl diaeosuccinate is acted on by cold slightly acidified water, mulamic and f umalramic acids are produced.Malamic acid, NH,*CO*CH ( OH)*CH2*COOH, crystallises in colourless prisms easily solnble in water, alcohol, and ether, and melts a t 146" ; its methyl salt yields silky sca1e.s soluble in alcohol, ether, and water, and melting a t 105". illethyl furnuramate, NHz*CO*CzH,*COOMe, crystallises in colourless plates, soluble in alcohol, and melts at 160-162". EihyZ benzoyZmaZamute, NH,*CO~CH(OBz)~CH,~COOEt, was obtained by heating together equal molecular proportions of benzoic acid and ethyl diaxosuccinamate a t 140-150". It forms colourless clinorhombic crystals soluble in water, alcohol, and ether, and melts at 96-97". It decomposes easily when heated. The corresponding methyl salt form8 colonrless crystals, melting at 78-80".By the action of iodine on an ethereal solution of ethyl diazosuccinamate an unsymmetrical ethyl diiodowxinamate, NH,*CO*CI,*CH,* COOEt, is formed. This crystallises in long, greenish-white needles which darken at 110", melt a t 132", and decompose at 150". The methyl salt and come- sponding methyl and ethyl hromo-salts are oils. Dichloropyromucic Acid. By A. DENARO (Gazzetta, 16, 333- 335).-1f a current of dry chlorine gas is passed into the ethyl salt of pyromucic acid, a thick oil is at first obtained, probably consisting of the tetrachloride of the acid. This on decomposition with alcoholic potash and subsequent acidification, yields a dichlorqyromucic acid which crystallises in white needles, melting at 167". Its barium salt crystallises with 3 mols. HzO i n prisms, the calcium salt with 3$ mols. H,O in scales; both become completely anhydrous when heated to 110".v. 1%. v. By 0. WIDMANN (Ber., 19, 2477- 2$82).-As the mode of formation and reactions of this substance are best explained by the formula CO' /GO, which 1111- doubtedly belongs to acetylenecarbamide, the author has carefully re-examined these two compounds with the view of determining whether they are isomeric or identical. He finds that the latter is the case, and that the apparent differences in their reactions are due to erroneous observation. When boiled with concentrated baryta-water, acetylenecarbamide does not, as previously asserted, yield carbonic anhydride, but, like glycoluriI, is decomposed into hydantoic acid and carbamide. The solubility of acetylenecarbamide i 3 given by Schiff as 1 in 333 parts of water a t 15".The author fiads that pure acetylenecarbamide requires 1090 parts of water for solution, whilst a similar determination af the solubility of glycoluril showed a Methyl diazosuccinumate, L. T. T. Constitution of GIycoluriI. NH*CH*NH, I \NH.CH*NHORUA'NlC CHENISTRY. 35 ratio of 1 : 1060. Similar agreement was also found in the siher sdts, crystalline form, &c., both compounds crystallising variously in needles, prisms, or octahedra according to the solvent employed. Glycoluril and acetylenecarbamide are therefore identical, and the author pro- pofies the adoption of the latter name as the more suitable. Hydrocarbons from Tar-oils Boiling between 170" and 200". By 0. JACOBSEN (Ber., 19, 2511--2515).-The author has examined a sample of coal-tar oil free from thiophen, of boiling point 170-200".By combined fractional distillation, conversion into sulphonic acids, sulphonic salts, and sulphonamides, he succeeded in isolating naph- thalene, pseudocumene, hemellithene, and another hydrocarbon, boiling like the last-named at 175-175*5", but yielding a very soluble mi+mwnide melting a t about 122-123". On oxidation, the hydro- carbon yields an acid which crystallises in needles melting at 119- 121" and volatile in steam, aud also small quantities of a second acid melting at 90". The acid of higher melting point yields isophthalio acid when oxidised with permanganate. Chloropropylbenzene.. By G. ERRERA (Gazzzetta, 16,310-325) .- I n order to determine the constitution of the chloropropylbenzene obtained by the action of chlorine on the boiling hydrocarbon, the three alcohols derivable from propylbenzene have been prepared and converted into tbe corresponding chloro-derivatives.Phenylpropyl oloohoJ, C&Ph*CH2*CH20H, obtained from crude fitorax by Rugheimer's process, is not altered by gaseous hydrogen chloride, but when heated in a sealed tsbe with saturated hydro- chloric acid solution, it yields tbe chloro-derivative CH,Ph-CH,-CH,Cl. This compound i s a pale-yellow liquid, boiling at 219", and resembling cymene in odour; when pure, it is very stable, being unaltered by prolonged treatment with fused xinc chloride or, silver acetate. Heated with alcoholic potttsh, it yields phenylpropyl ethyl ether, CH2Ph*CHe*CH20Et, a colourlem liquid boiling a t 220", insoluble in water.NethyZ benzykd carbinoE, CHePh*CHMe*OH, obtained together with, allylbenzene and stilbene by the reduction of methyl henzyl ,ketone with sodium amalgam, is a, liquid boiling at 215", of, a pale-yellow colour and agreeable odour. Heated with hydrochloric acid in sealed tubes, it yields the chloro-derivative, CH,Ph*CHClMe, a yellowish liquid, boiling at 204-2Q7" with partial decomposition into allyl- benzene and hydrogen chloride. A similar reaction occurs with alGQ- holic potash, metallic zinc or its chloride. EthyZphenyZ carhino& CHPhEt-OH, prepared by prolonged reduction of the corresponding ketone with sodium amalgam, as described by Barry, is a liquid boiling at 215-217'. It is converted by gaseous hydrogen chloride, even at ordinary temperatures, into the chloride CHPhEtCl, a yellow liquid.bailing about 200-205", but with con- siderable decomposition into bydrogen chloride and allylbenzene, 8 change which takes place even on distillation in a vacuum. It is distinguished from the two preceding chloro - derivatives by the readimss with which it reacts with silver acetate, .xielding tbe itcetyl- L. T. T. L, T. T. d P36 ARSTRACTS OF CHEMICAL PAPERS. derivative, CIAPh'EkOAc, a liquid %oiling trt 227", of fruity odonr, and imsolixble in water. The chloropropylbenaene obtained by the direct dhlorination of the hydrocarbon is identical with the second of the above chloro-compounds, i n that it is decomposed by distillaticm and by alcoholic potash, as also by its stability towards silver aoebate.Iu these properties, the chloro-derivatives of propylbenzene are directly comparable to those of ethylbenzene. Reduction-of Trinitro-+-cumene. By F. MAYER (Ber., 19,2312 -2314) .-In preparing nitrocnmidine by passing hydrogen sulphide through a boiling alcoholic solution of trinitro-+xmene, the chief product is a new acid, CgH12N&305. T t is insoluble in alcohol, ether, glacial acetic acid, '&c., soluble in' hot water, from which it crystallises on the addition of a few drops of hydrochloric acid in splendid, white or yellowish plates. Salts were prepared. 'N. H. M. Hemellithene. By 0. JAUOBSEN (Ber., 19, 2517-2520).--The author has investigated this compound, which he has now isolated from the fraction of coal-tar oils boiling between 170-200" (see p.35). Hemellithene, CsH3M, [ 1 : 2 : 31, boils at T75-175.5", and does not solidify a t - 20". Tribrow~ohenl,ellithene, C9H9Br3, forms long needles melting at 245", and is very sparingly soluble in alcohol ; trinitrdhenzelli- tliene forms prisms melting at 209". The monnosulphonic acid crys- tallises in hydrated rhombic or hexagonal plates, and yields crys- talline salts ; its sulphonamide melts at 99tL-196". Hemellithehenol, C,H,,*OH [Me : Me : Me : OH = 1 : .2 : 3 : 51, is obtained by fusing the mlphonic acid with alkali. It is soluble in dcohol and ether, and crystallises in needles melting at 81". Hemelli- thy& acid, C,H,Me,*COOH [Me : Me: COOH = 1 : 2 : 31. is furmed by the oxidation of the hydrocarbon by dilute nitric acid.It is volatile in steam, and crystallises in wales melting a+ 144". Its 8aZcim salt is described. Distilled with lime, it yields mthoxylene. a - Sz~~rph.aminehemellithy1ic acid [Me : Me : COOH : SO,NH, = 1 : 2 : 3 : 51, is formed by the oxidation of the above sulphonamide. It melts art Z W , and with hydrochloric acid yields a sulphohemelli- thylic acid melting at 180-190". ~-Szclprphaminehemellithylic acid [Me : "Me :COOH : SOZNHz = 1 : 3 : 2 : 51, formed a t the same time as the-a-ackl, is more solhble, and melts a t 174". It yields avery soluble sulphonic acid when ' hwted with hydrochloric acid. Both acidR when fused with potash yielded an easily soluble hydroxyhemellithylic acid, which does not give a blue coloration with ferric chloride.Hemellithene may be readily extracted from the tar oil by means of the sparing solubility of its barium sulphonate. Reciprocal Transformations Of Cymene and Cumenederi- vatives. By M. FILETI (Guzzetta, 16, 300-310).-In this paper are collected the hitherto observed transformations of cumene and cymene- derivatives, the one into the other, and from them is drawn the following generalisation :--A propy1-poup in the para-position rela- tively to a carbon-atom combined with other elements or with non- oxygenated groupings, is transformed into the isopropyl-group, if this V. H. V. It melts at 240" and carbonises. L. T. T.ORGANIC CHEJIISTRT. 37 element or grouping is displaced by an oxygenated radicle whose oxygen is directly united to the carbon-atom compound, and conversely ail isopropyl, is converted into a propyl-group when these substitutions are reversed.(Compare Widman, Abstr., 1886, 453.) Chlorocymene and Bromocymene from Thymol. By M. FILETI and F. CROSA (Gazzetta, 16, 287 - 300). - Chlorocymene (parapropylmetachlorotohene), C6H3MePrC1, is obtained almost in theoretical proportions by heating in a reflux apparatus 4 mols. of thymol with 1 mol. phosphoric chloride. On oxidation with nitric acid, Gerichten (Abstr., 1879, 238) obtained an acid, believed to be a hydrochlorocinnamic acid, C,H,n/Ie~1*Cil2.CH2*C0OH. It is here, however, shown that under these conditions three acids are formed, namely, chlorocumic, orthochloroparatoluic, and chloroterephthalic acids. Sixty per cent. of the theoretical quantity of bromocymene, calcu- hted according to the equation 4C,HI3*OH + PBr5 = CloH13Br + PO(OCloHlJ3 + 4HBr, can be obtained by the gradual addition of 26 grams of bromine to 45 grams of phosphorus tribromide, and heat- i n g the resulting perbromide with 100 grams of thymol.On oxidn- tion with nitric acid of sp, gr. 1.2, bromocymene yields bromocumic acid ; with acid of sp. gr. 1.29, bromonitrocymene with bromocumic, bromonitrotoluic, and bromoterephthalic acids, whilst nitric acid of sp. gr. 1.39 yields the same acids without the bromonitrocy- mene. The bromcumic acid is identical with that obtained by the direct bromination of cumic acid ; it has, therefore, the constitution C6H,PrBr*COOH. The broinoizdrotoluic acid crys tallises in laminae, which melt at 200" without decomposition; it is isomeric with the acid obtained by the nitration of bromotoluic acid ; its barium salt crystallises in long, yellow needles.The brornoterephthalic acid is identical with that obtained by Fischli by the oxidation of bromopara- toluic acid. V. H. V. V. H. V. Ethylxylenes, By 0. JACOBSEN (Ber., 19, 2515--2516).-For the purposes of comparison with hydrocarbons obtained from the fraction of coal-tar oils boiling between 170" and 200" (this vol., p. 35), the author prepared the three isomeric ethylxylenes from the three corre- sponding xylenes, using Fittig's method. Etlzylorthoxyle~~e yields a crystalline sulphonic acid, giving a sulphonamide crystallising in needles melting at 126". Ethylmetaxylene boils a t 184-186", and is still liquid a t - 15" ; its sulpphonic acid is crystalline, and yields crystal- line barium and sodiwm salts; its sulphoibamide melts at 148".Jbhyl- paraxylene boils at 185", and is still liquid a t - 20"; its suZphonic acid crystallises in rhombic scales, forms crystalline barium and sodium salts, and yields a crystalline suZpphonamide which melts at 117". Ethereal Carbonates. By. G. BENDER (Ber., 19, 2265-22.71 ; compare Abstr., 1881, 48). -When naphthyl ethyl carbonate, OCloH,*CO-OEt, is boiled f o r some time, carbonic anhydride and alcohol are given off, and the residue consists of a, mixture of a-naphthol and a, compound C2,H1202 (Zoc. cit.). The formation of L. T. T.38 ABSTRACTS OF OHEJIICAL PAPERS. diphenylene ketone oxides from salicylic acid (Perkin, Tmna, 1883, 35) and the intermolecular change of sodium phenyl carbonate to sodium salicylate, suggest that Ohe naphthyl ethyl carbonafe may have become changed to the ethyl salt, OHCl,H6~COOEt, and that 2 mols.of the latter have condensed with formation of the compound CZ1H1",2 ; this would then be dinaphthylene ketone oxide, ClOH6<CO>ClO'Il6* 0 The isonaeride obtained by boiling P-dinapht hyl diethyl orthocarbonate (loc. cit.) crystallises from benzene in thin prisms melting a t 194". When phenyl ethyl carbonate is heated a t 300" for 3-4 hours diphenylcarbonate is formed. Paraditoly 1 carbonate is obtained by heating paratolyl ethyl carbo- nate at 300"; it is insoluble in water, moderately soluble in hot alcohol, and melts at 115". Tlynayl ethyl carbonate is a thick liquid boiling at 260"; a t 300" it decomposes into dithyrnly 1 carbonate, melting a t 60".Orthoaitrophenyl ethyl carbonate is prepared by the action of ethyl chlorocarbonate on potassium orthonitrophenoxide. It is a heavy yellow oil which boils with decomposition a t 275-285". The arnido- salf, NHE,*C6HrO*C0.0Et, melts a t 95"; it is soluble in alcoho!, moderately soluble i n boiling water. When distilled, it gives off alcohol with formation of ar~hydro-orthamid~~7~e~~yl carbonate, C,H,NO, ; the latter dissolves in alkalis. The silver salt, C7H4AgN02, forms an amorphous, colourless precipitate. The ethyl salt is obtained by boiling the compound with alcoholic potash and ethyl iodide. When heated with fuming hydrochloric acid, it yields ethyl orthamido- phenol and carbonic anhydride ; the constitution of the substance is therefore c6H,<~~~>co.Tbe phenylhydrazine compound of anhy- dro-orthamidophenyl carbonate, C6&<-O->C : N*NHPh, crys- tallisee in yellow needles, which melt at 208". The acetyZ-derivative melts at 97-98". A InorLonrtro-co~npound was prepared ; it forms long yellow needles melting at 256". Bromine acts on the anhydro-corn- pound with formation of a nzonobromo-derivative ; this crystallises from water in plates melting at ,196". When treated with phosphoric chloridc, the compound C7H4ClN02 is .formed. Parahydroxybenzyl Alcohol. By J. BIEDERMANN (Ber., 19,2373- 2376).-Parahydroxybenzt~l alcohol, OH*C6H4*CH20H, is prepared by dissolving parahydroxybenzaldehyde (I part) in a mixture of water (10 parts) and alcohol (5 parts) ; it is then acidified with dilute sulphuric acid and gradually treated with 3 per cent.sodium amalgam (40 parts). Grey crystals of diparahydroxyhydrobenzoin and oily drops of dipnra- hydroxyisohydrobenzoh separate. When hydrogen is no longer evolved, the solution is made strongly acid and left for 12 hours, it is then filtered, the filtrate extracted with ether, and the ethereal extract treated with hydrogen sodium sulphite. On evaporating the ether, the alcohol separates in needles ; these are purified by dissolving tlhem in hot chloroform and precipitating with light petroleum. It forms slender N H N. H. M.ORG AKIU CHEMISTRY. 39 white needles, readily soluble in water, alcohol, and ether, sparingly in benzene and chloroform; sulphuric acid dissolves it, yielding a splendid 1-ed-violet solution.It melts a t 110". The alcohol is also formed when parahydroxybenzaldehyde is kept dissolved in aJcoholic potash for several weeks, but the reaction is still very incomplete. The acety I-derivative, OH*C6H4*CH,.0Ac, is prepared by heating the alcohol with a mixture of glacial acetic acid and sulphuric acid. It crystallises from water in small yellow needles, melting at 84", and is readily soluble in alcohol and ether, spariiigly in water, benzene, chloroform, &c. The diucetyl - derivative, OAc*CcH4*CH2*OAc, is obtained by heating pnrahydroxybenzyl alcohol with an excess of acetic anhydride a t 160" for 5-6 hours. It forms yellowish needles melting a t 75", readily soluble in alcohol and ether, sparingly in benzene, &c.Br~isic alcohol, OMe*C6H4*CHI,0H[ = 1 : 41, is formed when para- hydroxybenzyl alcohol is dissolved in methyl alcohol and digested with potash and methyl iodide for some hours at 100". The product is treated with wzter, heated to expel methyl alcohol and iodide, and extracted with ether. On evaporating the ether, it is obtained as an oil which gradually solidifies when kept over sulphuric acid. It crp- tallises from water in needles melting a t 45" (compare hbstr., 1888, 460). N. H. 11. Synthesis of Betorcinol (p-Orcinol). By S. V. KOSTANECKI (Bey., 19, 22 18-2324 ; comr are Abstr., 1886, 242) .-Z'araxylorcinol [Me2 : (OH), = 1 : 4 : 3 : 51 was prepared from metadinitroparaxylene by rcplacing the nitro-groups successively by amido- and hydroxyl- groups ; it is identical with Stenhouse and Groves's betorcinol (Trans., 1880, 396).The crude product obtained by nitrating paraxylene is crystallised from alcohol to remove most of the orthodinitroparaxylene, dissolved in hot alcoholic ammonia, and treated with hydrogen sul- phide for about one hour; i t is then evaporated to dryness. The paradinitro-compound, being more readily reduced than the meta- compound, is thus converted into paranitroparaxylidine, which is extracted by means of hydrochloric acid. The residue, insoluble in acid, was extracted with boiling alcohol, and yielded crystals of pure metadinitroparaxylene. This was reduced by dissolving in alcoholic ammonia and treating for two hours with hydrogen sulphide, and the nitroxylidine [ Me2 : 50, : NH2 = 1 : 4 : 3 : 51 so obtained was converted into the corresponding nitroxylenol. The latter crystallises in yellow plates melting at 91".It was reduced with tin and hydrochloric acid, and the amidoparaxylenol diazotised ; to 1 gram of the hydrochloride 10 grams of sulphuric acid and 100 grams of water were used, and the whole kept cold by means of ice and salt. Paraxylorcinol so prepared has all the properties ascribed to it by Stenhouse and Groves (Zoc. cit.), except that it yields a green fluo- rescent solution when treated with dilute soda and chloroform. Metaxylorcinol (Pfaff, Abstr., 1883, 918) crystallises from chloro- form in white monocliniccrystals, a : b : c = 1.7237 : 1 : ? ; p = 38" 21'. It boils a t 276-279". When heated with sodium carbonate solution a t lSO", metaayZol.ci,rLoZcurborylic acid, CsHMe2( OH),*COOH, is formed.40 ABSTRACTS OF OHEMICAL PAPERS.The latter crystallises from dilute alcohol in well-formed prisms which nielt with decomposition at 196", and give a deep blue coloration with ferric chloride. N. H. M. AcetalsesoscinoL By - CAUSSE (J, Pharm. [ 5 ] , 13, 354-358). -The author has examined the action of sulphuric acid and heat on a solution containing acetaldehyde and resorcinol. The crystals obtained are insoluble i n water, ether, chloroform, and ben- zeue. They are soluble in alcobol, which yields them again partly changed. Anhydrous ether dehydrates them, converting them in to II powder, which in time aggregates to yellow, translucent crystals. Thus purified, the compound decomposes on fusing with regenera- tion of resorcinol.Its composition is indicated by the formula c14Hl404 = C2H40 + 2C6H602 - H20. The action of heat on the compound apparently removes the elements of water. Heated a t 120°, a reddish powder was formed which could be obtained in large brown crystals. These had the composition CzeE,60, = 2CI4H,,O4 - The reactions indicate that the yellow crystals are st molecular combination of aldehyde and resorcinyl ether, C,l&O,O( C6Ha*OH)2. Benzylarnine. By T. CURTIUS and G. LEDERER (Rer., 19, 2462- 2463) .-When benzaldehyde and amidoacetic acid are heated together a t 130", carbonic anhydride is evolved and benzylamine formed. Similar reactions seem to take place when cinnamaldehgde, salicylaldehyde, or orthonitrobenzaldehyde, are substituted for the Benzaldehyde, but the products are not so easily isolated.Citric Acid Derivatives of Paratoluidine. By J. M. G:LL H2O. The diacetyl compound, C36H1B012, melts a t 28'2". J. T. L. T. T. (Ber., 19, 2352-2354) -Citroparatoluidide, C6H,04(NH.C7H7),, is obtained by heating citric acid (1 rnol.) and' paratoluidine (3 mols.) at, 140-145" for 10 hours. It crystallises from alcohol, in which it is sparingly soluble, in lustrous, microscopic needl'es, melting a t 189". Citrodlparatoluide, C6H504(NH*C7B7) N.C7H,, is formed when citric acid (1 mol.) and paratoluidine (2 mols.) are heated at 160-170" for three hours. . It melts at 205", is insoluble in water, rather readily soluble i n ether and alcohol, and separates from the latter solvent in small, yellow, well-formed crystals. When heated with citric acid at 140-145", it is converted into citroparatoluidide. Ammonia acts on it, yielding a salt of citrTaraditoluidic acid, C6H,04(NHC7H7)2*OH. The latter crystallises from alcohol in groups of needles, melting at 161".NC7H,, is prepared by adding paratoluidine (1 mol.) to a hot concentrated alcoholic solution of citric acid (1 mol.). On cooling, the solution yields clear prismatic crystals; these are heated for two hours at 160-170", and crystal- lised from water. It melts a t 172*5", and dissolves readily in alcohol, ether, and hot water. N. H. M. By 0: WALLACH (Annalen, 234, 350-364) .- Paxace tometatoluylenediamine, obtained by the action It is soluble in water, insoluble in alcohol and ether.Citroparafoluidic acid, C6H5O4(0H) Azo- and Diazo-compounds.ORGANIC OHEMISTRY. 41 of acetic anhydride on metatoluylenediamine (Abstr., 1883, 329) can also be prepared by converting nitrotoluidine (m. p. 77.5") into the aceto-compound (m. p. L44-5"), and reducing this substance with iron filings and acetic acid. By means of the diazo-reaction, the aceto- metatoluylenediamine is converted into acetamidocresol (m. p. 225"), proving t hatl the acetyl-group occupies the para-position. Parucetamidotolueneorthazodimethy lanild-ne, NHBc*C6H~e.N,*C6H4*N~e2, is formed when a, solution of the diazo-csmpound is poured into an ice-cold alcoholic solution of dimethylaniline. The substance crystal- lises in golden plates and melts at 200". It unites withacids to form salts, which dissolve in water, yielding deep-red solutions. The acetyl-group can be eliminated by boiling with dilute sulphuric acid.P(rramidoto1ueneorthazodimethy Ianilins mystallises in golden scales. It melts a t 145", and dissolves in hot alcohol, chloroform, and ben- zene. The diazo-compound unites with phenol, fomning totueneazo- dirnethy l a d b eparawphenol, NMe2.C6~*N,*C6H3Me.N2*CsH4*OH. . This substance dissolves in dilute solutions of the alkalis, and is reprecipitabed by carbonic acid. It also dissolves in strong acids, and is reprecipitated by the addition of water. It dissolves freely in alcohol, ether, chloroform, and benzene. It is insoluble in water, sparingly soluble in alcohol, b u t dissolves in strong sulphuric acid, with a red coloration.Pai.acRt~idotoluensorthazodiethzJlaniEine crystallises in needles of a reddish-brown colour. It melts at 159", and dissolves freely in alcohol, ether, chloroform, and in acids. The sdts are decom- posed by large quantities of water. Orthacetometatoluylenediamine, NHAc*C6H&le*NH, [Me : NHAc : NH, = I : 2 : 41, prepared from orthoamidoparanitrotoluene (m. p. 107"), crystallises in white needles, and melts at l4W. It is soluble in alcohol, in ether, and in hot water. Orthacetamidotolzceneljarazodintethylamili,ne melts at 192", and dissolves freely in almhol, chloroform, benzene, and ether. Orthamidotoluene- parazodirnethyllanili~~e melts at 215P, and is freely soluble in chloroform, Acetnmido b ,onZen emet azodimet h y landhe, NH Ac*C,H,*&*C,H,*NMe,, crystallises in plates, and melts at 184".Amidobenzenmzodimeth?yl- aniline forms golden scale% soluble in alcohol, which melt at. 165- 166". w. c. w. The corresponding P-naphthol-compound melts about 24". Quinone-oximes. By 3;. SUTKOWSKI (Ber., 19, 2314-2317).- When thymoquinone-oxime is dissolved in cold, fuming hydrochloric acid, a yellow precipitate is formed, consisting of dichlorothymo- quinone and monochlbramidothymol (Andresen, Abstr., 1881, 590). When the precipitate is boiled with glacial acetic acid, a splendid red dye is formed. The reaction is of interest, as itl d ~ o a s the analogy between the Beactions of thymoquinone and of thymoquinone-oxime with fuming hydrochloric acid. Andresen also obtained the same products from thymoquinonechlorimide. The oxime is therefore the hydroxyl-derivative corresponding with the quinonechlorimide.42 ABSTRACTS OF CHEMICAL PAPERS.When chloramidothyrnd hydrochloride and chloranil are hmted in glacial acetic acid solution, the red dye above mentioned is formed. Tetrachloroquiriol is formed in the reaction ; it crystallises in long colourless needles melting at 832". Analyses of the dye point to the formula C30H35C13N203. In a similar manner, a dye was obtained by the action of parsmido- thymol on chloranil in glacial acetic acid solution. It has the cam- position expressed by the formula C,H38N203. (It dissolves in acetic acid, alcohol, ether, and benzene, but not in water. Ammonia dissolves it with formation of a blue solution. Lead acetate gives a blue preoi- pitate.N. H. M. By M. LOEB (Ber., 19, 2340-2344) .-- When the compound Cl6Hl2N2CI2O2, prepared by the action of car- bony1 chloride on ethenyldiphengldiamine (Abstr., 1885, ,1213), is treated with alkalis or acids, it is reconverted into the amidine. Boiling water has no action on it ; 'boiling alcohol converts it into carbanilide, ethyl acetate, and ethyl chloride. The ethyl salt, OEt*CO*NPh*CMe : N*C6H4-COOEt, separates from its ethereal solp- tion in hard, lustrous, rhombic crystals which melt at 90.5". When the chloride is dissolved in benzene and treated with dry ammonia, i t is converted into ethenyldiphenyldiamine and ammonium chloride ; aniline acts like ammonia. Amidine-derivatives. Ethenylimidobenzanilide, CMe<,,,>CO, N.CeH4 is prepared by the action of carbonyl chloride dissolved in benzene on an excess of ethenyldiphenyldiamine ; i t crystallism from benzene in large, lustrous plates melting at 118".It is identical with the compound to which the formula CO( C11H13N2)P was previou-sly ascribed (Zoc. cit.). Dilute hydrochloric acid decomposes it wihh formation of aniline and phengl cyanate. When a saturated ethereal solution of ethenyldiphenyldiamine is treated with two or three drops of water and then with cyanogen until it has a wine-red colour, and allowed to remain for 16 hours, a black crust is formed which yields a compound, C16H16W40; the latter forms a white, crystalline powder very sparingly soluble in ether and benzene, and cannot be recrystallised, as it at once resinifies when heated with solvents.It becomes violet at ;120", and melts with decomposition at 165". Its constitution is probably analogous to that of Griess' cyanocarbimidoamidobenzoic acid, as shown in the formula NPh : CMe*NPh*C(NH)CN + H20. Ethyl allophanate is formed when urethane (7 partsl) and carbonyl chloride (1 part) are dissolved in benzene and heated at 75". N. H. M. Preparation of Aromatic Amides. By 34. FEILETII (Gaxzei%a, 16, 281--284).-The method, proposed by Letts, for the preparation of the nitriles by heating the carboxylic acids with potassium thio- cyanate, has been shown to yield the amides, if ammonium thio- cyanate be substituted for the potassium mlt. The former chaiige is attributed by Keku16 to the greater dehydrating action of the potassium salt, an interpretation confirmed by the observation ofORGANIC CIIEMISTRY.48 Muller that in the above method benzamide is formed if the process is conducted quickly, but phenyl nitrile if slowly. In the course of the preparation of cumonitrile, a small quantity of cuminamide is obtained from the crude product of the reaction, if the aqueous solution, prerioudy rendered alkaline by ammonia, is agitated with benzene. This amide crystallises .in glittering lamins melting a t 153*5", insoluble in cold, sparingly goluble in hot water, soluble in alcohol. It is not decomposed by boiling with hydrochloric acid or potash of moderate concentration. With mercuric oxide, i t yields a derivative, ( CsH4Pr*CONH),Hg + 1+H,O ; this crystallises in needles melting a t 190", insoluble in water, soluble in alcohol.V. H. V. Action of Alkyl Iodides on Dibenzylthiocarbamide. By C. REIMARUS (Ber,, 19, 2348--2349).-Will has shown (Abstr., 1882, 723) that alkyl iodides react with diphenyl- and dibenzyl-thiocarb- amide, with formation of hydriodides of bases in which the alkyl- group is directly combined with sulphur. The author has found that the isomeric dibenzykthiocarbamide behaves analogously. Brnzy Zimidobei,zyZcarbuminethiomefhg I, SMe-C (NHCTH,) : NC7H7, is formed when methyl iodide and dibenzylthiocarbamide are heated for 2-3 hours at 100". Thelproduct is dissolved in water, treated with sodium carbonate, and extracted with ether. The suZphate of the base crystallises in lustrous needles readily soluble in water and alcohol ; i t melts a t 145". The hydrochloride forins large rhombic plates melting a t 125" ; the h!jdriodide crystallises in splendid octahedrii melting at 99", readily soluble in hot water.Benzy ZimidlJbelzzy Zcarbaminethioet~i yl, SEt.C(NHC&) NGTH,, crys- tallises in wide prisms, apparentlF monoclinic, which melt at 93" ; it dissolves readily in alcohol, sparingly in water. %he suZphate forms large rhombic plates readily soluble in water and alcohol ; the plutiiio- chloride crystallises in needles. Corresponding compouuds were also prqpared from propyl iodide and amyl iodide. Phenylseleniocarbimide and Diphenylseleniocarbamide. By H. STOLTE (Ber., 19, 2350-2352).--Yh enyZseZeniocarbimide, CSe*NPh, is prepared by passing hydrogen selenide into aqueous soda, evapo- rating, and adding isocyanophenyl chlolride diluted with ether to prevent the reaction becoming too violent.After a day, the product is filtered, the ether evaporated, and the residue steam-distilled and dried in a vacuum over sulphuric acid. It is.a yellowish-red oil, insoluble in water, readily soluble in alcohol and ether, and has only a slight odour. When the ethereal solution of the substance is treated with ammonia, it is converted into monophenylseleniocarb- amide (Abstr., 1886, 781). Di13heiayZseleniocurbur)aide, CSe (NHPh),, is prepared from phenyl- seleniocarbimide by treating its ethereal solution with aniline. The product is washed with ether, and crjstallised from alcohol. It melts at 1M3 with decomposition. N. H. M. N. H. 31.44 ABSTRACTS OF CHEMICAL PAPERS. Substituted Nitrogen Chlorides.By G. BENDER (Ber., 19, 2272--2274).-When the compound C,H4<-5H> CO (this vol., p. 38) is treated with bleaching powder and hydrochloric acid the cowpomzd C7H,N02C12 separates in colourless needles. When the latter is brought into contact with quinol, an odour of quinone is given off, and on cooling crystals of quinhydrone separate. The componnd is decomposed by alcohol, alkalis, aniline, &c., into the =TTT compound C,H,Cl<f~>CO (Zoc. cit.) . Acetanilide, when treated with bleaching powder in presence of acetic acid, yields the compound NPhCl*COMe. The latter has the properties of the compound described above. It melts at 91' ; when heated to.l72", it becomes yellow, effervesces violently and is converted into its isomeride, parachloracetanilide, melbing at 172".The same change takes place when the substance is treated wibh cold hydro- chloric acid or when warmed with absolute alcohol; if more t,han 2 grams be employed, a violent explosion takes place. The compound reacts with paranitranibine, yielding acetanilide and ort bochloropara- nitrani line. The comPound <C&CO cH2*co >NC1 was prepared from succinimide : it crystallises from benzene in large colourless crystals melting at 148". Ihnaamide yielded the cornpzclzd COPh*N€€Cl. This crystallises fPom water in long prisms melting at 116". Condensation of Nitrobenzaldehyde with Hydrocarbons. By 0- TSCHACHER (Ber., 19; 2463-2464).-Baeyer has shown that fatty aldehydes, in the presence of concentrated sulphuric acid, form condenmtion products with aromatic hydrocarbons, whilst aromatic aldehydes do not.The author finds that the ilbtroduction of a nitro- group into the phenyl-ring gives to aromatic aldehydes the power of forming such condensation products With benzene, metanitrobenzaldehyde yields metanitrotripheny2;- methane, forming crystals melting at 90". With toluene, rnstanitro- phenydditoly ZmethaNe is formed. N. H. M. L. T. T. Compound of Pymvic Acid with Hippuric Acid. By A. HOFFMBNN (Ber., 19, 2554--2557).-6 grams of pyrnric acid were di esCed with 11 grams of sodium hippurate and 25 grams of acetic aniydride on a water-bath. In a short time, a vigorous reaction takes place and the temperature of the mixture rises to 108". The producf is dissolved in alcohol, the solution diluted with water, evaporated, and the brownish crgstala recvystallised from petpoleurn. Analyses of the compound point to the formula CJ&NO4; the sub- stance is therefore formed by the iinion of its two constituents (equal mols.) with elimination of the elements 0% water (2 mds.).I t forms colourless, flat needles melting at 157"'; iD is very readily soluble i n alcohol, ether, and acetic acid; insoluble in water. It yields salts corresponding with a, bibasic acid, C1'LHllNOO. The barium salt, Cl2HEN'O5Br + 2H20, was prepared; when treated with acid, itORGANIC CHEMISTRY. 45 yields the anhydride, ClzH9NOa, the acid not being capable of existing in the free state. When the anhydride is heated with hydrochloric acid at 140°, benzoic acid is formed. N. H. N. Phenyliodohydracrylic Acid.By E. ERLENMEXER and J. ROSENHEK (Ber., 19, 246&2465).-Ph eny l i o d ~ h y d r u ~ m ~ l ic (a-iodo- 6-pheny Zh ydroxypropionic) acid, OH-CHPh-CH I*COOH, was obtained by theaction of iodine chloiPide on cinnamic acid. A chloriodophenyl- propionic acid is probably fimt formed, whieh is then converted into the hydroxy-acid by the action of water. The acid forms large crystals which melt with decomposition at 137-139", and are soluble in benzene. When treated with hydrochloric acid, this acid yields a compound C18H16CI104, which the author believes to have the formula n CHPh : CHG (OH) <g>C(OH) *CHI. CHClPh. L. T. T. Creasolcarboxylie Acid. By H. WENDE (Ber., 19, 2324-2327). -CreosoZcarbozylk acid, OH*C6H2&fe(O?Y1e).COOH [= 4 : 1 : 3 : 51, is prepared by gradually adding 4 grams of sodium to 50 grams of creosol through which a current of dry carbonic anhydride is being passed.The reaction takes place slowly with evolution #of hydrogen and slight development of heat, and is assisted by gently warming; much heat is then developed, and the reaction becomes rather violent. The product, when cold, is treated with dilute hydrochloric acid, extracted with ether, and the ethered solution extracted with sodium carbonate solution. It erystallises in needles melting at lHO-lX'i', dissolves sparingly in water, readily in alcohol, ether, and chloroform, and is almost insoluble in benzene and light petroleum. It sublimes unchanged when carefully heated, and aequires a deep blue colous when trea%ed with ferric chloride.The ammonium saIt crystallises in globular groups of needles ; the potassium salt forms small, readily soluble needles ; the barium salt is sparingly soluble ; the copper salt is a yellow powder; it is very electric when dry. The inethyl salt forms small, rhomhic crystals, a : 'b : c = 0.5285 : 1 : 0.7334 ; it melts at 92", and gives a bluish-green coloration with ferric chloride. The ethyl salt crystallises in s m d l needles or prisms melting at 77". N. H. M. Derivatives of Op'ianic Acid. By C. LIEBERMAWN (Ber., 19, 2275 - 2287 ; compare Abstr., 1886, 550). - Amidohemipinphenyl- ,C : N -- NPh hydrazide (az~ianpheny lhydrnzide), NH( I I , is prepared C6H ( OMe) 2mc 0 by the action of phenylhydrazine on azopianic acid. It separates from its solution in benzene in small, honey-coloured, tetragonal crystals, having a glassy lustre, a : c = 1 : 0.5947. It melts at 222", and dissolves in strong sulphuric acid and in fuming hydrochloric acid.Amido-opianpheny7hydrazide, NH2*C6H(OMe)2<-CH CO-NPh N->, is ob- tained by reducing the nitro-compound (Zoc. cit.) with tin and fuming46 ABSTRACTS OF CHEMICAL PAPERS. hydrochloric acid, care being taken t o prevent the reaction from becoming too violent from the heat developed. On adding water to its alcoholic solution, it crystallises in slender needles melting at 157 -143". is formed when nitro-opianphenylhydrazide is boiled with alcoholic potash, and the potassium salt thus obtained' treated with hydro- ehloric acid. It crystallises in Fellow, glittering, rbombic plates melt- ing at 191". The potassium salt is a carmine-red powder.Oyianoxime anliydride (hemipiniinize), CJ&NO,, is prepared by boil- ing opianic acid (1 mol.) dissolved in nine times its weight of 80 per cent. alcohol with, hydroxylamine hydrochloride ( I t mol.) for two to three hours. It crystallises from alcohol in long, very slender needles melting at7 228-230". An aqueous or alcoholic solution con- taining only a trace of the subdance has a fine blae fluorescence. It sublimes unchanged, and can be heated with strong sulphuric acid without decomposition. Cold aqueous a1 kali dissolves it, forming a, yellow solution which soon ldecomea colourless. When heated with alkali, it, yields hemipinic acid and ammonia. The compound was alm prepred by heating ammonium hemipinate.The potassium salt, CloH80NK, is a white compound almost insoluble in cold absolute alcohol. Hemipinethyl imide, ClnH804 : NEt,.is obtained by heating potassium hcmipinimide with ethyl iodide at 150". It crystallises from boiling water in colourless- needles resembling hemipiuimide ; the solution shows the same fluorescence. It diksolveR very readily in alcohol, acetone, and benzene, and melts a t 96-98". The formation of hemipinimide is interesting on account of its complete analogy with observations lately made in the phthalic acid series. The author a,ssigns to the compounds phthalimide and hemi- pinimide the respective constitutional formulae. CO<-O'>C : NH 0- and Co<G,(OMe), Anilido-opianic acid, Cl6HI5NOd, is obtained by boiling a solution of equal weights of opianic acid and aniline, dissolved in gIacial acetic acid, for 10 minutes.On cooling, the whole solidifies to a, white mass, which is washed with water, dissolved in benzene, and precipitated with ether. It dissolves only in Btrong alkali solution. Artilidonitropianic acid, C16H14N20s, is prepared from ni tr- opianic acid in a manner similar t o the above compound. It, cr-ystal- lises in needles melting a t 183-184". When treated with alkali, it yields n sparingly soluble potassiwn salt. Nitrohemipinic acid, K02*CsH(OXe)2(COOH)o, is very readily p1.e- pared by boiling nitropianic acid with fuming nitric acid (4 parts) for one hour. It melts a t 166" (not 155"), but has all the other properties ascribed to it by Prim (Abstr., 1882, 402).Wben heated above its melting point, it gives up water and yields a yellowish compound, probably the anhydride. The silver s@Zt was also prepared. c6H4 >C : NH. It melts at 186-187'.ORGANIC CHEMISTRY. 43 Opianic anhydride, [ CHO*C,H,(OMe),*CO],O, is formed when opianic acid is heated at 160" in a current of dry air. It crystallises well from acetone and melts at 234". It is identical with the coni- pound described by Wegscheider (Ahstr., 1883, 996) as triopiarnide, 0,H,aO14. When boiled with alkali, it, is gradual17 transformed into opianic acid. Strong nitric acid converts it into nitropiauic acid. Opianic Acid Derivakives. By C. IJTEBERMANN and S. KLEEMAKN N. H, M. (Ber., 19, 2287-2299).-AcetyZupinnic acid, is prepared by heating opianic acid and dry sodium acetate with acetic anhydride.The excess of. acetic anhydride is then removed by contact with cold watey for 24 hours, and the remaining compound crptallised from boiling water. It is inso- luble in cold aqueous alkali, and when boiled with it, is decomposed into opianic and acetic acids. >CH*OAb, is prepared Acetylnitropianic acid, < in a manner similar to acetylopianic acid. I& is a yellow substance insoluble in cold sodium carbonate solution. Propiony lopa'anic acid, C13H1406, crystallises in needles melting at 111". An hyaraceta nt id oh emip inic acid, G ,,H,AcN O,, and trhe pi-opion y 1- compound, C,,H,( C3H,0)N0,, melt at 164" and 139" respectively ; they ape very unstable. )CH*CH,*COO@ is obtained by heating opianic acid (3 parts), rnalonic acid @+ part), glacial acetic acid (2 park), and sodium acetate (li Rart) for five hours at 100" ; the colourless, crystalline product IS crystallised from water.It forms lustrous needles melting at 167" ; it has an aoid reaction and dissolves i n ammonia. The silver, calciunz, &c., salts were prepared. The ethyl salt crystallises in plates soluble in alcohol, ether, and hot water; it melts at 82.5". The reactions of the acid are analogous to those of phthalylacetic acid. When boiled with baryta, and the excess of baryta afterwards removed by means of carbonic anhydride, barium opianylacetate" is obtained ; it forms lustrous prisms. The free acid is not capable of existence. When the silver salt is treated with methyl iodide, it yields, not methyl opianjlacetate, but methyZ m ecoiline-acetate ; the latter crystallises in lustrous plates melting at 124".It melts at 120-121". (JO--- C6H(N0,) @Me), co- CsH2(0Me)2 Necouiw-acetic acid, < >CH*CH,*COOH, is pre- co--0 Normecortine-acetia acid, <C,H,(OH), pared by heating rneconine-acet& ahd with hydriodic acid and phos- phorusi ; the product is diluted with water and filtered. It crystal- lises from water in long plates melting a t 218". The calcium and buriuwt saZts form white crystalline precipitates. When the acid is * The fmmtda slnd azalp:s given in the original do not agree.48 ABSTRACTS OF CHEMICAL PAPERS. heated with ferric chloride, it acqfiires a characteristic blue colour, which changes to green in presence of an excess of ferric chloride, The ethyl salt separates from its solution in boiling water as an oil, which then solidifies and melts at 131".Its solution is fluorescent and reduces silver solution, but to a smaller exbenltthan the free acid. I t has an acid reaction and precipitates from baryta solution a yellow barium salt of the ether. This acid property and the power of reducing silver solutions is due t o the presence of pylrocatechol- hydroxyl. Ort h onitrom econine- acetic acid, co -o>CH.CH2*COOH [NO2 : CH*CH2*COOH=1 : 21, <C,H(N02) is obtained by dissolving meconine-acetic ncid in fuming nitric acid and afterwards precipitating with water. It forms colourless crystals melting at 176". The ethyl salt crystallises in lustrous needles, rcadily soluble in alco'hol and benzene ; it melts at 129".Nitromeconine-acetic acid dissolves in sulphnric acid, forming a. yellow solution ; this, when warmed, acquires a cherry-red colour, characteristic of compounds containing a nitro- group in the ortho-position to a long side-chain (Baeyer, Abstr.. 1882, 620). When the nitro-compound is reduced with tin and hydro- c hloric acid, dimethox y hy drocarbostyril- lactone, The calcitwt saZt forms yellow needles. is formed. This crystallises from water in colourIess needles, melt- inq with evolution of carbonic anhydride at 256". It is readily soln'ble in alcohol and glacial acetic acid, insoluble in ether and benzene. It dissolves in baryta; when the solution is boiled and treated with carbonic anhydride and evaporated down, Iastrous needles of barium dimethoxyhydrocarbostyrilcarboxylate are ob- tained.Dilnetliox~IddihydrochZoroquinoline lactone, 6C12Hl0N Clod, is prepared by heating the lactone just described with phosphorus pentachloride and some phosphorus oxychloride for two hours at 165-170"; the product is poured into iced water, and the precipitate crystallised froni alcnhol, from which it separates in needles ; these melt at 218" with evolutim of carbonic anhydride. The barium) salt, obtained by boiling the lactone with baryta, and the silver salt were prepared. Dihydroxydihydroquinoli?ie lactone, CloH,IIU'O,, is obtained by heating the above chloro-derivative dissolved in glacial acetic add for one hour at 120" with hydriodic acid. It melts at 220" with decomposition. By H. GRCNR (Ber., 19, 2299-23@5).- Azo-opianic acid, prepared from nitropianic acid, melts at 200" with decomposition (not 184" as given by Prim, Abstr., 1888, 404).The pofassium salt is a white crystalline powder. The et?iyl salt crystal- 1ises in needles melting at 98" ; the methyl salt melts at 127". The author confirms the statement of Prinz ( ZOC. cit.) that azopianic acid, when boiled with barytzt in excess, yieIdrJ barium amidohemipinate N. H. M. Azo-opianic Acid.ORQAXIC CHEMISTRY. 49 The yield is almost quantitative. Sodium amidohenzipinate crystallises from alcohol with 3 mols. H,O, in long, almort white needles ; it is very readily soluble in water. The copper salt (with i mols. H,O) erystallises in stellate groups of slender, green needIes. The aqueous solution of the free acid has a fine green fluorescence which disappears when alkalis or acids (except acetic acid) are added. It reduces a cold animoniacal silver solution, and Fehling's solution when warmed.ob- tained when a cooled solution of sodium amido-hemipinate is treated with sodium nitrate and hydrochloric acid. It is a bright yellow, micro- crystalline powder which becomes superficially red when exposed to light, and explodes at 140-150" or when struck. It dissolves readily in alkalis and acids ; when boiled with water, it gives off nitrogen and yields a hydroxy-acid, which gives an intense blue-violet colour with ferric chloride. The hydrochloride, COOH*CsH( OMe),( COOH)*N,Cl + H20, crystallises in long, colourlew needles ; in presence of water, it decomposes into hydrochloric acid and free anhydroazohemipinic acid.When the diazohemipinic acid is boiled with alcohol undsr slight pressure, it is converted, with evolution of nitrogen, into hemi- pinic acid. Nitrohemipinic acid was prepared by Liebermann's method (this vol., p. 46). The potacsium sult crystallises in deep yellow prisms, readily soluble in water and alcohol, the silver saZt is also yellow. 21Titrohen2ipinic rcnhydride, NO,*CsH( OMe) <co > 0, is prepared by heating the acid at 160-165" for two hours ; it crystallises from benzene in bright yellow prisms melting a t 145". When nitrohemi- pinic acid is reduced with ferrous sulphate and soda, amidohemipinic acid is formed identical with the acid obtained by boiling azo-opianic acid with baryta. The results of the experiments above described confirm the view brought forward by Liebermann (loc cit.) that Prinz's so-called azo- opianic acid is not an azo-derivative of opianic acid but an internal anhydride of orthamidohemipinic acid.When nitrohemipinic acid is reduced with tin and hydrochloric acid, the compound COOH.C6H,( OMe)2*NH2,HC1 is formed. N. H. M. Derivatives of Normethylnitropianic Acid. By K. ELBEL (Ber., 19,2306-2312) .-Normethylnitropianic acid COH* C6H ( C 0 OH) (OH) ( OMe) *NO,, is best prepared by heating finely powdered nitropianic acid with fuming hydrochloric acid (10 parts) for 15 hours at loo", with a reflux condenser, hydrogen chloride being passed in all the time. The product is evaporated down, when the normethyl-compound sepa- rates ; the yield is 80 per cent.of the theoretical. Normethylorthanhyd~-lzmidohemipinic acid (normethylazo-opianic acid), OMe*C6H(OH)(COOH)<~~> [OMe: OH : COOH : CO : NH = 4 : 3 : 2 : I : 61, is obtained by treating a boiling saturated aqueous N,-0 Anhydrodiazohenzipinic acid, COOH*C6H(O~e)2< co >, is co VOL. LII. e50 ABSTRACTS OF CHEMICAL PAPERS. fiolution of normethylnitropianic acid with tin and hydrochloric acid. It is dissolved in alcohol and precipitated with water. It crystallises i n colourless, lustrous needles which melt at 174-175" with decom- position ; i t is readily soluble in alcohol, sparingly in benzene, and insoluble in ether. When boiled with baryta, crystals of barium normet h ylamido hemi pinate are formed. The diacety I-d erivative, O&fe*C6H(OAc) (COOH)<NA:>, co oMe*C,H(oAc)(CooH)<,,>, co melting at 198'.is obtained by boiling normethyl- anhydramidohemipinic acid with sodium acetate and acetic anhydride (10 parts) for one hour. It melts a t 205", dissolves readily in ben- zene; the alcoholic solution has a fine blue fluorescence. It is very unstable and changes when kept into the monacetyl compound, Normethy/nit?.opianic acid phenylh ydrazine crystallises in red needles which melt a t 178-179" with decomposition. When boiled with glacial acetic acid, it parts with the elements of water and yields norrnethy Znitropiaxide, No2*C6H(0Me) (OH) < ca: : N->. The latter crystallises in lustrous, lemon-coloured, rhombic plates melting at 191". I t dissolves unchanged in dilute potash solution.The potassium salt is very readily soluble in water, almost insoluble in absolute alcohol. Normethy Zamido-opiaxide is obtained by boiling the nitro-compound suspended in ammonia with ferrous sulphate. It crystallises from alcohol in short, almost colourlesv prisms. CO*NPh Normethy1rritro~'anoximic acid, NO2*CsH(OMe) (OH)(COOH)*CH :NOH [ = 6 : 4 : 3 : 2 : 11, is formed b;j- mixing a boiling solution of normethylnitropianic acid in water (40 parts) with an aqueous solution of hydroxylamine hydro- chloride and sodium acetate. It crystallises from alcohol in lustrous yellow needles which become brown when warmed, and melt at 252". It has a slight reducing action on Fehling's solution. It dissolves in alkali with SL deep-red colour, and the solution gives off ammonia, when boiled, with formation of normethylnitrohemi~inic acid, NO,*C,H(OMe) (OH)(COOH), [ = 6 : 4 : 3 : 2 : 11.The latter crys- tallises from alcohol in almost white, silky needles, readily soluble in water and alcohol; it melts at 220". The hydrogen potassium salt forms bright yellow prisms. The same acid is formed when nor- methylhemipinic acid is nitrated with dilute nitric acid, Normethylnitrohemipinimide, N02*C6H( OMe) (OH) <C CO.0- H)>, is obtained by boiling an alcoholic solution of normethylnitropianic acid with hydroxylamine hydrochloride, or better by boiling normethyl- nitropianoximic acid with glacial acetic acid. It crystallises in bright yellow needles which melt a t 252" with decomposition. Homo-orthophthalimide. By S. GABEIEL (Ber., 19,2363-2367 ; compare Abstr., 1886, 812, and this vol., p.61).-When a solution of homo-orthophthalimide (2 grams) and potash (1 gram) in methyl alcohol (15 c.c.) is digested with methyl iodide (4 grams) at loo", N. H. M.ORQANIC CHEMISTRY. 51 dimethylhomo-orthophthalimide, CgH5Me2NO2. is formed. The latter crystallises from water in flat needles melting at 119-120"; it is readily soluble in the usual solvents and in alkali. When heated with potash and methyl iodide a t loo", it yields the trimethyl- derivative, CDHaMe3NO2 ; this cry stallises in long needles melting at 102-103" : it is readilv soluble. Alkali does not dissolve it. CH G O Howio- ort hophthalmeth y limide, C&< .kMe > , is formed by evaporating a mixture of homo-orthophthalic acid and methylamine, arid distilling the residue.It forms long, colourless needles, which melt a t 123" and boil at 314-318". I t is readily soluble in the usual solvents and dissolves in alkalis. When heated with methyl iodide and potash, it yields trimethylhomophthalimide melting at 102-103". In the latter compound, therefore, one of the methyl-groups is attached to nitrogen. Trimethylhomophthalimide is hardly attacked by fuming hydrochloric acid at 100", and so cannot contain methoxyl; when heated with the fuming acid a t 230-240", the anhydride of a co This crystallises in flat crystals melting at, 82.5-83" ; the silver salt, Cl1HI6OkAg2, was pre.. pared. The anhydride is also formed when dimethylhomophthalide (fi-om homophthalide, potash, and methyl iodide) is heated a t 230" with fuming hydrochloric acid; ammonia is formed in the reaction.Tri- and di-methylhomophthalimide and the anhydride (m. p. 82.5433") have probably the constitution expressed in the formula- , bibasic acid, C,H,Me,<CO>O, is obtained. Action of Amines on Phthalylacetic Acid. By E. MERTENS (Bey., 19, 2367--2373).--Pure phthalylacetic acid is stiriaed with water and treated with a 33 per cent. solution of ethylamine until it is dissolved ; it is then filtered and saturated with hydrogen chloride, being kept cold the whole time. A white crystalline substance gradually separates with ,slight evolution of carbonic anhydride, Analyses show the compound to have the formula C~~&,O~NZ. It melts at 129", dissolves readily in warm alcohol, ether, and chloro- form, more sparingly in benzene ; boiling water decomposes it.2Methylei~eyphthalethimidine, CO< z g i > C CHz, is formed when the compound C,H,,O,N, is heated above its melting point ; carboriio anhydride and water are evolved. It has a carrot-like odour, distils with steam, and is readily soluble in alcohol, ether, and chloroform, &c. It strongly resembles Gabriel's methylenephthalomethimidine (Abstr., 1885, 1228). Phthalethimidylacetic acid, C@< %g(>C : CH-COOH, is obtained by keeping a solution of the compound C,H24N205 in sulphuric acid (10 parts) for 24 hours, and then pouring it into water. The white crystalline precipitate is crystallised from dilute alcohol, from which it eCL52 ABSTRACTS OF CHEMICAL PAPERS. separates in yellow needles melting a t 180" with effervescence.It is readily soluble in hot water, alcohol, and ether, less soluble in benzene. The silver salt forms a flaky crystalline precipitate; the barium saZt crystallises in yellow lustroufi needles. Propylamine and phthalylacetic acid yield the compound C,,H,,O,N,. It forms large well-formed prismatic crystals which melt with effervescence a t 103". It behaves similarly to the ethylamine compound. Acetophenone-orthocarboxa.,7iZideJ COMe*C6H4*CO*NHPh, is obtained by warming phthalylacetic acid with aniline. After the evolution of carbonic anhydride has ceased, the whole is left for 24 hours, when the substance separates in white crystals. It crystallises from benzene in large, well-formed cubes which melt at 189- 192", and dissolve readily in warm alcohol, ether, or chloroform.When heated a t 204" and afterwards a t 2.30". it is converted with evolution of aniline and water into rnethylene~hthal~~enimiLJine, CO<::~>C CH,. The latter crystallises in yellowish prisms readily soluble in alcohol, ether, and chloroform; it melts at 100". When acetophenonecarboxanilide is kept dissolved in strong sol- sulphuric acid for 24 hours, it is converted into a compound, C16H11N0, isomeric with the compound just described. It is sparingly soluble in alcohol and ether, readily in benzene, chloroform, and light petroleum ; it melts at 265". N. H. M. Bromoterephthalic Acid. By M. FILETI (Gaxzetta, 16, 284- 287).--Pischli (Abstr., 1879, 639) states that the monobromotere- phthalic acid obtained by the oxidation of bromotoluic acid retains 1 mol.H,O, even after drying a t 120". As the same acid obtained from bromocymene was found to be anhydrous, the author has repeated Pischli's experiments. The analytical results obtained for the proportion of carbon and bromine show that this acid is also anhydrous. Its silver salt is precipitated as a white, gelatinous mass, somewhat soluble in water. The methyl saZt, C6H,Br(COOMe)2, obtained from the said chloride (Fischli), as also from the acid itself (Fileti), crystal- lises in acicular prisms, melting at 5 2 " ; it presents a well-marked chromatic polarisation. V. H. V. It melts a t 296", and at the same time sublimes. Curnidic Acids. By E. SCHNAPAUFF (Ber., 19, 2508--2511).-The author prepared a-cumidic acid, C6H&fez(GOf)H,), [Me : Me : COOH : COOH = 1 : 3 : 4 : 61, by a modification .of Wurtz's process, by the action of efhyl chloro- carbonate and sodium amalgam on dibromometaxylene, This acid forms glittering prisms melting much above 320"' and subliming with only slight decomposit,ion.It is easily soluble in boiling alcohol, very sparingly in boiling water. Its barium salt crystallises with 1+ mol. H,O, and is very soluble in water: the methyl salt forms long needles or plates and melts a t 76". Cumidic acid, obtained as described by Jannasch (this Journal, 18'71, 240) by the oxidation of durene, was converted into the methylORQANIC CHEMISTRY. 53 salt, and this by crystallisation from alcohol was separated into two parts, the one melting a t 76" the other crystallising in needles and.melting at 114". The former was the methyl salt of the a-acid j u s t described. The ether melting a t 114" yielded @-cur/lidic acid [Me : Me : COOH : COOH = 1 : 4 : 2 : 51 on hydrolysis. This acid is easily soluble in boiling alcohol, very sparingly in boiling water ; it rr\-stnllises in hexagonal prisms, and sublimes at high temperatures without previous fusion. Its barium salt crystallises with 24 mols. H20; its methyZ salt melts at 114" and boils at about 297" (corr.). When the barium salt is distilled with excess of lime, paraxylene is formed, so that the above formula may be regarded as established. Jannasch's acid is, therefore, a mixture of two isomeric cumidio acids. L. T. T. Reaction of Stilbene. By (3.ERRERA (Cazzetta, 16, 325).-Kade (Abstr., 1880, 46) states that stilbene in alcoholic solution gives a red coloration when heated with a solution of ferric chloride. It is here shown that this change is in reality due to the presence of water in the alcohol, which causes a partial decomposition of the ferric chloride into hydrochloric acid and some stable form of ferric hydroxide. Stilbene is not even necessary for the reaction ; if absolute alcohol is used no colour-change ensues. By T. ZINCKE (Ber., 19, 2493-25Q2) .-In the hope of elucidating the constitution of the two compounds, C3,H,,N,0s and CB1HP2NCOG (Abstr., 1882, 736, and 1883, 210), ob- tained by the action of nitrous acid on P-naphthaquinone-anilide and -toluide respectively, the author has undertaken similar investigations with phenanthraquinone.I n the present communication, the author details some preliminary experiments as to the action of alkalis on halogen-derivatives of /I-naphthaquinone, which were made to deter- mine whether @-naphthaquinone-deriva tives undergo changes similar t o the conversion, by the action of alkalis, of phenanthraquinone into di phenyleneglycollic acid. the action of bromine in acetic solution on p-naphthaquinone, and crystal- lising in red prisms melting at 177-178", dissolves readily in cold tlilute alkalis. From these solutions, acids precipitate hjdroxybromo- /3-naphthaquinone, described by Merz and Baltzer. Aniline and am- monia also act on bromo-/j-naphthaquinone, forming corn pounds analogous to naphthaquinoneanilide. Dibrorno - /3 - naphthayuino,he, [0 : 0 : Br : Br = 1 : 2 : 3 : 41, could not be obtained directly from naphthaquinone, but was formed by the action of excess of bromine on an acetic solution of the monobromo-derivative.It is best ob- tained, however, by the action of bromine on a-amido-p-naphthol. It crystallises in red: rhombic scales or tables, sparingly soluble in ;~lcohol and ether, and melts a t 172-174". With ammonia and aniline, it yields the same compounds as the monobromo-derivative. It dissolves in cold dilute alkalis, and from these solutions acids Irecipitate a substance, crystallising in small white needles ; this has not beeu further investigated. V. H. T. p-Naphthaquinorre. Rro.rrLo-@-nuphthaqIcinone, [0 : 0 : Br = 1 : 2 : 31, obtained54 ABSTRACTS OJ!' CHENICAL PAPERS.ChEoro-P-naphthaphone, [0 : 0 : C1 = 1 : 2 : 31, is formed when chlorine is passed through a solution of p-naphthaquinoiie in ten times its weight of glacial acetic acid, until a precipitate begins to be formed. It crystallises in red needles, soluble in alcohol, glacial acetic acid, and benzene, ahd melts a t 172". It gives an additive product with hydrochloric acid which forms white cr,ystals. It dissolves in dilute alkalis, and this solution when acidified yields hydroxychloro-a-naphthaquinone. The unstable p- hydroxy-compound undoubtedly first formed passes into the more stable a-derivative. When chloro-P-naphthzquinone is reduced with sulphurous acid i n acetic solution, chloro- p - naphthapuinol, C,H,Cl(OH),, is formed, and crystallises in long, colourless needles melting a t 116-117".The anilide and imide of chloro-p-naphthaquinone both crystnllise in dark-coloured scales having a metallic lustre, the former substance melting a t 253", the latter at 260". Dichloro-p-naphthczpi~inzone, [0 : 0 : C1 : C1 = 1 : 2 : 3 : 41, may be obtained directly from the quinone, but is best prepared by the action of chlorine on a-amido-p-naphthol. It crystallises i n red scales, needles, or tables, easily solnble in chloroform and boiling benzene, sparingly in alcohol, melts a t 184", and sublimes without decom- position. With ammonia or aniline, it forms the imide or anilide respectively. When reduced with sulphurous acid in acetic solution, it yields dichloro-/3-naphthaquinone, crystallising in white needles which melt a t 125". Ik dissolves in cold dilute alkali, and this Eolution when heated becomes cloudy, and deposits a greyish-white precipitate.If the cold alkaline solution be treated with excess of acid, an acid of the formula C,H,Cl?03 is liberated. This acid crys- tallises with 1 mol. H20 in small white needles, melts a t 98-100", and is easily soluble in alcohol, sparingly so in water. Its methyZ smZt forms colourless scales or hexagonal plates melting a t 13'7-138". The action of the alkali on the dichloroquinone appears to take place according to the equation C,oH4Cl,0, + H,O = CloH,Cl,O,. The author considers the action to be similar to the action of alkalis on phenanthrsquinone, and the most probable constitution of the acid t o he CCl<ccl:> C6 I3 C( OH)-COOH.The acid forms an ncety Z-dericative, melting at 75-76'. Boiling baryta-water or alkalis cause a separa- aion of carbonic anhydride. When a solution of the acid in glacial acetic acid is treated with concentrated sulphuric acid at 120", hydrogen chloride is evolved, and a yellow crystalline compound melting at 224-226" is produced. The acid is decomposed on heating its aqueous solution, a yellow compound of intense odour and volatile in steam being amongst the products of reaction. The experiments on the bromo-derivatives were carried out in conjunction with Weltner, those on the chloro-derivatives with C. Frolilich. L. T. T. Benzene- and Toluene-azonaphthols and their Isomeric Hydrazine-derivatives. By T. ZINCKE and I?. RATHGEN (Ber., 19, 2482 - 2493).- W $en the two position-isomerides, benzeneazo-p- naphthol and P-napl -thaquinonehydrazide (see Zinckc and Bindewald,ORGANIC CHEJIlSTRY. 55 Abstr., 1%35, 391), are reduced by means of stannous chloride, the former yields a-amido-@-naphthol, the latter P-amido-a-naphthol. When a-amido-/I-naphthol is oxidised, P-naphthaquinone is formed, but the authors find that p-amido-a-naphthol yields under similar conditions P - diriaphthaquinone (/3 - dinaphthadiquinone). Both quinones yield with bromine dibromo-p-naphthaquinone. When heated with nitric acid, benzeneszo-P-naphthol yields dinitro- P-naphthol, CloH5(OH)(N0,), [NO, : OH : NO, = 1 : 2 : 41, whilst p-naphthaquinonehydrazide yields dinitro-a-naphthol [OH : NOz : NO, = 1 : 2 : 41. When the above isomeric hydraside and azo-compound are reduced in alkaline solution, they are both decomposed into aniline and amido-naphthol. The author disputes the correctness of Denaro's assertion (Abstr., 1886, 246) that two isomeric benzeneazonaphthols can be obtained from p-naphthol.The authors have also investigated the corresponding toluene-deriva- tives. Pitratolueneazo-a-naphthol, OH*CloH6*Nz*C7H7 [OH : N, = 1 : 41, was prepared like the similar benzene-compound. It crys tallises in dark-red flakes having a metallic lustre, aud melts with decomposition a t 208". It is easily soluble in acetone, aniline, and alkalis, sparingly so in alcohol and acetic acid. No bromo-derivative could be obtained. Nitric acid yields dinitro-a-naphthol (b. p. 139"). The hydrochlorida and hydrobromide form bluish-green scales, which are slowly decom- posed by water, rapidly by alcohol.It also Eorms metallic derivatives. The ethoxide crystallises in red needles, which appear yellow by transmitted light, and melt a t 126-127"; the methoxide melts a t 103-104" ; the acetyl-derivative crystallises in yellow needles melting a t 101-102". Orthotolueneazo-a-naphthol, [OH : N, = 1 : 41, forms red needles melting a t 144-146', soluble in alcohol, benzene, and ncetic acid. It forms dinitro-a-naphthol with nitric acid, and yields salts resembling those of the para-compound. The sthoxide crys- tsllises in red scales melting at 94", the methoxide in reddish- brown needles melting a t 93". Para- and ortho-tolylhydrazides of a-naphthaquinone are identical with the corresponding azo-com- pounds.Parato Zuene-@naphthol, ClOH~ON,H*C,H7, or C10H6 (0 H) *Nz*C7R7 [0 : N, : : 2 : 11, forms red crystals with green flnorescence, is soluble in alcohol, benzene, and acetone, and melts a t 134-135". It forms very unstable salts with acids. The dibrorno-derivative forms intensely red needles melting at 190". Nitric acid converts the azo-componnd into dinitro -P-napht hol (m. p. 194"). 0 rthotol ueneazo +-nap ht h ol, [O : N, = 2 : 11, crystalliscs in small red needles or scales which melt a t 131". With nitric acid, it yields a dinitro-p-naphthol melting a t 167". The tolylhydrazides of P-naphthaquinone are, like the similar phenylhydrazide, isomeric and not identical with the nzo-compounds. They resemble them, however, very closely, the chief difference being their greater solubility i n alkalis. P-Naphfhaquinone-iuaratolylhydr- azide, CIOH60*N2H*C7H7 [0 : NP = 1 : 21, crystallises in small, red, glistening needles which melt at 145".The dibromo-dericative, CliH12B~-20, forms red, sparingly soluble needles melting at 236". B-NallhthapuinrJne-o~t~iotol~~li y draxide crystallises in red scales with a The P-derivative melts at 1!34", the a- a t 138".56 ABSTRACTS OF CHEMICAL PAPERS. golden-yellow fluorescence. It is easily soluble i n the usual solvents and melts at 156". Its dibromo-derivative melts at 254". Besides these hydrazides, the product of the action of the tolylhydrazinc on the p-naphthaq uinone always contained considerable quantities of di- naphthyldiquinol. L. T. T. New Diamidodinaphthyl.By P. JULIUS (Ber., 19,2549-2552). -am-Dinaphthyl is best prepared by distilling a-dinaphthol with zinc- dust (10-15 parts) : the distillate is re-distilled in a vacuum and recrgstallised from glacial acetic acid. Mononitrodinaphthyl, C10H7*C10H6*N02, is obtained by adding nitric acid, of sp. gr. 1.3 (20 grams), to a solution of dinaphthyl (10 grams) in 150 C.C. of glacial acetic acid. It crystallises in lustrous, orange- coloured plates melting at 188". It dissolves easily in hot benzene and glacial acetic acid, less readily in alcohol and ether. Dinitrodinaphthyl, N02*C10H6*C10~6*N01, is prepared by treating a solution of 10 grams of dinaphthyl in 150 C.C. of glacial acetic acid with 80 grams of nitric acid, and then heating at 60". It crystallises in bright yellow, volumiiious needles which melt at 280°, it dissolves very sparingly in benzene, xylene, and glacial acetic: acid, and is practically insoluble in other solvents.Uiczmidodinaphthyl hydrochloride, ~H,*C,oH6~C,oH60NHz,2H~l, is prepared by treating 10 grams of the dinitro-compound, suspended in 200 C.C. of glacial acetlic acid, with hydrochloric acid, and50 grams of zinc-dust. It is readily soluble in water, sparingly in strong hydro- chloric acid ; when exposed to the air, it quickly becomes green. The free base could not be isolated. The diacety 1-derivatiue crystallises in almost colourless needles which melt above 300" ; it is insoluble. When the hydrochloride is treated with ferric chloride, dark-brown, lustrous needles of diimidodinaphthyl h?ydrochloride, CZoH,,N,C1,, .are obtained ; this is reconverted by reducing agents into the diamido- compound.N. H. M. Tetrahydroxyanthraquinones. By E. NOAH (Ber., 19, 2337- 2340) .-When metahydroxybenzoic and gallic acids (equal mols.) are heated with sulphuric acid (10 parts) for 20 hours at 170", two tetrahydroxyanthrapuinones, ClaHa( OH),O,, are formed, together with hexahydroxjanthraquinone. The product is extracted with alcohol, the solution evaporated to dryness, and the residue extracted with benzene. The solution contains +now only one tetrahydroxyant hra- quinone. This crystallises in long, slender, red, lustrous needles, which do not melt at 350", and sublime with difficulty, becoming partly carbonised. I t is readily soluble in alcohol, acetone, and glacial acetic acid, sparingly in benzene, xylene, &c.The solutions in sulphuric acid and in caustic alkali are violet and emerald coloured respectively. The tetracety 1-derivative crystallises in yellow micro- scopic needles, which melt with decomposition at 207-2U9". The second tetrahydroxpnthraquinonc is extracted by means of dilute alcohol from the residue undissolved by benzene. It crystallises in small, red needles which do not melt at 380" ; it sublimes in small, yeilow needles, but is mostly decomposed. It dissolves readily inORGANIC CHXMISTRT. 57 alcohol, glacial acetic acid, and acetone, sparingly in ether and ~ a t e r . The solution in sulphuric acid is brownish-yellow; that in caustic alkali emerald-coloured. The tetracetyl-compound crystallises in lemon- coloured prisms, which are very readily soluble in glacial acetic acid, alcohol, and chloroform ; it melts at 189".N. H. M. Methylanthragallols. By E. L. CAHN (Ber., 19, 2333-2336 ; compare Abstr., 1886, 556).-l-~Methylanthragallol, is prepared by heating orthotoiuic acid (3 parts) with gallic acid (2 parts) for 12 to 15 hours up to 130-135". It crystallises from alcohol in gold-coloured flakes consisting of microscopic needles. It sublimes in long, orange-coloured needles, and melts at 297-298" with decomposition. It is readily soluble in hot alcohol and glacial acetic acid, sparingly in benzene ; it also dissolves in hot water, yield- i n g a red solution. The triacety 1-derivative crystallises in sulphur- coloured microscopic plates melting at 208-210", readily soluble in chloroform, acetone, hot alcohol, &c.When methylanthragallol is distilled with zinc-dust, a hydrocarbon, crystallising in white plates and melting at 197", is formed. When oxidised, it is converted into a quirione melting at 278-2279". 3-~etl~ylanthragallol is prepared in a manner similar to the above compound from paratoluylic acid. It melts at 275', and sublimes in orange-coloured needles. It resembles its isomeride. The triacetyl- derivative crystallises in well-formed, lustrous, golden prisms melting at 203-208' with decomposition. 2- Methyl- and 4-methy l-anthragallol are formed simultaneously from metatoluylic and gallic acids. The separation of the isomerides is difficult, and is best performed by converting the mixed product into the acetyl-derivative and recrystallising repeatedly from glacial acetic acid.The one methylanthragallol has a slight golden lustre, and melts at 31 2-313" ; the other crystallises in small, well-formed prisms melting at 235-5240". The acetyl-derivatives melt at 188-190" and at 217-218" respectively. The four methylanthragallols closely resemble one another and anthragallol. They are readily soluble in alcohol, and dissolve in strong and in dilute alkalis, yielding green and violet solutions respec- tively. The solution in hot ammonia has a fine blue colonr, in sul- phuric acid it is red; the latter changes to green on addition of a trace of nitric acid. The absorption-spectra of the red solutions of anthragallol and of the methylanthragallols in sulphuric acid are almost the same.N. H. M. Acid from Santonin : Isophotosantonic Acid. By S. CANNIZ- ZARO and G. FABRIS (Ber., 19, 2260-2265) .-Isophotosantonic acid, C15H3206, is obtained by exposing 1 kilo. of santonin dissolved in 52 litres of acetic acid to the action of light for several months ; one-ninth of the acetic acid is then boiled off under diminished pressure, and the58 ABSTRACTS OF CHEMICAL PAPERS. residue filtered from the photosantonic acid which separates on cool- ing. A further quantity of photosantonic acid is precipitated by adding water. The solution is then nearly free from photosantonic acid and still contains almost the whole of the isorneride. It is treated with sodium carbonate (which dissolves the photosantonic acid alone) and extracted with ether.It separates from its alcoholic solution in thick, triclinic crystals, rather soluble in ether, and sparingly in water. When heated a t loo", it is converted into the lactone, C,,H,,O*. It is dextrorotatory, [a]= = f 3 24" 17'. Photosantonic acid has nearly the same specific rotatory power, but is lsevorotatory. Isophotosan- tonic acid dissolves in alkalis and in warm solutions of alkaline carbonates ; the solutions are orange-red. The barium salt, (C15H,106)2Ra + H,O, is an amorphous powder, readily soluble i n alcohol and in water. The monacetyl-compoimd crystallises from alcohol in transparent needles which melt a t 183" ; it is dextrorotatory, [ a ] D = + 58" 16'. The diacetyl-cowpound is very sparingly soluble ; it melts a t 163-166".It is very unstable, and when often recrys- tallised changes to the monacetyl-derivative. The results ahove described point to the following constitutional formule for the lactones of isophotosantonic and photosantonic acids respectively :- CH : CH*CH-CHMe*C(OH)z CH 1 CH*CH*CHMe*CH*CH<;?>CO I I and CH : CH*CH*CHMe*COOH CH CH* C H*C HMe*CH2*CH < :?> C 0. N. H. M. I I Cinchol. By 0. HESSE (Annulen, 234, 375--379).-A further comparison of i he properties of cinchol and Liebcrmann's oxyquino- terpene or cliolestole (Abstr., 1885, 1075) confirms the author's pre- viously expressed opinion (Abstr., 1885, 1076) that these two substances are identical. They both melt at 115", and are identical in crystalline form. The acetates melt at 1 2 4 O , and also exhibit identical crystalline forms.w. c. w. Alkaloids. By 0. DE CONINCK (Contpt. rend., 103, 640-641.)- Piperidine methiodide gives no colour reaction with potassium hydr- oxide (Abstr., 1886, 897), and this difference furnishes a means of distinguishing between a pyridic base and its hexhydyide. Cicutine methiodide also gives no colour reaction, but the solution acquires an amber tint. The reaction is always obtained with colli- dines, and therefore will most probably be given by conyrine, the collidine of which cicutine is the hexhrdride. No similar colour reaction is obtained with the methiodides of aniline, orthotoluidine, or metaxylidine. When methiodides of pyridic bases are mixed with a fragment of solid potassium hydroxideORGANIC CHEMISTRT. 59 and sn6cient water to form a paste, and then heated, a peculiar odour is developed owing to the formation of pyridic dihydrides.No similar reaction is given by methiodides of pyridic hexhydrides, nor by the methiodides of aniline and its homologues. C. H. 33. Extraction of Pyrroline from Animal Oil. By G. L. CIAMICIAN and M. DENNSTEDT (Gazzetfa, 16,356) .-Pyrroline may be extracted as the potassium-derivative by using caustic potash instead of the metal as heretofore practised. The reaction is probably CIH,NH + KOH = C,H,NK + H,O; the excess of potash serving as a dehydrating agent. The fraction of the oil, freed previously from nitriles, which passes over at 125-140", is heated in an oil-bath with an excess of fused pofash, using a reflux apparatus. At the conclusion of the rcaction, the liquid separates into three layers, the heaviest of which is the excess of potash, the next the potassium compound, and the lightest the unaltered hydrocarbons.On cooling, the potassium com- pound solidifies, and is washed with anhydrous ether. The substance thus obtained, distilled in a current of steam, yields pyrroline of boil- ing point 130-138' ; with chloroform, it yields chloropyridine (Abstr., 1881, 820). V. H. V. Pyridine Bases. By A. LADENBURG (Compt. rend., 103? 692- 695 ; see also Abstr., 1884 and 1885).--a-MetlzyZ~yridine (picoline), C6NH7, is obtained in the form of hydriodide by heating p-j-ridine methiodide at 300". The base boils at 138-129", and is miscible with alcohol and water ; sp. gr. a t 0' = 0.9656. It forms a characteristic mercuriochloride, C,NH7,HCI,HgC12, by means of which i t can be isolated in a state of purity; this compound is very soluble in hut water, but only slightly soluble in cold water.p-MethyZpyridine is best prepared by Zanoni's method of heating glycerol and acetamide with phosphoric anhydride. I t boils a t 142" ; sp. gr. at 0" = 0.9771. The platinochloride crystallises with 1 mol. H,O and melts at 214" ; the aurochloride is anhydi-ous and melts a t 183" ; the mercuriochloride is also anhydrous, melts a t 143", and forms slender needles which can be crystallised from water. .y-iWethy@yridi?~e is formed only in small quantity by the action of heat on pyridine mdhiodide; it boils a t 144-145" ; sp. gr. at 0" = 0.9708. The platinochloride is anhydrous, melts a t 225", and is only slightly soluble in water.aa'-Dimethyl- pyridiite is isolated from the fraction of animal oil boiling a t 138- 145" by means of the mercuriochloride, C7NH9,HCI,HgCl2, which can he crystallised from water, and melts a t 183". When decomposed, it yields lutidine boiling at 142-143"; .sp. gr. at 0" = 0.9924. The aurochloride forms yellow needles which melt at 124" ; the platino- chloride crptalliees in large monoclinic crystals isomorphous with /3-picoline platinochloride, although the former is anhydrous, whilst the latter contains 1 mol. H,O. The picrate is only slightly soluble in water and melts a t 159". When the base is oxidised, it yields a bibasic acid, C5NH3( COOH),, crystallising in beautiful needles which melt a t 226", and at the same time decompose into pyridine and carbonic ttnbjdride.oc-y-Dimefk$pyridine exists in large quantity in Dippel's60 ABSTkACTS OF CHEMICAL PAPERS, oil, and can be isolated from the fraction which boils at 1S5--160" by acidifying with hydrochloric acid and adding mercuric chloride. The precipitated mercuriochloride, 2(C,NHg,HC1,2HgC12) + HzO, is re- peatedly recrystallised, and forms beautiful needles which melt at 129'. When decomposed, it, yields the base ; this boils at 157", and is only slightly soluble in cold water, still less soluble in hot water. The platinochloride is somewhat solnble, crystallises readily, and melts at 219-220'. The aurochioride, C7HgN,HL4uC11, is less soluble and does not crystallise so well. This lu tidine is identical with the lutidine prepared synthetically by Hantzsch.When oxidised, it yields lutidinic acid, which crystallises in plates which melt at 235". a-Ethy7pyridine is the principal product of the action of a, high temperature on pyridine ethiodide ; it boils at 150", is miscible with alcohol, but is only slightly soluble in water. The platinochloride is somewhat soluble in water, and melts at 168-170" ; the aurochloride melts at 120" and crystallises readily from hot water; the picrate melts at 110". When the base is oxidised, it yields picolinic acid only. y-Ethykym'dine is also formed in smaller quantity by the action of heat on pyridine ethiodide, and is separated from its isomeride by taking advantage of the comparative insolubility of its salts, especially the platinochloride or ferrocyanide.The base boils at 163'; sp. gr. at 0" = 0.9522. The plstinochloridie melts at 208", the picrate at 163", the aurochloride at 138". The ferrocyanide is precipitated even from very dilute solutions. When the base is oxidised, it yields isonico- tinic acid. a-y-DietkyZpyridine is also obtained in small quantity by the action of heat on pyridine ethiodide ; it boils at 187-188", has a, disagreeable odour, and is only slightly soluble in water. When care- f u l ! ~ oxidised, it yields lutidinic acid which melts at 235". a-lsopropylpyridine, obtained by heating pyridine with propyl or isopropyl iodide at SOO", boils at 158-159", is slightly soluble in water, and has a very disagreeable odour ; sp. gr. at 0" = 0.9342. The platinochloride, (C8Hl,N),,HZPtCI6, is somewhat soluble and melts at 168" ; the aurochloride crystallises from dilute solutions in yellow plates which melt at 9l"and are only slightly soluble in water; the picrate forms yellow needles which melt at 116".When the base is oxidised by potassium permanganate, it yields picolinic acid. y l s o - propyZppidipLe is obtained in smaller quantity by the same reaction, arid is separated by means of the platinochloride, which is only slightly soluble in water, and melts at 203". The base boils at 177-178"; sp. gr. at 0" = 0.9439. The picrate melts at 180". When oxidised, it yields isonicotinic acid. C. H. B. Quinoline. By A. CLAUS and F. COLTJSCHONN (Bey., 19, 2502- 2508).-The authors describe a number of halogen additive products of the propio-haloid compounds of quinoline.Quinoline propio- bromide is easily formed when its constituents are heated alone, or better, with alcohol, at 90-100". It is easily soluble in alcohol and water, and crystallises from water in colourless plates containing 2 mols. H,O, and melting at 66" ; from absolute alcohol, it separates in anhjdrous crystals melting at 148". It is easily soluble in chloro- form, and horn this solutiou crystallises with 1 mol. CHC1, in quadraticORGANIC CHEMISTRY. 61 prisms which cradually lose chloroform and become opaque, soften at 65", and melt with evolution of chloroform a t 128-129". Quinoline propiodide forms yellow anhydrous ctptals me1 ting at 145", and becoming rapidly discoloured in the light. This also crystallises with 1 mol. CHCI, in quadratic prisms which begin to evoke chloroform at 92".Quinoline propiochloride cannot be easily prepared directly from its constituents, but is best obtained by acting on the corre- sponding bromide with silver chloride. It is very soluble in water, and crystnllises in colourless prisms or plates containing 1 mol. H,O and melting a t 95". The hygroscopic anhydrous salt melts at 135" ; it also crystallises with 1 mol. CHCI, in quadratic prisms melting a t 79". The additive products were obtained by treating a chloroform solu- tion of the propiohaloid salt with the halogen. Quinoline propiobroinide dibromide, CgNH,*PrBr?, forms glistening, red, triclinic crystals melting at 93". The di-iodide forms brown metallic needles melting a t 60". The dichloride forms yellow scales melting at 60".The tetriodide, CgH,N*PrBrId, yields small, almost black needles having a green fluorescence and melting at 49". Quinoline propiodide dibromide forms orange triclinic crystals melt- ing a t 77". The di-iodide forms thin, bronze-coloured scaleq melting at 62". The dichloride forms yellow needles melting a t 87". The tetrabromide, C9NH7*PrIBr4, is a very unstable orange-red powder which evolves bromine a t the ordinary temperature, and gave no con- stant malting point (48-58"). The tetriodide forms iodine-coloured plates melting a t 50'. The tetrachloridp crystallises in needles which show the high melting point 1 4 ~ 1 4 . 5 " . It is also formed when quinoline propiochloride is treated with iodine trichloride, and may therefore really he quinoline propiochloride iodide trichloride.When boiled with water, it is gradually decomposed into quinoline propio- chloride. Similar migmtion of the halogen-atoms may also very likely take place in others of the mixed halo'id compounds. Qziinoline propiochloride dibromide forms orange crystals melting at 84-85'. The &iodide melts a t 61-W. The dichloride is very unstable and could not be obtained in a pure state. A tetriodide is easily formed, but could not be obtained in a pure state. All these additive compounds decompose when heated a t 250-200", prop91 haloid salts, quinoline haloid salts, and halogenispd and alkglated quinolines being amonget the products of decomposition. These decompositions are being studied. All the above temperatures are uncorrected.L. T. T. Isoquinoline and its Derivatives. By S . GABRIEL (Ber., 19, 2354--2363 ; compare Abstr., 1886, 812) .-Dichlorisopuinoline, CH: CC1 C"""&y: N 2, is prepared by heating homo-orthophthalimide (8 grams) with phos- phorus oxychloride (24 grams) for three hours a t 150-170". The product is poured into alcohol ( 5 vols.), the mass of crystals so obtained treated with soda until alkaline, filtered. and recrystallised from alcohol. It is readily soluble i n hot alcohol, cold chloroform,62 ABSTRACTS OF CHEMICAL PAPERS. ether, and benzene; it boils at 305-307". The alkaline mother- liquor obtained in the preparation of this compound, when treated CCl : N >' with hydrochloric acid, yielded the cldoro-derivutive C6H4< CH,*CO or C6H4<~CH1_C"0H'> ; this crystallises from boiling alcohol in long needles melting at 195-197" with evolution of gas.It is rather soluble in hot alcohol, sparingly in hot benzene and in chloroform ; it dissolves in alcohol, but not in ammonia. The methyl-cornpoun,d, C,H5MeClN0, is obtained by dissolving half a gram of the substance in methylalcohol (10 c.c.), adding methyl iodide (2 grams), and heat- i n g a t 100". It forms slender, white crystals, readily soluble in alcohol, ether, benzene, &c., insoluble in alkali. It melts at 66-67', and has an odour of fruit. Chlorisopuinoline, C6H1< CH CH:N ' '">, - is obtained by reducing the dichloro-compound with phosphorus and hydriodic acid at 150- 170", or with tin and hydrochloric acid. It melts at 47-48', and boils at 280-281" under 753 mm.pressure, and is readily soluble. Methoxy pheiilJlclzloriso quinoline, C"H4<C(oMe) : N>, is formed when phenyldichlorisoquinoline (1 gram) and sodium methoxide are heated for three hours at 100". I t crystallises from alcohol in needles melting a t 76", readily soluble in ether, benzene, &c. It dissolves also in strong hydrochloric acid, but is precipitated by water. When heated with fuming hydrochloric acid at loo', it is conyerted, with evolution of methyl chloride, into the compound C16H&1N0, probably ch!orisobenzuZ phthliinidine, C6HH'<Co.~H->. It crystallises from alcohol in slender, lustrous needles, melting at 211-212", moderately soluble in ether and cold alcohol, readily in glacial acetic acid, ben- ztae, &c.The formation of this compound is analogous to that of isobenzslphthalimidine from phenylethoxyisoquinoline (Abstr., 1886, 631). Ethozychlorisoquiil.oline, CeH4<g$YgCk>, is prepared by heating dichloroisoquinoline with alcoholic soda at 100". It forms readily soluble needles melting at 37-37.5". The methoxy-derivative, CloH8XOC1, is prepared in a, similar manner. It melts a t 73-74", and is isomeric with the methyl-compound obtained from chloroxy quinoline. When heated at 150" in a current of dry hydrogen chloride, it is converted into oxychlorisoguinoline, C,H4<gt.&!!>. This crystallises from dilute alcohol in slender needles melting at 218-220' ; i t dissolves rather readily in ether, easily in alcohol and chloroform ; it is also readily soluble in dilute aqueous soda.The methylderivative, c6H4<gg.&z:>, crydxdlises in long, broad needles which melt at 111-112" ; it is readily solnble. c)xy chlorisoquinoline is formed in small quantities in the preparation of ethoxychlorisoquinolhe. CC1: CPh - CC1' CPhORGANIC CHEMISTRY. 63 Isoquinoline is conveniently prepared by heating dichlorisoquinoline (3 grams), and hydriodic acid, sp. gr. 1.96 (18 c.c.) for five hours at 230". The product is treated with alkali, and steam distilled ; the distillate being treated with hydrochloric acid and again steam dis- tilled to remove the unchanged chloro-base. Isoquinoline melts at 20-22", and boils at 236-236.5". The ethiodide crystallises in gold- coloured plates melting at 147-148", readily soluble in water and in warm alcohol. N.H. M. Synthesis of Hydroxyquinolinecarboxylic Acid. By E. ,LIPP- MANN and F. FLEISSNER (Ber., 19, 2467-2471) .-Unlike ordinary phenol-derivatives, the potassium compound of orthohydroxyquinoline is not acted on by carbonic anhydride even at 300". When, however, nascent carbonic anhydride (obtained by the action of potash on carbon tetrachloride) is employed, action takes place. Orthohydroxy- quinoline, carbou tetrachloride, and caustic potash are mixed in alco- holic solution in the proportions necessary for the equation C9NH7U + CCI, + 6KHO = 4KC1 + C9NH5(OK)*COOK + 4H20, and the ~ h o l e boiled for 12 hours. The product contains hydroxyquinoZine- ccirboxylic acid, OH.C,NH,*COOH, which when purified crystallises in yellow prisms melting at 280".?'his acid agrees in its salts and in all its properties, save melting point and oxidatiou products, with the a-hydroxycinchonic acid (m. p. 254-256") obtained by Weidel and Cobenzl from sulphocinchonic acid (Abstr., 1881, 742). The acid is sparingly soluble in the ordinary solvents. It dissolves in dilute hydrochloric acid to form a hydrochloride, which is precipitated on the addition of concentrated hydrochloric acid in the form of glistening needles. The platinochloride forms unstable, bright yellow needles. The acid forms a normal barium salt, the pale yellow solution of which, on the addition of baryta-water, yields white needles of the bask barium salt CloNH,BaO3 + H,O ; these only part with their water of crystallisation at 140-150". The silver salt is precipitated in the form of pale lemon-yellow flocks, which soon change to microscopic needles.The aqueous solution of the acid gives a green coloration with ferric chloride, but none with ferrous sulphate. When subjected t o dry distillation, the acid yields orthohydroxyquinoline. When oxidised by potassium permanganate in alkaline solution, the acid yields a pyridinedicarboxylic acid, C,NEIQ04, forming bright yellow crystals melting at 234-235". With ferrous sulphate, it give8 a blood-red coloration, and forms a silver salt which is gelatinous when first precipitated, but soon becomes crystalline. This acid is probably identical with Bottinger's pyridiuedicarboxylic acid, and isomeric with Weidel's isocinchomeronic acid. Weidel and Cobenzl's a-hydroxyvcinchonic acid, when similarly oxidised, yields a-pyridinetricarboxylic acid.The authors are further investigating this subject. By 0. FISCHER and H. VAN Loo (Ber., 19, 2471--2476).--This is a continuation of the authors' previous work (Abstr., 1884, 1372). When P-diquinoline is heated with ethyl iodide in closed tubes at 90-loo", P-diquinolirbe L. T. T. Peculiar Formation of 6-Diquinoline.64 ABSTRACTS OF CHEMICAL PAPERS. ethiodide, Cl,N2H12EtI, is formed in long, ruby-red crystals. It is very unstable, and is decomposed by water and by boiling alcohol. Ro diethiodide could be obtained. When bromine is allowed t o act on P-diqiiinoline in chloroform solution, a tetrabromc-additive product, CI,N2H,,Br4, is produced. This crystallises in pale yellow needles melting at 192", and is decomposed at once by sulphurous acid, diquinoline sulphnte being formed./3- DiquinolinedisuZphonic acid, ClsN2H,,(S03H)2, is produced when P-diquinoline is heated with a large excess of fuming sulphuric acid. It is very soluble in water, and is precipitated from this solution by a mixture of alcohol and ether in yellowish flocks. Its potassium salt crystallises from 50 per cent. alcohol in glistening white prisms containing 3 mols. HzO. The anaquinolinecarboxylic acid described in the former paper (loc. cit.), as obtained by the oxidation of the base by chromic acid in acetic solution, is undoubtedly identical with that lately obtained by Skraup and Brunner (m. p. 247"). The melting. point previously given by the authors was obtained from a sample crystallised from benzene ; when crystallised from water, it melts at 248-249".The author con- siders this acid to be metaquinolinecarboxylic acid, and that the name anaquinolinecarboxylic acid should be transferred to the acid melting at 357O, and hitherto designated metaquinolinecarboxylic acid. If chromic acid is dissolved in sulphuric acid in place of acetic acid, the oxidation takes place in quite a different way. Under these circumstances p yridy 7quinolinecarbon: y Zic acid, C,NH,*C,NH,.C OOH, i8 formed. This crystallises in glistening needles, which melt with decomposition at 271-273". It is sparingly soluble in water, easily in alcohol, and forms salts both with acids and bases. The silver saIt, when heated, yields a p y r i d y lqzcinohe, C14N2H10, which crystaliises in white needles melting at 104", and gives a reddish-yellow crystalline platinoch lorid e.Piperidine Bases. By A. LADENBURG (Compt. rend., 103, 747- 74{9).-The bases are obtained by treating boiling alcoholic solutions of the corresponding pyridine bases with a large excess of sodium. Piperidine obtained in thh way is identical with the base prepared from piperine. a-Methylpiperidine or a-pipecoliqe boils at 118-119", has the same odour as piperidine, and dissolves readily in water; sp. gr. at 0" = 0.860. The hydrochloride is very soluble, but not deliquescent, and melts at 189". The hydrobromide is less soluble, and forms confused needles which melt at 182" ; the platinochloride is very soluble. With carbon bisulphide, the base yields a thiocarbamate, CS2,'2C6HI3N, which crystallises readily, melts at 118", and is analogous to that! formed from piperidine.p-Methylpiperidine or P-pipecoline boils at 125", and dissolves readily in water; sp. gr. at 0" = 0.8684. The hydriodidc crystallises in beautiful, non-deliquescent needles, which melt at 131". It combines with cadmium iodide, forming the compound Cd12,2C6H13NHI, a wbite precipitate soluble in warm water, from which it crystallises in white tables melting at 145". The platinochloride is somewhat soluble, and forms orange prisms melting at 192" ; the aurochloride is very soluble, and melts at 231" ; the picrate nielts at 136". aoc'-Dimethy~~peridinR or aa'-lupetidine boils at 128- L. T. T.ORGANIC CHE_1IISiTlZI'. 6 5 130", and is very soluble in water and alcohol ; sp.gr. at 0" = 0.8492, The hydrochloride and hydrobromide crystallise in non-deliquescent needles ; the platinochloride forms large orange crystals which melt a t 212". ay-Dirnethypip~ridz'ne boils at 141", has an odour of piperi- dine, and dir,solves readily in water, though not in all proportions : sp. gr. a t 0" = 0.8615. The hydrochloride crystallises in beautiful needles which melt a t 235" ; the hydrobromide is even more soluble ; the platinochloride is not very soluble, and crystallises in nodules ; the aurochloride is an oil. a-Ethylpiperidine boils at 143", and dis- solves slightly in water, but separates from the solution on heating, and has an odour resembling that of piperidjne and coniciiie ; sp. gr. a t 0" = 0.8674.The hydrochloride forms non-deliqiiescent crystals ; the platinochloride cryst,aliises in large tablea which melt a t 178". The methyl-derivative boils at 143-152"; sp. gr. at 0" = 0.8495. ~,-.E&yZpiperitline boils at 1 -57", has a disagreeable odour, is only s,lghtly soluble in cold water, and still less soluble in warm water ; sp. gr. a t 0" = 0.8795. The hydrochloride is deliquescent ; the platino- chloride forms yellow tables which meltl at 170-173" ; the auro- chloride crystallises from warm water in lamella which melt a t 105". a- IsopropyZpiperiditLe boils at 160-162", and is slightly soluble in water, but separates from the solution when gently heated ; sp. gr. a t 0" = 0.8676. Its odour and its properties generally resemble those of its isomeric-le, conicine, but it is much less poisonous.The platinochloride is much less soluble in water. and is not soluble in alcohol or ether ; i t melts a t 193" ; the hydrochloride melts a t 240", the hydrobromide a t 230", the hydriodide at 24 Lo. All these derivatives crgstallise readily. The iodide combines with cadmium iodide, forming a slightly soluble double salt, which crystallises readily and melts at 132". The picrate and aurochloride crystaUise readily, and are only slightly soluble. With carbon bisulphide, the base yields a crystalline compound, CS (C,H,,N)SH,C,H1,N, which melts a t 105", dissolves readily in alcohol, but is only slightly soluble i n water. The methrl-dvivative of or-isopropy~piperidine boils a t 166" ; sp. gr. at 0" = 0 85P3. Its hydrochloride is extremely soluble in water ; the aurochloride forms shining lamellae, and is also very soliihle in water ; the platinochloride is somewhat soluble, and melts a t 100" ; the picrate crystallises readily, and nielts a t 149".ry-Isop,.opyZpiperi~~//e boils at 168-171", dissolves slightly in water, and has a very disagreeable odour. The hydro- chloride crystallises, but is not stable in moist air ; the platinochloride is crystalline, and is only slightly soluble in water, but dissolves in alcohol and ether, arid melts at 172"; the aurochloride is also crgstal- line, and only slightly soluble. Method of Preparing Extracts of Pepsin. By W. PODWYSSOZKI ( P J ~ g p r ' . c A T C ~ L ~ U , 39, 62-74). -If the gastric mucous membrane of carnivora and herbivora be placed in glycerol almost immediately after death, very little pepsin is extracted.Ebstein and Grutzner state that glycerol dissolves pepsin only, but the author finds that a certain amonut of pepsin precursor, or as he t,c.rmq it " propepsin," is dissolved also. Mucous membrane exhausted with glycerol still yields an important C. H. B. VOL. 1.11 f66 ABSTRACTS OF CHEMICAL PAPERS. amount of pepsin when treated with hydrochloric acid or hydrochloric acid and glycerol. It appears, therefore, that gastric mucous mem- brane contains two propepsins, one soluble in glycerol, the other insoluble. I f the mucous membrane is kept in a warm place for 24 hours before it is extracted, a much larger yield of pepsin is obtained, provided no putrefaction has set in. Hydrogen and carbonic anhydride have no influence on the forma- tion of pepsin, but oxygen, on the other hand, appears to favour its development ; more pepsin is formed when the mucous membrane is allowed to remain in contact with oxygen than when it is in contact with air.Chlorine gas passed through any extract entirely destroys the ferment. J. P. L. Comparative Estimation of Preparations of Pepsin. By .A. A. LIPSKI (Russlcayrc Medifsiiza, 35,583-584).-The powdered pepsins were examined by digesting 0.2 gram of the preparation with 10 grams of white of egg and 100 C.C. of hydrochloric acid (0.25 per cent.) for four hours at 40". The undissolved albumin being then determined, the weight of this in grams was :-Perret acidifih 8.756, Marquart 8 577, Lamatch 8.557, Merck 7.213, Boudault neutre (No.4) 2 62, Witte 2.195, Boudault acidifit5 1.2, Russicum solubile (of the Russian Ph.) 0.721, do. do. recent 0.47, do. do. without the sugar contained in the official preparation 0.157. The Russian pepsin is, therefore, far more active than any of the German or French pre- parations tested. The same holds good for the pepsin wines.24 ABSTRACTS OF CHEMlCAL PAPERS.Organic Chemistry.Volatility of Methane-derivatives. By L. HENRY (Compt.rend., 103, 603-606) .-The volatility of methane-derivatives followsthe same order as that of the substituted elements when the latterare arranged in natural families in the order of their atomic weights.The boiling point rises as the molecular weight increases, but thedifferences between the volatility of the methane-derivatives are muchless than those between the boiling points of the electronegativeelements which they contain.B.p. Diff.cl, gas ...... - 35") 96"Br, liquid .... + 63I, solid . . , . . + 250 }O , ~ R S ........ - 181N, gas. ...... - 193S, solid ...... + 448) 629P, solid ...... + 287}480B. p. Diff.MeC1, gas .... - 23" } 27.5Me20, gas ..... - 23 } 60.04- } 50.0 Me3N, gasMeBr, gas .... + 4.5MeI, liquid ...Me,S, liquid. .. + 37Me3P, liquid.. . + 4144 } 39'5.....The differences show that electronegative elements in the samenatural family are far from being comparable in the free state, whilstip methane-derivatives they may be regarded as existing underanalogous physical conditions.I n each of the groups of methane-derivatives, the rise of the boilingpoint is not proportional to the increase in the molecular weight ; infact the greater the increase in the molecular weight resulting fromsubstitution, the less proportionally is the rise of the boiling point.The substitution of sulphur causes proportionally less rise in the boil-ing point than the substitution of oxygen, and the snbstitution ofphosphorus less than the substitution of nitrogen, although sulphurand phosphorus are solids, whilst oxygen and nitrogen are gases.The atomic weights being nearly equal, the diminution of volatilityresulting from substitution is greater the more strongly marked theelectronegatire character of the substituted element, or, in otherwords, the more distinctly its properties differ from those of hydro-gen. This is well seen in the case of the nitrogen- and boipon-deriva-tives.Me3N, mol.wt. 59, a liquid boiling at 9.3".Me3B, mol. wt. 36, a gas which liquefies at -10" under a pressureof 3 atmos.This phenomenon is doubtless connected with the fact that the heatof combination of carbon with electronegative elements diminishes asthe atomic weight of the latter increases.Sugars. By BERTHELOT (Compt. rend., 103, 533-537).--8 soh-tioh of invert sugar which had been kept for nearly 30 years,deposited spheroidal groups of radiating crystals, which when care-C. H. BORGANIC CHEMISTRY. 25fully dried on filter-paper resembled purified glucose. The crystalshave the composition C6H,,0e when anhydrous ; their reducing poweris equal to that of glucose, and they are completely fermentable, buttheir rotatory power is only [a]= = + 32.2, or little more than halfthat of glucose.The crystals are a compound of glucose and levu-lose, in which one constituent behaves like water of crystallisation.The compound is decomposed by solvents ; its rotatory power showsthat the ratio of levulose to glucose is 1 : 5. A similar compoundprepared by G6lis has the rotatory power of +15O, which correspondswith a ratio of levulose to glucose of 1 : 3.The compound formed as an intermediate product in alcoholic fer-mentation is most probably formed by the union of one molecule oflevulose with two of glucose, but it does not seem to have been ob-tained in crystals.In the process of extracting raffinose from cotton-seed cake, crys-tals were obtained which when dried on filter-paper without treatmentwith any solvent had all the properties of mellitose from the manna ofeucalyptus. When the aqueous solution of this substance is treatedwith yeast, only half the sugar undergoes fermentation, and the liquidcontains a non-fermentable sugar with the properties of eucalpe.Ifthe mellitose is treated with boiling alcohol, it splits up into rafflnose,which crystallises after some time, and eucalyne, which remains insolution. An alcoholic solution of ra5nose and eucalyne when allowedto remain, deposits crystals which seem to be formed by the recom-bhation of the rnffinose with the eucalyne.Mellitose, which is widely diffused in the vegetable kingdom, isthe result of the association of raffinose, a true saccliarose, witheucdyne, a non-fermentable carbohydrate. This association bearsno resemblance to the union of glucoses to form saccharoses, and theconstitution of mellitose is analogous to that of hydrates and alco-holates rather than to that of ethereal salts.C. H. B.Sugar formed in the Inversion of Lichens. By P. KLASON(Ber., 19, 2541).-Bauer showed (Abstir., 1886, 869) that dextrose isformed by inverting lichens. The author previously obtained thesame results (Lund’s Pysiogr. Sallskops Minneskr., 1878, 61). Appa-rently no other sugar is formed in the inversion. N. H. M.Action of Dilute Acids on Grape-sugar and Fruit-sugar,By M.CONRAD and &I. GUTHZEIT (Ber., 19, 2569-2574).-Accordingto Tollens and v. Grote (Annnnlen, 175, 181, and 206, 207), dextroseas well as levulose when boiled with sulphuric, or better with hydro-chloric acid, .Fields acetopropionic acid in very small quantity.Quantitative experiments on the decomposition of cane-sugar byhydrochloric acid, made by the authors (Abstr., 1885, 743), pointedto the formation of a small amount of acetopropionic acid from dex-trose. Experiments described in the present paper show that thisview (the formation of acetopropionic acid chiefly from levulose) onlyholds good for the decomposition of cane-sugar with dilute sulphuricacid, and not with hydrochloric acid.Quantities of dextrose and levulose corresponding with 20 grams o26 ABSTRACTS OF OHEMICAL PAPERS.cane-sugar were heated for 17 hours with the same amounts of acidand water as those previously used (Zoc.cit.).1. Decomposition with dilute sulphuric acid-Aceto-Humic propionic Formiosubstances. Dextrose. acid. acid.Dextrose.. .... 52.6 0.83 43-70 2.78 1.21Levulose.. .... 32.6 13.78 - 16.78 6.46Cane-sugar.. .. 100.0 = 14.61 43.70 19.56 7-872. Decomposition with dilute hydrochloric acid-Aceto-.Humic propionic FormicDextrose., .... 52.6 4-76 14-52 15.53 6-51Levulose.. .... 52.6 10.65 - 16.28 8-78substances. Dextrose. acid. acid.Cane-sugar, , . . 100.0 = 15.41 14-52 31.81 15.29Decomposition of Milk-sugar by Dilute Hydrochloric Acid.By M. CONRAD and M. GUrHZElT (Bey., 19, 2575--2576).-The follow-ing results were obtained froni three experiments, in which 21, 21,and 10.5 grams of milk-sugar were heated with 50 C.C.of water and4.87, 5.0, and 487 grams of hydrochloric acid respectively :-substances, (unchanged). acid. acid.N. H. M.Humic Milk-sugar Acetopropionic Pormic1 ...... 3.68 5.54 6-29 2.392 ...... 3.94 - 5-80 2.243 ...... 1-60 L 3.32 1.33In 2 and 3, the milk-sugar was not determined. N. H. M.Carbohydrates. By 0. WALLACE (Annalea, 234, 364-375).-The rhizome of the water lily, Iris pseudacorw, contains a peculiarCarbohydrate, called " irisin " by the author. Irkin, CaHl0O5 + HzO,closely resembles inulin, but is distinguished from the latter byits more powerfal action on polarised light; [dc]D = -49' 90 for a2 per cent.solution of irisin, and [ a ] D = - 37" 27' for a soIution ofinulin of the same strength. Fehling's Rolution is not reduced byirisin, but the carbohydrate is easily attacked by dilute acids, yieldinglevulose as the chief product. Irisin is four times as soluble asinulin in water s t 22". Under the microscope, the globules of irisinresemble the minute globules of inulin in size, but they do not exhibitdouble refraction. w. c. w.Animal Gum. By H. A. LANDWEHR ( P f t i i g ~ ' ~ arc hi^, 39,193-204) .--The animal carbohydrates may be arranged in parallel groupswith those occurring in the vegetable kingdom, and animal gumresembles vegetable gum in yielding oxrzlio acid after treatment withnitric acid. Mwiin was prepared It is obtained readily from m u c ORGANIC CHEMISTRY. 27by precipiktion with acetic acid from an extract of submaxillaryglands, made with a 1 per cent.sodium carbonate solution. The pre-oipitate was washed with weak acetic acid, and then dissolved in weakhydrochloric acid by the aid of heat. On neutralising with soda, a whiteflocculent preciFitate is obtained, which is increased in amount on theaddition of sodium sulphate and boiling. The precipitate is collectedand freed from salt by dialysis; i t consists of an ordinary proteid.The filtrate contains no nitrogen, biit contains animal gum. Fromtendon mucin, the same carbohydrate is obtained, in spite of whatLoebisch (Abstr., 1886, 166) says to the contrary; it may also beobtained from synovia, collo'id cysts, and from the mucin of thesnail's mnntle. nilucin and animal gum both yield lsvulic acid whentreated with hydrochloric acid.By long boiling withwater, chondrin splits into gelatin, animal gum, and possibly a thirdsubstance not yet further investigated.Pure chondrin is soluble inhot water, and its solutions gelatinise when cold, if not too dilute ;this power of gelatinising is lost after prolonged boiling. A dilutesolution gives the following reactions :-Dilute mineral acids cause aprecipitate soluble in excess ; acetic acid gives a precipitate insolublein excess ; acetic acid and potassium ferrocyanide give a precipitate,soluble in excess of the latter reagent. Sodium chloride solutiongives no cloud, but hinders the precipitation by acetic acid.Metaphos-phoric acid gives a cloudiness disappearing on warmth. Alum gives acloudiness, disappearing on adding excess. Lead acetate gives a preci-pitate, soluble in excess. Basic lead acetate gives a precipitate, partiallysoluble in excess. Lead acetate and ammonia give a flocculent preci-pitate, insoluble in excess. Tannin and acetic acid give a precipitate,insoluble in excess. Copper sulphate and sodium hydroxide colour theliquid violet, which becomes red on boiling. Boiling the solution forfire or six hours with 1 per cent. mlphuric acid gives it the power ofreducing copper salts, this being due to the formation of a reducingsugar from animal gum. Animal gum may be separated fromchondrin in the same way as from mucin.Metalbumin and paralbumin may also be used as sources of animalgum. It is also found in small quantities, but constantlly in the redblood corpuscles, brain, kidney, spleen, liver, and pancreas.Prote'idspi-opor do not yield it.Another source of animal gum is chondrin.W. D. H.Derivatives of Thioformaldehyde. By A. WOHL (Rw., 19,23444347) .-Thiometaforrnaldehyde, (CH,S),, is obtained whenan aqueous or alcoholic solution --of hexamethyleneamine saturatedwith hydrogen sulphide is heated on a water-bath. It separates as a,white, amorphous substance, which is washed with water and hydro4chloric acid, and extracted with boiling glacial acetic acid and alcohol.It is insoluble in all the usual solvents, and has a peculiar odour ; itmelts at 175-176", and decomposes at a high temperature.Itdissolves unchanged in strong sulphuric acid.Methy Zthi~formuldine, S2(CH2)sNMe, is prepared by diluting 50 C.O.of a 20 per cent.. solution of formaldehyde with an equal volume ofwa&er, 8nd saturating with hydrogen sulphide; 200 C.C. of wafer ar28 ABSTRACTS OF CHEMICAL PAPkXS.then added, the whole filtered and stirred with 20 C.C. of a 30 per cent.solution of methylamine. In 24 hours crystals separate. Morehydrogen sulphide i s then passed through the solution until it is nolonger turbid ; the crystals are collected, washed with water, and dis-solved in ether. I t crystallises in needles melting at 65", and isinsoluble in water, soluble in dilute mineral acids, alcohol and glacialacetic acid. It distils with steam, boils at about 185", being at thesame time converted into a compound melting at 130-140".Thehydrochloride forms needles readily soluble in water ; it melts at 188"with decomposition.Dimeth ylthioformuldinium iodide, SL(CH,),NMe,1, is formed bytreating the compound with methyl iodide. In two to three days theliquid solidifies to a mass of slender, lustrous needles. It melts at 161-163O, and dissolves readily i n water, sparingly in alcohol. The platino-chloride, [ Sz( CH2)3NMe]zMezPtC16, is a bright yellow, crystalline sub-stance. The iodide dissolves in hot aqueous potash and separatesunchanged on cooling. When boiled with silver oxide, it yields anammonium base, which, however, could not be isolated.Chloro-derivatives of Acetals. By 0.MAGNAMINI (Gazxetta, 16,330-3333) .-Trichlorometh y let hylacetal, CC13*C €3 (OMe) OEt, is ob-tained by heating tetrachlorether with methyl alcohol in sealedtubes. The reaction is as follows: CCI,*CHCI*OEt + MeOJ3 = HCl + CCl,GH(OMe)*OEt. It is a colourless liquid of camphor-likeodour ; it boils at 193.4; sp. gr. = '1.32.Trichlorodimethylacetal, UCI3*CH(CMe)?, obtained from tetrachlor-ethyl methyl ether, is a liquid of similar characters. It boils at 183.2" ;sp. gr. = 1.28.The tetrachlorethyl methyZ ether, CC13*CHC1*OMe, prepared by theaction of phosphoric chloride on chloral methylate, is a colourlessliquid boiling at 178"; sp. gr. at 0" = 1.84. I t does not appear tohave been previously isolated.Diisonitrosoacetone.By H. v. PECHMANN and R. WEHSARG (Ber.,19, 2465-2467).-V. Meyer and Zublin have shown that when accto-acetic acid is treated with nitrous acid, carbonic anhydride is evolved,and isonitrosoacetone formed. The authors find that when, in likemanner, acetonedicarboxylic acid is treated with water and sodiumnitrite, a rapid evolution of carbonic anhydride takes place, and diiso-nitrosoacetone, CO (CH-NOH),, is produced. This forms glisteningprismatic crystals, meltiug with decomposition at 143-144". It iseasily soluble in alcohol and ether, sparingly in cold water, chlorofoim,and benzene. Itsaqueous solution when heated decomposes into hydrocyanic acid, car-bonic anhydride, and water. Acids cause a similar decomposition, buthydroxylamine is also among the products. It is more stable in nlka-line solutions, and forms alkali saEts, which crystallise in orange-yellowneedles.Its salts, especially the red crystalline silver salt, explodewhen heated. When warmed with phenol and Rulphuric acid, thenitroso-compound gives a red coloration, with ferric chloride a brown.The authors are further investigating the subject.N. H. M.V. H. V.I t is very unstable, and detonates when heated.L. T. TORGANIC CHEMISTRY. 29Hetines. By L. CON OM IDES (Ber., 19, 2524--2527).-When avery dilute solution of diethylketine, CloH,,N2, is treated with thetheoretical amount of potassium permanganate, a ketinedicarboxylicacid is obtained, identical with that prepared by Wleugel by reducingethyl isonitrosoethylacetate (Abstr., 1882, 949). If the oxidationtakes place in a warm solution, other and more unstable acids areformed.When 5 grams of ethyl imidoisonitrosobutyrate are care-fully warmed with powdered zinc chloride at 60-70" for a long time,and the product saponified with alcoholic potash, a small quantity ofan acid melting at l90-195", identical with Wleugel's acid (Zoc. c i t . ) ,is formed. The above reactions, together with the fact that the ketine-acid does not yield an anhydride, point to the following constitutionalformulae for methylketiiie and the ketine-dicarboxylic acid :-CMe*CH CMe* C (C 0 OH)NeCH: CMeyN and NeC(COOH): CMeyN*N. H. M.Pure Bntyric Acid. By A. BANNOW (Ber., 19, 2552-2554).-Pure butyric acid is best prepayed by converting the commercial acidinto the ethyl salt, which is then fractionally distilled.The fractionboiling at 120-121" is reconverted into acid. N. H. M.Xoc., 1886, 287-297).--Tiglic (methylcrotonic) acid,Derivatives of Tiglic Acid. By P. MELIKOFF (J. RUSS. C h m ~CHBle: CNeCOOH,was prepared either by the saponification of the oil of Roman chamo-mile (Kopp, Abstr., 1879, 454), or by heating a-methyl-p-hydroxy-butyric acid (Rohrbeck, Abstr., 1878, 136). The acid was treatedunder water with an aqueous solution of hypochlorous acid, the pro-duct of the reaction extracted with ether, and the solvent; distilled off.The residue, after remaining for some time over sulphuric acid, solidifiedto a crystalline mass, which was found to consist of two isomericchlorhydroxyvaleric acids, C5H9C103. A concentrated aqueous solu-tion of this mixture was neutralised with zinc carbonate : a crystallinezinc salt was precipitated, and the mother-liquor on being evaporatedleft another salt in the form of an amorphous humoid substance, Thetwo acids obtained by decomposing these salts with sulphuric acidare both easily soluble in water, alcohol and ether ; the one forming acrgstalline sparingly soluble zinc salt, melts at 75", and crjstallisesfrom ether in thin prisms; the other isomeride melts at 111*5", and isobtained from its ethereal solution in the form of large, translucentprisms.When a mixture of these acids, or each of them separately, istreated with alcoholic potash, the potassium salt of an anhydro-acid,CHMe <--,- >CMe*COOH, is formed.The free acid forms silky, crystal-line needles having the odour of butyric acid, easily soluble in water,alcohol, and ether, melting at 62". The energy with which i t entersinto direct combination is in the main the same as that shown byp-rnethylglycidic acid : a-methj lglj cidic acid in this respect exhibitin30 ABSTRACTS OF CHEMICAL PAPERS.much greater energy. This circumstance, established by experimentson the hydration of the potassium salt by heating with water, is inaccordance with the results obtained by the author in a former workon glycidic and a- and p-methylglycidic acids (Abstr., 1885, 650). Theenergy of direct combination is diminished with increasing molecular-weight in acid8 of analogous constitution ; at the same time amongisomeric acids the greatest energy is exhibited by the one containingtertiarily united carbon in its molecule.a-p-Dimethylglycidic acidcontains one CH,-group more than a- and P-methylglycidic acids, but,on the other hand, one of its carbon-atoms combined with oxygen is intertiary union.By the action of hydrochloric acid on a-P-dimethylglycidic acid,a-methy E-P-clLZor-a-hydroaybzLtyric acid, OH*CHMe*CMeCI*COOH, isformed ; it melts at 75", and is identical with one of the chlorhydroxg-valeric acids above described, the other isomeride being thereforea-methtyl-a-clLZoro-~-~~~droxyLUt~r~c acid, CHMeCl*CMe(OH)-COOH.An aqueous solution of a-/3-dimethylgl@dic acid, when heated during6-10 hours at 99", is converted into a-P-dimethyZqlycidic acid,OHCHMe*CMe(OH)*COOH, melting at lo?", readily dissolving inwater, alcohol, .and ether.A. T.Constitution of Chlorhydroxybutyric and DichlorobutyricAcid. . By E. MELIKOFF (J. Buss. Chem. SOC., 1886, 227-303).-Chlorhydroxybutgric acid (formed by the combination of crotonic withhypochlorous acid, Abstr., 1884, 1302, and 1885, 650), when heatedwith concentrated sulphuric acid, yields monochlorocrotonic acid, crys-.fallising in long, thin prisms, melting at 98", sparingly soluble incold, more readily in hot water, easily soluble in alcohol and ether.This acid yields normal crotonic acid (m. p. 72") ou reduction byzinc and sulphuric acid. The chlorocrotonic acid above mentionedis an a-chlorinated product, the isomeric &derivative being obtained,amongst other methods, by the action of phosphorus pentachloride onethyl acetoacetate; hence, the chlorhydroxybutyric acid in questionmust be a-chloro-P-hydroayB?~tyric acid.This acid was heated with hydrochloric acid, and a-/%diChloTObUt?/riCacid was obtained; it crystallises in long prisms and melts at 69".An alcoholic solution of the latter compound, when treated withalcoholic potmh, gives a-monochlorocrotonic acid.a-p-Dichlorobutyricacid is formed in like manner when a-monochlorocrotonic acid isheated with hydrochloric acid. A. T.Hydroxystearic Acids of Different Origin. By A. C. andM. SAYTZEFF (J. RUM. Chem. Xoc., 1886, 328--348).-A hydroxp-stearic acid was prepared by one of the authors some time ago in hiswork on the oxidation of oleic acid (Abstr., 1886, 140).Anotheracid of this composition was discovered by Fr6my (AnnuZen, 19, 296 ;20, 50; 33, lo), who obtained it by the action of concentratedsulphuric acid on oleic acid, and described it under t,he name of hydro-rnargaritic acid. Although the main points of the reaction had beensatisfactorily explained by FrBmy's work, yet subsequent work onthis question has mostly led to unsatisfactory results. SnbaneiefORGANIC CHEMISTRY. 31(Qbst?., 1886, 442) ha4 at last succeeded in throwing some new lighton the processes involved, but the authors do not in all cases obtainresults in agreement with his.Oleic acid was obtained by the saponification of oil of almonds, andpurified in the ordinary way by conversion into its lead salt.Theaction of sulphuric acid was regulated in such a manner as to preventthe temperature rising above 35". The mixture was then allowedto remain 20 hours a t a temperature below O", and decomposed bywater. In order to increase the yield of hydroxystearic acid, thefatty layer, separated by the action of water and solidifying a t theordinary temperature to a crystalline mass, was treated with alcoholicpotash, whereby the anhydrides of this acid are decomposed. Thesaponified product was then converted into the acid by boiling withsulphuric acid. When the products of the action of sulphuric acidon oleic acid are left for some time even at low temperatures, thequantity of hydroxystearic acid is diminished, whilst the quantity ofits anhydrides increases.Hydroxpstearic acid was extracted fromthe above-mentioned crystalline mass by repeated recry stallisationfrom ether and alcohol. So obtained, hydroxystearic acid,CH,. ( C H,) 13-CH,.CH( 0 H) CH2*C 0 OH,melts at 83-85", and resolidifies a t 68-65". At 20" alcohol (99p Ti-.)dixsolres 8.78 per cent., ether 2.3 per cent. of the acid. Tlydroxy-stearic acid does not absorb bromine. The free acid and the hydroxy-stearates of sodium, calcium, barium, copper, zinc, and silver, wereanalysed, and the formula of the acid shown to be C18H,0,.With hydriodic acid, hydroxystearic acid yields iodostenric acid.CH,*(CH,)13 CH,*CHI*CH2*COOH ; the latter can be converted intoordinary stearic acid by reducing its alcoholic solution with zinc andhydrochloric acid.When hydroxystearic acid is heated at 100" in sealed tubes withfuming hydrochloric acid, a syrupy liquid is formed, soluble in ether,insoluble in alcohol m d water, and having the composition of oleicacid.It does not show acid properties, nor give additive productswith bromine or iodine (in Hubl's solution); it is therefore consideredto be a complete anhydride of hydroxystearic acid,formed by elimination of 2 mols. of water from 2 mols. of the acid(analogous to glycolide or lactide). The anhydride is decomposedinto hydroxystearic acid by treatment with alcoholic potash a t tem-peratures above 150". Heated with dilute sulphuric acid (in sealedtubes at looo), hydroxystearic acid yields the same anhjdride, butwhen concentrated salphnric acid is iised a t ordinary temperature, twoother products of non-saturated character are formed, one corn biningwith 17 per cent., the other with 33 per cent., of iodine, when heatedwith it on the water-bath.These substances bear a great resemblanceto FrBmy 's metoleic acid, and will be further investigated.It wag shown that the hydroxystearic acid prepared by $he actio32 ABSTRACTS OF CHEMICAL PAPERS.of moist silver oxide on iodostearic acid was identical with thatdescribed above.Finally, the authors have studied the action of alcoholic potash oniodostearic acid. After heating the mixture in a reflux apparatus,and expelling the alcohol by distillation, the product of the reactionwas decomposed by sulphuric acid.An acid was obtained, solidifyingak ordinary temperatures to a crystalline mass, and consequently notidentical with oleic acid. It was purified by converting it into thesodium salt, recrystnllising this salt from alcohol, precipitating withzinc sulphate, recrystallising from boiling alcohol, and decompodngthe zinc salt by sulphuric acid. Thus purified, the substance crys-tallises from ether in translucent, rhombic tables, easily soluble inalcohol, sparingly in ether, and melts at 40-45". The compositionof this acid was found to be the same as that of oleic and elaidicacids. It is a non-saturated compound, taking up two atoms ofbromine 01' iodine. When oxidised by potassium permanganate i nalkaline solution, it yields dihydroxystearic acid, melting a t 78".The authors intend to continue the investigation of this solid oZeic acid.Another acid, melting a t 20-25", simultaneously formed by theaction of potash on iodost,earic acid, was found to be a mixture ofordinary and solid oleic acids.The constitution of solid oleic acid isCH,*( CH2) Is*CH2*CH : CH*COOTJ, ordinary oleic acid being repre-sented by CH3*(CH2)13*CH : CH*CH,-COOH. A. T.Action of Trimethylene Bromide on Ethyl Acetoacetate,Benxoylacetate, and Acetonedicarboxylate. By W. H. PKRKIN,Jun. (Ber., 19, 2.557-2561 ; comp. Abstr., 1886, 689).-When theacid C7Hl0O3 (from trimethylene bromide and ethyl sodacetoacetate)is boiled with aaker, carbonic anhydride is evolved, and Lipp'sacetobutyl alcohol (Abstr., 1886, 218) is formed. When the acid isdistilled, the anhydride of acetobutyl alcohol, CH2<cCH2.C,2-->0, CH : CHMeis obtained; it is a mobile oil.The same compound is also formedwhen acetobu tyl is heated. Strong hydrobromic acid dissolves theethyl salt C9Hla03, and decomposes it into bromobntyl methyl ketone( Lipp, Zoc. cit.) and carbonic anhydride. Benzoyltetramethylene-carboxylic acid is decomposed by hydrobromic acid in a similarmanner, with formation of the compound COPh*CH2*CHz*CH2*CHzBr ;this cyystallises in plates melting a t 61". The instability towardshydrobromic acid of the products obtained by the action of tri-methylene bromide on etbyl acetoacetate and benzoylacetate respec-tively, distinguishes them sharply from tetramethylenedicarboxylicacid.Trimethylene bromide acts on the sodium compound-CO(CHNa*COOEt)2(from ethyl acetonedicarboxglate and sodium ethoxide), yieiding thecompound C O O E t * C H ~ ~ ~ , ~ ~ C > O .The latter is a colour-less oil boiling at 238-240-(under 150 mm. pressure). The mon-et/t,yl salt melts at 114"; the free acid at 185--190" with decomORGANIC CHEMISTRY. 33position. When the monethyl salt is distilled, a subtance is obheinedapparently identical with the product of the reaetion between tri-methylene bromide and ethyl acetoacetate. The dicarboxylic acid isdecomposed by boiling water into acetobutyl alcohol and carbonicanhydride. N. H. M.Ethyl Acetotrimethyleneearboxylatk By W, H. PERBIN, Jun.,and P.C. FREER (Ber., 19, 2561--2569).-The fact that trimethylenobromide reacts with ethyl malonate, yielding a tetramethykne-derivative, and with ethyl acetoacetate with formation of an ether,sugges6ed the possibility that the product of the reaction betweenethylene bromide and ethyl acetoacetate (Trans, 1885, 801) is not atrimethylene-derivative bdt an ether. The aesults of determinationsof the magnetic circular polarisation, and the optical properties point,however, to the trimethylene formula first ascribed to the compound,E t h yZic brometh y Zucetoacetate, CH2Br+H2-CHAc*C00Et, is obtainedby dissolving ethyl acetyltrimethylenecarboxylate, well cooled., inhydrobromic acid, sp. gr. 1.85 (3 parts) ; after being left for 10minutes at the ordinary temperature, it is poured into ice water..Itis a yellowish oil, having an odour of camphor ; when exposed to airit becomes brown, and gives off hydrobromic aeid.. When reducedby means of zinc-dust and acetic acid, it is converted into ethyl aceto-acetate.Acetopropy I aZcohoZ, COMe*CHz-CH2-CH2-OH, is prepared by boiling20 grams of the above homo-compound for two hours with 5 gramsof hydrochloric acid and 20 grams of water. The reaction is analo-gous to that by means of which Lipp obtained acetobutyl alcoholfrom ethyl bromopropylaeetoacetate (Abstr., 1886, 216). It i s acolourless oil, very soluble in water; the solution very readily reducesammoniaeal silver solution but not Yehling's solution. It is veryunstable. A phenylhydrazine-compound was prepared.When thealcohol is heated, it is converted with evolution of water into a mobileoil, having an ekhereal odour ; it is probably an anhydride,CMe-cHqCH2* CH2>0(comp. A'bstT., 1886, 219).y-PeNty Zeme glycol, OH-CHMe*CH2-CR2.CH2-OH, is obtained byreducing acetopropyl alcohol with sodium amalgam. I t is a verythick, colourless oil, extremely soluble in water. It boils a t 210-220" with partial decomposition. When heated above its boilingDoint. or with 50 to 60 Der cent. of sulDhuric acid at 100'. it is con- I ' CHM - verted into the anhydride, CH2< CH,. &,>O, boiling at 78- 83".- -Pentylene glycol dissolves in hydrobromic acid (sp. gr, 1-85) withconsiderable development of heat ; when the solution is heated at W",the momobromohydrin of the glycol, C5HI13&, is formed, This is acolourless oil, which boils (under 150 man.pressure) at 144-145".N. H. M.Derivatives of Diaxosuccinic Acid. By T. C m r m and F.KOCH (Ber., 19, 2460--2462).--This is a continuation of the authors'previous work on this subject (Abstr., 1885, 885). Aspartic acid wslsVUL. LIr. 34 ABSTRACTS OF CF-IElIICAL PAPERS.obtained by the reduction of ethyl diazosuccinate with zinc-dust andacetic acid, thus proving the correctness of the formula formerlyascribed to diazosuccinic acid.NHz* CO* CN,*CHz*CO ONe(from the action of ammonia on methyl dia zosuccinnte), crystallisesin long, golden-yellow prisms soluble in ether and alcohol, and meltingat 84". When ethyl diaeosuccinate is acted on by cold slightlyacidified water, mulamic and f umalramic acids are produced. Malamicacid, NH,*CO*CH ( OH)*CH2*COOH, crystallises in colourless prismseasily solnble in water, alcohol, and ether, and melts a t 146" ; its methylsalt yields silky sca1e.s soluble in alcohol, ether, and water, and meltinga t 105".illethyl furnuramate, NHz*CO*CzH,*COOMe, crystallises incolourless plates, soluble in alcohol, and melts at 160-162". EihyZbenzoyZmaZamute, NH,*CO~CH(OBz)~CH,~COOEt, was obtained byheating together equal molecular proportions of benzoic acid and ethyldiaxosuccinamate a t 140-150". It forms colourless clinorhombiccrystals soluble in water, alcohol, and ether, and melts at 96-97". Itdecomposes easily when heated. The corresponding methyl salt form8colonrless crystals, melting at 78-80".By the action of iodine onan ethereal solution of ethyl diazosuccinamate an unsymmetricalethyl diiodowxinamate, NH,*CO*CI,*CH,* COOEt, is formed. Thiscrystallises in long, greenish-white needles which darken at 110",melt a t 132", and decompose at 150". The methyl salt and come-sponding methyl and ethyl hromo-salts are oils.Dichloropyromucic Acid. By A. DENARO (Gazzetta, 16, 333-335).-1f a current of dry chlorine gas is passed into the ethyl saltof pyromucic acid, a thick oil is at first obtained, probably consistingof the tetrachloride of the acid. This on decomposition with alcoholicpotash and subsequent acidification, yields a dichlorqyromucic acidwhich crystallises in white needles, melting at 167". Its barium saltcrystallises with 3 mols.HzO i n prisms, the calcium salt with 3$ mols.H,O in scales; both become completely anhydrous when heated to110". v. 1%. v.By 0. WIDMANN (Ber., 19, 2477-2$82).-As the mode of formation and reactions of this substanceare best explained by the formula CO' /GO, which 1111-doubtedly belongs to acetylenecarbamide, the author has carefullyre-examined these two compounds with the view of determiningwhether they are isomeric or identical. He finds that the latteris the case, and that the apparent differences in their reactionsare due to erroneous observation. When boiled with concentratedbaryta-water, acetylenecarbamide does not, as previously asserted,yield carbonic anhydride, but, like glycoluriI, is decomposed intohydantoic acid and carbamide.The solubility of acetylenecarbamidei 3 given by Schiff as 1 in 333 parts of water a t 15". The author fiadsthat pure acetylenecarbamide requires 1090 parts of water for solution,whilst a similar determination af the solubility of glycoluril showed aMethyl diazosuccinumate,L. T. T.Constitution of GIycoluriI.NH*CH*NH,I \NH.CH*NORUA'NlC CHENISTRY. 35ratio of 1 : 1060. Similar agreement was also found in the siher sdts,crystalline form, &c., both compounds crystallising variously in needles,prisms, or octahedra according to the solvent employed. Glycoluriland acetylenecarbamide are therefore identical, and the author pro-pofies the adoption of the latter name as the more suitable.Hydrocarbons from Tar-oils Boiling between 170" and 200".By 0.JACOBSEN (Ber., 19, 2511--2515).-The author has examined asample of coal-tar oil free from thiophen, of boiling point 170-200".By combined fractional distillation, conversion into sulphonic acids,sulphonic salts, and sulphonamides, he succeeded in isolating naph-thalene, pseudocumene, hemellithene, and another hydrocarbon, boilinglike the last-named at 175-175*5", but yielding a very solublemi+mwnide melting a t about 122-123". On oxidation, the hydro-carbon yields an acid which crystallises in needles melting at 119-121" and volatile in steam, aud also small quantities of a second acidmelting at 90". The acid of higher melting point yields isophthalioacid when oxidised with permanganate.Chloropropylbenzene.. By G.ERRERA (Gazzzetta, 16,310-325) .-I n order to determine the constitution of the chloropropylbenzeneobtained by the action of chlorine on the boiling hydrocarbon, thethree alcohols derivable from propylbenzene have been prepared andconverted into tbe corresponding chloro-derivatives.Phenylpropyl oloohoJ, C&Ph*CH2*CH20H, obtained from crudefitorax by Rugheimer's process, is not altered by gaseous hydrogenchloride, but when heated in a sealed tsbe with saturated hydro-chloric acid solution, it yields tbe chloro-derivative CH,Ph-CH,-CH,Cl.This compound i s a pale-yellow liquid, boiling at 219", and resemblingcymene in odour; when pure, it is very stable, being unaltered byprolonged treatment with fused xinc chloride or, silver acetate.Heated with alcoholic potttsh, it yields phenylpropyl ethyl ether,CH2Ph*CHe*CH20Et, a colourlem liquid boiling a t 220", insoluble inwater.NethyZ benzykd carbinoE, CHePh*CHMe*OH, obtained together with,allylbenzene and stilbene by the reduction of methyl henzyl ,ketonewith sodium amalgam, is a, liquid boiling at 215", of, a pale-yellowcolour and agreeable odour.Heated with hydrochloric acid in sealedtubes, it yields the chloro-derivative, CH,Ph*CHClMe, a yellowishliquid, boiling at 204-2Q7" with partial decomposition into allyl-benzene and hydrogen chloride. A similar reaction occurs with alGQ-holic potash, metallic zinc or its chloride.EthyZphenyZ carhino& CHPhEt-OH, prepared by prolonged reductionof the corresponding ketone with sodium amalgam, as described byBarry, is a liquid boiling at 215-217'.It is converted by gaseoushydrogen chloride, even at ordinary temperatures, into the chlorideCHPhEtCl, a yellow liquid. bailing about 200-205", but with con-siderable decomposition into bydrogen chloride and allylbenzene, 8change which takes place even on distillation in a vacuum. It isdistinguished from the two preceding chloro - derivatives by thereadimss with which it reacts with silver acetate, .xielding tbe itcetyl-L. T. T.L, T. T.d 36 ARSTRACTS OF CHEMICAL PAPERS.derivative, CIAPh'EkOAc, a liquid %oiling trt 227", of fruity odonr, andimsolixble in water. The chloropropylbenaene obtained by the directdhlorination of the hydrocarbon is identical with the second of the abovechloro-compounds, i n that it is decomposed by distillaticm and byalcoholic potash, as also by its stability towards silver aoebate.Iuthese properties, the chloro-derivatives of propylbenzene are directlycomparable to those of ethylbenzene.Reduction-of Trinitro-+-cumene. By F. MAYER (Ber., 19,2312-2314) .-In preparing nitrocnmidine by passing hydrogen sulphidethrough a boiling alcoholic solution of trinitro-+xmene, the chiefproduct is a new acid, CgH12N&305. T t is insoluble in alcohol, ether,glacial acetic acid, '&c., soluble in' hot water, from which it crystalliseson the addition of a few drops of hydrochloric acid in splendid, whiteor yellowish plates. Salts wereprepared. 'N.H. M.Hemellithene. By 0. JAUOBSEN (Ber., 19, 2517-2520).--Theauthor has investigated this compound, which he has now isolatedfrom the fraction of coal-tar oils boiling between 170-200" (see p. 35).Hemellithene, CsH3M, [ 1 : 2 : 31, boils at T75-175.5", and does notsolidify a t - 20". Tribrow~ohenl,ellithene, C9H9Br3, forms long needlesmelting at 245", and is very sparingly soluble in alcohol ; trinitrdhenzelli-tliene forms prisms melting at 209". The monnosulphonic acid crys-tallises in hydrated rhombic or hexagonal plates, and yields crys-talline salts ; its sulphonamide melts at 99tL-196". Hemellithehenol,C,H,,*OH [Me : Me : Me : OH = 1 : .2 : 3 : 51, is obtained byfusing the mlphonic acid with alkali. It is soluble in dcoholand ether, and crystallises in needles melting at 81".Hemelli-thy& acid, C,H,Me,*COOH [Me : Me: COOH = 1 : 2 : 31. is furmedby the oxidation of the hydrocarbon by dilute nitric acid. It isvolatile in steam, and crystallises in wales melting a+ 144". Its8aZcim salt is described. Distilled with lime, it yields mthoxylene.a - Sz~~rph.aminehemellithy1ic acid [Me : Me : COOH : SO,NH, =1 : 2 : 3 : 51, is formed by the oxidation of the above sulphonamide.It melts art Z W , and with hydrochloric acid yields a sulphohemelli-thylic acid melting at 180-190". ~-Szclprphaminehemellithylic acid[Me : "Me :COOH : SOZNHz = 1 : 3 : 2 : 51, formed a t the same time asthe-a-ackl, is more solhble, and melts a t 174". It yields avery solublesulphonic acid when ' hwted with hydrochloric acid.Both acidRwhen fused with potash yielded an easily soluble hydroxyhemellithylicacid, which does not give a blue coloration with ferric chloride.Hemellithene may be readily extracted from the tar oil by means ofthe sparing solubility of its barium sulphonate.Reciprocal Transformations Of Cymene and Cumenederi-vatives. By M. FILETI (Guzzetta, 16, 300-310).-In this paper arecollected the hitherto observed transformations of cumene and cymene-derivatives, the one into the other, and from them is drawn thefollowing generalisation :--A propy1-poup in the para-position rela-tively to a carbon-atom combined with other elements or with non-oxygenated groupings, is transformed into the isopropyl-group, if thisV. H. V.It melts at 240" and carbonises.L.T. TORGANIC CHEJIISTRT. 37element or grouping is displaced by an oxygenated radicle whoseoxygen is directly united to the carbon-atom compound, and converselyail isopropyl, is converted into a propyl-group when these substitutionsare reversed. (Compare Widman, Abstr., 1886, 453.)Chlorocymene and Bromocymene from Thymol. By M.FILETI and F. CROSA (Gazzetta, 16, 287 - 300). - Chlorocymene(parapropylmetachlorotohene), C6H3MePrC1, is obtained almost intheoretical proportions by heating in a reflux apparatus 4 mols. ofthymol with 1 mol. phosphoric chloride. On oxidation with nitricacid, Gerichten (Abstr., 1879, 238) obtained an acid, believed to be ahydrochlorocinnamic acid, C,H,n/Ie~1*Cil2.CH2*C0OH. It is here,however, shown that under these conditions three acids are formed,namely, chlorocumic, orthochloroparatoluic, and chloroterephthalicacids.Sixty per cent.of the theoretical quantity of bromocymene, calcu-hted according to the equation 4C,HI3*OH + PBr5 = CloH13Br +PO(OCloHlJ3 + 4HBr, can be obtained by the gradual addition of26 grams of bromine to 45 grams of phosphorus tribromide, and heat-i n g the resulting perbromide with 100 grams of thymol. On oxidn-tion with nitric acid of sp, gr. 1.2, bromocymene yields bromocumicacid ; with acid of sp. gr. 1.29, bromonitrocymene with bromocumic,bromonitrotoluic, and bromoterephthalic acids, whilst nitric acidof sp. gr. 1.39 yields the same acids without the bromonitrocy-mene. The bromcumic acid is identical with that obtained by thedirect bromination of cumic acid ; it has, therefore, the constitutionC6H,PrBr*COOH. The broinoizdrotoluic acid crys tallises in laminae,which melt at 200" without decomposition; it is isomeric with theacid obtained by the nitration of bromotoluic acid ; its barium saltcrystallises in long, yellow needles.The brornoterephthalic acid isidentical with that obtained by Fischli by the oxidation of bromopara-toluic acid. V. H. V.V. H. V.Ethylxylenes, By 0. JACOBSEN (Ber., 19, 2515--2516).-For thepurposes of comparison with hydrocarbons obtained from the fractionof coal-tar oils boiling between 170" and 200" (this vol., p. 35), theauthor prepared the three isomeric ethylxylenes from the three corre-sponding xylenes, using Fittig's method. Etlzylorthoxyle~~e yields acrystalline sulphonic acid, giving a sulphonamide crystallising inneedles melting at 126".Ethylmetaxylene boils a t 184-186", and isstill liquid a t - 15" ; its sulpphonic acid is crystalline, and yields crystal-line barium and sodiwm salts; its sulphoibamide melts at 148". Jbhyl-paraxylene boils at 185", and is still liquid a t - 20"; its suZphonic acidcrystallises in rhombic scales, forms crystalline barium and sodiumsalts, and yields a crystalline suZpphonamide which melts at 117".Ethereal Carbonates. By. G. BENDER (Ber., 19, 2265-22.71 ;compare Abstr., 1881, 48). -When naphthyl ethyl carbonate,OCloH,*CO-OEt, is boiled f o r some time, carbonic anhydride andalcohol are given off, and the residue consists of a, mixture ofa-naphthol and a, compound C2,H1202 (Zoc.cit.). The formation ofL. T. T38 ABSTRACTS OF OHEJIICAL PAPERS.diphenylene ketone oxides from salicylic acid (Perkin, Tmna, 1883,35) and the intermolecular change of sodium phenyl carbonate tosodium salicylate, suggest that Ohe naphthyl ethyl carbonafe mayhave become changed to the ethyl salt, OHCl,H6~COOEt, and that2 mols. of the latter have condensed with formation of the compoundCZ1H1",2 ; this would then be dinaphthylene ketone oxide,ClOH6<CO>ClO'Il6* 0The isonaeride obtained by boiling P-dinapht hyl diethyl orthocarbonate(loc. cit.) crystallises from benzene in thin prisms melting a t 194".When phenyl ethyl carbonate is heated a t 300" for 3-4 hoursdiphenylcarbonate is formed.Paraditoly 1 carbonate is obtained by heating paratolyl ethyl carbo-nate at 300"; it is insoluble in water, moderately soluble in hotalcohol, and melts at 115".Tlynayl ethyl carbonate is a thick liquid boiling at 260"; a t 300" itdecomposes into dithyrnly 1 carbonate, melting a t 60".Orthoaitrophenyl ethyl carbonate is prepared by the action of ethylchlorocarbonate on potassium orthonitrophenoxide.It is a heavyyellow oil which boils with decomposition a t 275-285". The arnido-salf, NHE,*C6HrO*C0.0Et, melts a t 95"; it is soluble in alcoho!,moderately soluble i n boiling water. When distilled, it gives offalcohol with formation of ar~hydro-orthamid~~7~e~~yl carbonate, C,H,NO, ;the latter dissolves in alkalis.The silver salt, C7H4AgN02, formsan amorphous, colourless precipitate. The ethyl salt is obtainedby boiling the compound with alcoholic potash and ethyl iodide.When heated with fuming hydrochloric acid, it yields ethyl orthamido-phenol and carbonic anhydride ; the constitution of the substance istherefore c6H,<~~~>co. Tbe phenylhydrazine compound of anhy-dro-orthamidophenyl carbonate, C6&<-O->C : N*NHPh, crys-tallisee in yellow needles, which melt at 208". The acetyZ-derivativemelts at 97-98". A InorLonrtro-co~npound was prepared ; it forms longyellow needles melting at 256". Bromine acts on the anhydro-corn-pound with formation of a nzonobromo-derivative ; this crystallises fromwater in plates melting at ,196". When treated with phosphoricchloridc, the compound C7H4ClN02 is .formed.Parahydroxybenzyl Alcohol.By J. BIEDERMANN (Ber., 19,2373-2376).-Parahydroxybenzt~l alcohol, OH*C6H4*CH20H, is prepared bydissolving parahydroxybenzaldehyde (I part) in a mixture of water(10 parts) and alcohol (5 parts) ; it is then acidified with dilute sulphuricacid and gradually treated with 3 per cent. sodium amalgam (40 parts).Grey crystals of diparahydroxyhydrobenzoin and oily drops of dipnra-hydroxyisohydrobenzoh separate. When hydrogen is no longerevolved, the solution is made strongly acid and left for 12 hours, it isthen filtered, the filtrate extracted with ether, and the ethereal extracttreated with hydrogen sodium sulphite. On evaporating the ether, thealcohol separates in needles ; these are purified by dissolving tlhem in hotchloroform and precipitating with light petroleum.It forms slenderN HN. H. MORG AKIU CHEMISTRY. 39white needles, readily soluble in water, alcohol, and ether, sparinglyin benzene and chloroform; sulphuric acid dissolves it, yielding asplendid 1-ed-violet solution. It melts a t 110". The alcohol is alsoformed when parahydroxybenzaldehyde is kept dissolved in aJcoholicpotash for several weeks, but the reaction is still very incomplete.The acety I-derivative, OH*C6H4*CH,.0Ac, is prepared by heating thealcohol with a mixture of glacial acetic acid and sulphuric acid. Itcrystallises from water in small yellow needles, melting at 84", and isreadily soluble in alcohol and ether, spariiigly in water, benzene,chloroform, &c.The diucetyl - derivative, OAc*CcH4*CH2*OAc, isobtained by heating pnrahydroxybenzyl alcohol with an excess ofacetic anhydride a t 160" for 5-6 hours. It forms yellowish needlesmelting a t 75", readily soluble in alcohol and ether, sparingly inbenzene, &c.Br~isic alcohol, OMe*C6H4*CHI,0H[ = 1 : 41, is formed when para-hydroxybenzyl alcohol is dissolved in methyl alcohol and digestedwith potash and methyl iodide for some hours at 100". The productis treated with wzter, heated to expel methyl alcohol and iodide, andextracted with ether. On evaporating the ether, it is obtained as anoil which gradually solidifies when kept over sulphuric acid. It crp-tallises from water in needles melting a t 45" (compare hbstr., 1888,460).N. H. 11.Synthesis of Betorcinol (p-Orcinol). By S. V. KOSTANECKI(Bey., 19, 22 18-2324 ; comr are Abstr., 1886, 242) .-Z'araxylorcinol[Me2 : (OH), = 1 : 4 : 3 : 51 was prepared from metadinitroparaxyleneby rcplacing the nitro-groups successively by amido- and hydroxyl-groups ; it is identical with Stenhouse and Groves's betorcinol (Trans.,1880, 396). The crude product obtained by nitrating paraxylene iscrystallised from alcohol to remove most of the orthodinitroparaxylene,dissolved in hot alcoholic ammonia, and treated with hydrogen sul-phide for about one hour; i t is then evaporated to dryness. Theparadinitro-compound, being more readily reduced than the meta-compound, is thus converted into paranitroparaxylidine, which isextracted by means of hydrochloric acid.The residue, insoluble inacid, was extracted with boiling alcohol, and yielded crystals of puremetadinitroparaxylene. This was reduced by dissolving in alcoholicammonia and treating for two hours with hydrogen sulphide, and thenitroxylidine [ Me2 : 50, : NH2 = 1 : 4 : 3 : 51 so obtained was convertedinto the corresponding nitroxylenol. The latter crystallises in yellowplates melting at 91". It was reduced with tin and hydrochloric acid,and the amidoparaxylenol diazotised ; to 1 gram of the hydrochloride10 grams of sulphuric acid and 100 grams of water were used, and thewhole kept cold by means of ice and salt.Paraxylorcinol so prepared has all the properties ascribed to it byStenhouse and Groves (Zoc.cit.), except that it yields a green fluo-rescent solution when treated with dilute soda and chloroform.Metaxylorcinol (Pfaff, Abstr., 1883, 918) crystallises from chloro-form in white monocliniccrystals, a : b : c = 1.7237 : 1 : ? ; p = 38" 21'.It boils a t 276-279". When heated with sodium carbonate solution a tlSO", metaayZol.ci,rLoZcurborylic acid, CsHMe2( OH),*COOH, is formed40 ABSTRACTS OF OHEMICAL PAPERS.The latter crystallises from dilute alcohol in well-formed prisms whichnielt with decomposition at 196", and give a deep blue coloration withferric chloride. N. H. M.AcetalsesoscinoL By - CAUSSE (J, Pharm. [ 5 ] , 13, 354-358).-The author has examined the action of sulphuric acid andheat on a solution containing acetaldehyde and resorcinol.Thecrystals obtained are insoluble i n water, ether, chloroform, and ben-zeue. They are soluble in alcobol, which yields them again partlychanged. Anhydrous ether dehydrates them, converting them in toII powder, which in time aggregates to yellow, translucent crystals.Thus purified, the compound decomposes on fusing with regenera-tion of resorcinol. Its composition is indicated by the formulac14Hl404 = C2H40 + 2C6H602 - H20. The action of heat on thecompound apparently removes the elements of water. Heated a t120°, a reddish powder was formed which could be obtained in largebrown crystals. These had the composition CzeE,60, = 2CI4H,,O4 -The reactionsindicate that the yellow crystals are st molecular combination ofaldehyde and resorcinyl ether, C,l&O,O( C6Ha*OH)2.Benzylarnine.By T. CURTIUS and G. LEDERER (Rer., 19, 2462-2463) .-When benzaldehyde and amidoacetic acid are heatedtogether a t 130", carbonic anhydride is evolved and benzylamineformed. Similar reactions seem to take place when cinnamaldehgde,salicylaldehyde, or orthonitrobenzaldehyde, are substituted for theBenzaldehyde, but the products are not so easily isolated.Citric Acid Derivatives of Paratoluidine. By J. M. G:LLH2O.The diacetyl compound, C36H1B012, melts a t 28'2".J. T.L. T. T.(Ber., 19, 2352-2354) -Citroparatoluidide, C6H,04(NH.C7H7),, isobtained by heating citric acid (1 rnol.) and' paratoluidine (3 mols.)at, 140-145" for 10 hours. It crystallises from alcohol, in which itis sparingly soluble, in lustrous, microscopic needl'es, melting a t 189".Citrodlparatoluide, C6H504(NH*C7B7) N.C7H,, is formed when citricacid (1 mol.) and paratoluidine (2 mols.) are heated at 160-170" forthree hours.. It melts at 205", is insoluble in water, rather readilysoluble i n ether and alcohol, and separates from the latter solvent insmall, yellow, well-formed crystals. When heated with citric acidat 140-145", it is converted into citroparatoluidide. Ammonia actson it, yielding a salt of citrTaraditoluidic acid, C6H,04(NHC7H7)2*OH.The latter crystallises from alcohol in groups of needles, melting at161".NC7H,, is prepared by addingparatoluidine (1 mol.) to a hot concentrated alcoholic solution ofcitric acid (1 mol.).On cooling, the solution yields clear prismaticcrystals; these are heated for two hours at 160-170", and crystal-lised from water. It melts a t 172*5", and dissolves readily in alcohol,ether, and hot water. N. H. M.By 0: WALLACH (Annalen, 234,350-364) .- Paxace tometatoluylenediamine, obtained by the actionIt is soluble in water, insoluble in alcohol and ether.Citroparafoluidic acid, C6H5O4(0H)Azo- and Diazo-compoundsORGANIC OHEMISTRY. 41of acetic anhydride on metatoluylenediamine (Abstr., 1883, 329) canalso be prepared by converting nitrotoluidine (m. p. 77.5") into theaceto-compound (m. p. L44-5"), and reducing this substance with ironfilings and acetic acid. By means of the diazo-reaction, the aceto-metatoluylenediamine is converted into acetamidocresol (m.p. 225"),proving t hatl the acetyl-group occupies the para-position.Parucetamidotolueneorthazodimethy lanild-ne,NHBc*C6H~e.N,*C6H4*N~e2,is formed when a, solution of the diazo-csmpound is poured into anice-cold alcoholic solution of dimethylaniline. The substance crystal-lises in golden plates and melts at 200". It unites withacids to formsalts, which dissolve in water, yielding deep-red solutions. Theacetyl-group can be eliminated by boiling with dilute sulphuric acid.P(rramidoto1ueneorthazodimethy Ianilins mystallises in golden scales.It melts a t 145", and dissolves in hot alcohol, chloroform, and ben-zene. The diazo-compound unites with phenol, fomning totueneazo-dirnethy l a d b eparawphenol, NMe2.C6~*N,*C6H3Me.N2*CsH4*OH.. This substance dissolves in dilute solutions of the alkalis, and isreprecipitabed by carbonic acid. It also dissolves in strong acids, andis reprecipitated by the addition of water. It dissolves freely inalcohol, ether, chloroform, and benzene.It isinsoluble in water, sparingly soluble in alcohol, b u t dissolves in strongsulphuric acid, with a red coloration.Pai.acRt~idotoluensorthazodiethzJlaniEine crystallises in needles ofa reddish-brown colour. It melts at 159", and dissolves freely inalcohol, ether, chloroform, and in acids. The sdts are decom-posed by large quantities of water. Orthacetometatoluylenediamine,NHAc*C6H&le*NH, [Me : NHAc : NH, = I : 2 : 41, prepared fromorthoamidoparanitrotoluene (m. p. 107"), crystallises in white needles,and melts at l4W.It is soluble in alcohol, in ether, and in hot water.Orthacetamidotolzceneljarazodintethylamili,ne melts at 192", and dissolvesfreely in almhol, chloroform, benzene, and ether. Orthamidotoluene-parazodirnethyllanili~~e melts at 215P, and is freely soluble inchloroform,Acetnmido b ,onZen emet azodimet h y landhe, NH Ac*C,H,*&*C,H,*NMe,,crystallises in plates, and melts at 184". Amidobenzenmzodimeth?yl-aniline forms golden scale% soluble in alcohol, which melt at. 165-166". w. c. w.The corresponding P-naphthol-compound melts about 24".Quinone-oximes. By 3;. SUTKOWSKI (Ber., 19, 2314-2317).-When thymoquinone-oxime is dissolved in cold, fuming hydrochloricacid, a yellow precipitate is formed, consisting of dichlorothymo-quinone and monochlbramidothymol (Andresen, Abstr., 1881, 590).When the precipitate is boiled with glacial acetic acid, a splendid reddye is formed.The reaction is of interest, as itl d ~ o a s the analogybetween the Beactions of thymoquinone and of thymoquinone-oximewith fuming hydrochloric acid. Andresen also obtained the sameproducts from thymoquinonechlorimide. The oxime is therefore thehydroxyl-derivative corresponding with the quinonechlorimide42 ABSTRACTS OF CHEMICAL PAPERS.When chloramidothyrnd hydrochloride and chloranil are hmted inglacial acetic acid solution, the red dye above mentioned is formed.Tetrachloroquiriol is formed in the reaction ; it crystallises in longcolourless needles melting at 832".Analyses of the dye point to theformula C30H35C13N203.In a similar manner, a dye was obtained by the action of parsmido-thymol on chloranil in glacial acetic acid solution. It has the cam-position expressed by the formula C,H38N203. (It dissolves in aceticacid, alcohol, ether, and benzene, but not in water. Ammonia dissolvesit with formation of a blue solution. Lead acetate gives a blue preoi-pitate. N. H. M.By M. LOEB (Ber., 19, 2340-2344) .--When the compound Cl6Hl2N2CI2O2, prepared by the action of car-bony1 chloride on ethenyldiphengldiamine (Abstr., 1885, ,1213), istreated with alkalis or acids, it is reconverted into the amidine.Boiling water has no action on it ; 'boiling alcohol converts it intocarbanilide, ethyl acetate, and ethyl chloride.The ethyl salt,OEt*CO*NPh*CMe : N*C6H4-COOEt, separates from its ethereal solp-tion in hard, lustrous, rhombic crystals which melt at 90.5". Whenthe chloride is dissolved in benzene and treated with dry ammonia,i t is converted into ethenyldiphenyldiamine and ammonium chloride ;aniline acts like ammonia.Amidine-derivatives.Ethenylimidobenzanilide, CMe<,,,>CO, N.CeH4 is prepared by theaction of carbonyl chloride dissolved in benzene on an excess ofethenyldiphenyldiamine ; i t crystallism from benzene in large, lustrousplates melting at 118". It is identical with the compound to whichthe formula CO( C11H13N2)P was previou-sly ascribed (Zoc. cit.). Dilutehydrochloric acid decomposes it wihh formation of aniline and phenglcyanate.When a saturated ethereal solution of ethenyldiphenyldiamine istreated with two or three drops of water and then with cyanogenuntil it has a wine-red colour, and allowed to remain for 16 hours, ablack crust is formed which yields a compound, C16H16W40; thelatter forms a white, crystalline powder very sparingly soluble in etherand benzene, and cannot be recrystallised, as it at once resinifies whenheated with solvents.It becomes violet at ;120", and melts withdecomposition at 165". Its constitution is probably analogous to thatof Griess' cyanocarbimidoamidobenzoic acid, as shown in the formulaNPh : CMe*NPh*C(NH)CN + H20. Ethyl allophanate is formedwhen urethane (7 partsl) and carbonyl chloride (1 part) are dissolvedin benzene and heated at 75". N.H. M.Preparation of Aromatic Amides. By 34. FEILETII (Gaxzei%a, 16,281--284).-The method, proposed by Letts, for the preparation ofthe nitriles by heating the carboxylic acids with potassium thio-cyanate, has been shown to yield the amides, if ammonium thio-cyanate be substituted for the potassium mlt. The former chaiige isattributed by Keku16 to the greater dehydrating action of thepotassium salt, an interpretation confirmed by the observation oORGANIC CIIEMISTRY. 48Muller that in the above method benzamide is formed if the processis conducted quickly, but phenyl nitrile if slowly. In the course ofthe preparation of cumonitrile, a small quantity of cuminamide isobtained from the crude product of the reaction, if the aqueoussolution, prerioudy rendered alkaline by ammonia, is agitated withbenzene.This amide crystallises .in glittering lamins melting a t153*5", insoluble in cold, sparingly goluble in hot water, soluble inalcohol. It is not decomposed by boiling with hydrochloric acid orpotash of moderate concentration. With mercuric oxide, i t yields aderivative, ( CsH4Pr*CONH),Hg + 1+H,O ; this crystallises in needlesmelting a t 190", insoluble in water, soluble in alcohol.V. H. V.Action of Alkyl Iodides on Dibenzylthiocarbamide. By C.REIMARUS (Ber,, 19, 2348--2349).-Will has shown (Abstr., 1882,723) that alkyl iodides react with diphenyl- and dibenzyl-thiocarb-amide, with formation of hydriodides of bases in which the alkyl-group is directly combined with sulphur.The author has found thatthe isomeric dibenzykthiocarbamide behaves analogously.Brnzy Zimidobei,zyZcarbuminethiomefhg I, SMe-C (NHCTH,) : NC7H7, isformed when methyl iodide and dibenzylthiocarbamide are heated for2-3 hours at 100". Thelproduct is dissolved in water, treated withsodium carbonate, and extracted with ether. The suZphate of the basecrystallises in lustrous needles readily soluble in water and alcohol ;i t melts a t 145". The hydrochloride forins large rhombic plates meltinga t 125" ; the h!jdriodide crystallises in splendid octahedrii melting at99", readily soluble in hot water.Benzy ZimidlJbelzzy Zcarbaminethioet~i yl, SEt.C(NHC&) NGTH,, crys-tallises in wide prisms, apparentlF monoclinic, which melt at 93" ; itdissolves readily in alcohol, sparingly in water.%he suZphate formslarge rhombic plates readily soluble in water and alcohol ; the plutiiio-chloride crystallises in needles.Corresponding compouuds were also prqpared from propyl iodideand amyl iodide.Phenylseleniocarbimide and Diphenylseleniocarbamide. ByH. STOLTE (Ber., 19, 2350-2352).--Yh enyZseZeniocarbimide, CSe*NPh,is prepared by passing hydrogen selenide into aqueous soda, evapo-rating, and adding isocyanophenyl chlolride diluted with ether toprevent the reaction becoming too violent. After a day, the productis filtered, the ether evaporated, and the residue steam-distilledand dried in a vacuum over sulphuric acid. It is.a yellowish-red oil,insoluble in water, readily soluble in alcohol and ether, and has onlya slight odour. When the ethereal solution of the substance istreated with ammonia, it is converted into monophenylseleniocarb-amide (Abstr., 1886, 781).Di13heiayZseleniocurbur)aide, CSe (NHPh),, is prepared from phenyl-seleniocarbimide by treating its ethereal solution with aniline.Theproduct is washed with ether, and crjstallised from alcohol. It meltsat 1M3 with decomposition.N. H. M.N. H. 3144 ABSTRACTS OF CHEMICAL PAPERS.Substituted Nitrogen Chlorides. By G. BENDER (Ber., 19,2272--2274).-When the compound C,H4<-5H> CO (this vol., p.38) is treated with bleaching powder and hydrochloric acid thecowpomzd C7H,N02C12 separates in colourless needles. When thelatter is brought into contact with quinol, an odour of quinone isgiven off, and on cooling crystals of quinhydrone separate.Thecomponnd is decomposed by alcohol, alkalis, aniline, &c., into the=TTTcompound C,H,Cl<f~>CO (Zoc. cit.) .Acetanilide, when treated with bleaching powder in presence ofacetic acid, yields the compound NPhCl*COMe. The latter has theproperties of the compound described above. It melts at 91' ; whenheated to.l72", it becomes yellow, effervesces violently and is convertedinto its isomeride, parachloracetanilide, melbing at 172". The samechange takes place when the substance is treated wibh cold hydro-chloric acid or when warmed with absolute alcohol; if more t,han2 grams be employed, a violent explosion takes place. The compoundreacts with paranitranibine, yielding acetanilide and ort bochloropara-nitrani line.The comPound <C&CO cH2*co >NC1 was prepared from succinimide : itcrystallises from benzene in large colourless crystals melting at 148".Ihnaamide yielded the cornpzclzd COPh*N€€Cl.This crystallisesfPom water in long prisms melting at 116".Condensation of Nitrobenzaldehyde with Hydrocarbons.By 0- TSCHACHER (Ber., 19; 2463-2464).-Baeyer has shown thatfatty aldehydes, in the presence of concentrated sulphuric acid, formcondenmtion products with aromatic hydrocarbons, whilst aromaticaldehydes do not. The author finds that the ilbtroduction of a nitro-group into the phenyl-ring gives to aromatic aldehydes the power offorming such condensation productsWith benzene, metanitrobenzaldehyde yields metanitrotripheny2;-methane, forming crystals melting at 90".With toluene, rnstanitro-phenydditoly ZmethaNe is formed.N. H. M.L. T. T.Compound of Pymvic Acid with Hippuric Acid. By A.HOFFMBNN (Ber., 19, 2554--2557).-6 grams of pyrnric acid weredi esCed with 11 grams of sodium hippurate and 25 grams of aceticaniydride on a water-bath. In a short time, a vigorous reactiontakes place and the temperature of the mixture rises to 108". Theproducf is dissolved in alcohol, the solution diluted with water,evaporated, and the brownish crgstala recvystallised from petpoleurn.Analyses of the compound point to the formula CJ&NO4; the sub-stance is therefore formed by the iinion of its two constituents (equalmols.) with elimination of the elements 0% water (2 mds.).I t formscolourless, flat needles melting at 157"'; iD is very readily soluble i nalcohol, ether, and acetic acid; insoluble in water. It yields saltscorresponding with a, bibasic acid, C1'LHllNOO. The barium salt,Cl2HEN'O5Br + 2H20, was prepared; when treated with acid, iORGANIC CHEMISTRY. 45yields the anhydride, ClzH9NOa, the acid not being capable of existingin the free state. When the anhydride is heated with hydrochloricacid at 140°, benzoic acid is formed. N. H. N.Phenyliodohydracrylic Acid. By E. ERLENMEXER and J.ROSENHEK (Ber., 19, 246&2465).-Ph eny l i o d ~ h y d r u ~ m ~ l ic (a-iodo-6-pheny Zh ydroxypropionic) acid, OH-CHPh-CH I*COOH, was obtainedby theaction of iodine chloiPide on cinnamic acid.A chloriodophenyl-propionic acid is probably fimt formed, whieh is then converted intothe hydroxy-acid by the action of water. The acid forms largecrystals which melt with decomposition at 137-139", and are solublein benzene. When treated with hydrochloric acid, this acid yields acompound C18H16CI104, which the author believes to have the formulanCHPh : CHG (OH) <g>C(OH) *CHI. CHClPh. L. T. T.Creasolcarboxylie Acid. By H. WENDE (Ber., 19, 2324-2327).-CreosoZcarbozylk acid, OH*C6H2&fe(O?Y1e).COOH [= 4 : 1 : 3 : 51,is prepared by gradually adding 4 grams of sodium to 50 grams ofcreosol through which a current of dry carbonic anhydride is beingpassed. The reaction takes place slowly with evolution #of hydrogenand slight development of heat, and is assisted by gently warming;much heat is then developed, and the reaction becomes rather violent.The product, when cold, is treated with dilute hydrochloric acid,extracted with ether, and the ethered solution extracted with sodiumcarbonate solution.It erystallises in needles melting at lHO-lX'i',dissolves sparingly in water, readily in alcohol, ether, and chloroform,and is almost insoluble in benzene and light petroleum. It sublimesunchanged when carefully heated, and aequires a deep blue colouswhen trea%ed with ferric chloride. The ammonium saIt crystallises inglobular groups of needles ; the potassium salt forms small, readilysoluble needles ; the barium salt is sparingly soluble ; the copper saltis a yellow powder; it is very electric when dry.The inethyl saltforms small, rhomhic crystals, a : 'b : c = 0.5285 : 1 : 0.7334 ; it meltsat 92", and gives a bluish-green coloration with ferric chloride. Theethyl salt crystallises in s m d l needles or prisms melting at 77".N. H. M.Derivatives of Op'ianic Acid. By C. LIEBERMAWN (Ber., 19,2275 - 2287 ; compare Abstr., 1886, 550). - Amidohemipinphenyl-,C : N -- NPhhydrazide (az~ianpheny lhydrnzide), NH( I I , is preparedC6H ( OMe) 2mc 0by the action of phenylhydrazine on azopianic acid. It separatesfrom its solution in benzene in small, honey-coloured, tetragonalcrystals, having a glassy lustre, a : c = 1 : 0.5947. It melts at 222",and dissolves in strong sulphuric acid and in fuming hydrochloricacid.Amido-opianpheny7hydrazide, NH2*C6H(OMe)2<-CH CO-NPh N->, is ob-tained by reducing the nitro-compound (Zoc.cit.) with tin and fumin46 ABSTRACTS OF CHEMICAL PAPERS.hydrochloric acid, care being taken t o prevent the reaction frombecoming too violent from the heat developed. On adding water toits alcoholic solution, it crystallises in slender needles melting at 157-143".is formed when nitro-opianphenylhydrazide is boiled with alcoholicpotash, and the potassium salt thus obtained' treated with hydro-ehloric acid. It crystallises in Fellow, glittering, rbombic plates melt-ing at 191". The potassium salt is a carmine-red powder.Oyianoxime anliydride (hemipiniinize), CJ&NO,, is prepared by boil-ing opianic acid (1 mol.) dissolved in nine times its weight of 80 percent.alcohol with, hydroxylamine hydrochloride ( I t mol.) for twoto three hours. It crystallises from alcohol in long, very slenderneedles melting at7 228-230". An aqueous or alcoholic solution con-taining only a trace of the subdance has a fine blae fluorescence. Itsublimes unchanged, and can be heated with strong sulphuric acidwithout decomposition. Cold aqueous a1 kali dissolves it, forming a,yellow solution which soon ldecomea colourless. When heated withalkali, it, yields hemipinic acid and ammonia. The compound was almprepred by heating ammonium hemipinate. The potassium salt,CloH80NK, is a white compound almost insoluble in cold absolutealcohol.Hemipinethyl imide, ClnH804 : NEt,.is obtained by heating potassiumhcmipinimide with ethyl iodide at 150".It crystallises from boilingwater in colourless- needles resembling hemipiuimide ; the solutionshows the same fluorescence. It diksolveR very readily in alcohol,acetone, and benzene, and melts a t 96-98".The formation of hemipinimide is interesting on account of itscomplete analogy with observations lately made in the phthalic acidseries. The author a,ssigns to the compounds phthalimide and hemi-pinimide the respective constitutional formulae. CO<-O'>C : NH0-and Co<G,(OMe),Anilido-opianic acid, Cl6HI5NOd, is obtained by boiling a solution ofequal weights of opianic acid and aniline, dissolved in gIacial aceticacid, for 10 minutes. On cooling, the whole solidifies to a, white mass,which is washed with water, dissolved in benzene, and precipitatedwith ether.It dissolves only in Btrong alkalisolution. Artilidonitropianic acid, C16H14N20s, is prepared from ni tr-opianic acid in a manner similar t o the above compound. It, cr-ystal-lises in needles melting a t 183-184". When treated with alkali, ityields n sparingly soluble potassiwn salt.Nitrohemipinic acid, K02*CsH(OXe)2(COOH)o, is very readily p1.e-pared by boiling nitropianic acid with fuming nitric acid (4 parts) forone hour. It melts a t 166" (not 155"), but has all the other propertiesascribed to it by Prim (Abstr., 1882, 402). Wben heated above itsmelting point, it gives up water and yields a yellowish compound,probably the anhydride.The silver s@Zt was also prepared.c6H4>C : NH.It melts at 186-187'ORGANIC CHEMISTRY.43Opianic anhydride, [ CHO*C,H,(OMe),*CO],O, is formed whenopianic acid is heated at 160" in a current of dry air. It crystalliseswell from acetone and melts at 234". It is identical with the coni-pound described by Wegscheider (Ahstr., 1883, 996) as triopiarnide,0,H,aO14. When boiled with alkali, it, is gradual17 transformed intoopianic acid. Strong nitric acid converts it into nitropiauic acid.Opianic Acid Derivakives. By C. IJTEBERMANN and S. KLEEMAKNN. H, M.(Ber., 19, 2287-2299).-AcetyZupinnic acid,is prepared by heating opianic acid and dry sodium acetate withacetic anhydride. The excess of. acetic anhydride is then removed bycontact with cold watey for 24 hours, and the remaining compoundcrptallised from boiling water.It is inso-luble in cold aqueous alkali, and when boiled with it, is decomposedinto opianic and acetic acids.>CH*OAb, is prepared Acetylnitropianic acid, <in a manner similar to acetylopianic acid. I& is a yellow substanceinsoluble in cold sodium carbonate solution.Propiony lopa'anic acid, C13H1406, crystallises in needles melting at111".An hyaraceta nt id oh emip inic acid, G ,,H,AcN O,, and trhe pi-opion y 1-compound, C,,H,( C3H,0)N0,, melt at 164" and 139" respectively ;they ape very unstable.)CH*CH,*COO@ is obtained byheating opianic acid (3 parts), rnalonic acid @+ part), glacial aceticacid (2 park), and sodium acetate (li Rart) for five hours at100" ; the colourless, crystalline product IS crystallised from water.It forms lustrous needles melting at 167" ; it has an aoid reaction anddissolves i n ammonia.The silver, calciunz, &c., salts were prepared.The ethyl salt crystallises in plates soluble in alcohol, ether, and hotwater; it melts at 82.5". The reactions of the acid are analogous tothose of phthalylacetic acid. When boiled with baryta, and the excessof baryta afterwards removed by means of carbonic anhydride, bariumopianylacetate" is obtained ; it forms lustrous prisms. The free acidis not capable of existence. When the silver salt is treated withmethyl iodide, it yields, not methyl opianjlacetate, but methyZm ecoiline-acetate ; the latter crystallises in lustrous plates melting at124".It melts at 120-121".(JO---C6H(N0,) @Me),co-CsH2(0Me)2 Necouiw-acetic acid, <>CH*CH,*COOH, is pre- co--0 Normecortine-acetia acid, <C,H,(OH),pared by heating rneconine-acet& ahd with hydriodic acid and phos-phorusi ; the product is diluted with water and filtered. It crystal-lises from water in long plates melting a t 218".The calcium andburiuwt saZts form white crystalline precipitates. When the acid is* The fmmtda slnd azalp:s given in the original do not agree48 ABSTRACTS OF CHEMICAL PAPERS.heated with ferric chloride, it acqfiires a characteristic blue colour,which changes to green in presence of an excess of ferric chloride,The ethyl salt separates from its solution in boiling water as an oil,which then solidifies and melts at 131".Its solution is fluorescentand reduces silver solution, but to a smaller exbenltthan the free acid.I t has an acid reaction and precipitates from baryta solution a yellowbarium salt of the ether. This acid property and the power ofreducing silver solutions is due t o the presence of pylrocatechol-hydroxyl.Ort h onitrom econine- acetic acid,co -o>CH.CH2*COOH [NO2 : CH*CH2*COOH=1 : 21, <C,H(N02)is obtained by dissolving meconine-acetic ncid in fuming nitric acidand afterwards precipitating with water. It forms colourless crystalsmelting at 176". The ethylsalt crystallises in lustrous needles, rcadily soluble in alco'hol andbenzene ; it melts at 129". Nitromeconine-acetic acid dissolves insulphnric acid, forming a.yellow solution ; this, when warmed, acquiresa cherry-red colour, characteristic of compounds containing a nitro-group in the ortho-position to a long side-chain (Baeyer, Abstr.. 1882,620). When the nitro-compound is reduced with tin and hydro-c hloric acid, dimethox y hy drocarbostyril- lactone,The calcitwt saZt forms yellow needles.is formed. This crystallises from water in colourIess needles, melt-inq with evolution of carbonic anhydride at 256". It is readilysoln'ble in alcohol and glacial acetic acid, insoluble in ether andbenzene. It dissolves in baryta; when the solution is boiled andtreated with carbonic anhydride and evaporated down, Iastrousneedles of barium dimethoxyhydrocarbostyrilcarboxylate are ob-tained.Dilnetliox~IddihydrochZoroquinoline lactone, 6C12Hl0N Clod, is preparedby heating the lactone just described with phosphorus pentachlorideand some phosphorus oxychloride for two hours at 165-170"; theproduct is poured into iced water, and the precipitate crystallised fronialcnhol, from which it separates in needles ; these melt at 218" withevolutim of carbonic anhydride.The barium) salt, obtained by boilingthe lactone with baryta, and the silver salt were prepared.Dihydroxydihydroquinoli?ie lactone, CloH,IIU'O,, is obtained by heatingthe above chloro-derivative dissolved in glacial acetic add for onehour at 120" with hydriodic acid. It melts at 220" with decomposition.By H. GRCNR (Ber., 19, 2299-23@5).-Azo-opianic acid, prepared from nitropianic acid, melts at 200" withdecomposition (not 184" as given by Prim, Abstr., 1888, 404).Thepofassium salt is a white crystalline powder. The et?iyl salt crystal-1ises in needles melting at 98" ; the methyl salt melts at 127". Theauthor confirms the statement of Prinz ( ZOC. cit.) that azopianic acid,when boiled with barytzt in excess, yieIdrJ barium amidohemipinateN. H. M.Azo-opianic AcidORQAXIC CHEMISTRY. 49The yield is almost quantitative. Sodium amidohenzipinate crystallisesfrom alcohol with 3 mols. H,O, in long, almort white needles ; it isvery readily soluble in water. The copper salt (with i mols. H,O)erystallises in stellate groups of slender, green needIes. The aqueoussolution of the free acid has a fine green fluorescence which disappearswhen alkalis or acids (except acetic acid) are added.It reduces acold animoniacal silver solution, and Fehling's solution when warmed.ob-tained when a cooled solution of sodium amido-hemipinate is treatedwith sodium nitrate and hydrochloric acid. It is a bright yellow, micro-crystalline powder which becomes superficially red when exposed tolight, and explodes at 140-150" or when struck. It dissolves readilyin alkalis and acids ; when boiled with water, it gives off nitrogen andyields a hydroxy-acid, which gives an intense blue-violet colour withferric chloride. The hydrochloride, COOH*CsH( OMe),( COOH)*N,Cl+ H20, crystallises in long, colourlew needles ; in presence of water,it decomposes into hydrochloric acid and free anhydroazohemipinicacid.When the diazohemipinic acid is boiled with alcohol undsrslight pressure, it is converted, with evolution of nitrogen, into hemi-pinic acid.Nitrohemipinic acid was prepared by Liebermann's method (thisvol., p. 46). The potacsium sult crystallises in deep yellow prisms,readily soluble in water and alcohol, the silver saZt is also yellow.21Titrohen2ipinic rcnhydride, NO,*CsH( OMe) <co > 0, is preparedby heating the acid at 160-165" for two hours ; it crystallises frombenzene in bright yellow prisms melting a t 145". When nitrohemi-pinic acid is reduced with ferrous sulphate and soda, amidohemipinicacid is formed identical with the acid obtained by boiling azo-opianicacid with baryta.The results of the experiments above described confirm the viewbrought forward by Liebermann (loc cit.) that Prinz's so-called azo-opianic acid is not an azo-derivative of opianic acid but an internalanhydride of orthamidohemipinic acid.When nitrohemipinic acid is reduced with tin and hydrochloricacid, the compound COOH.C6H,( OMe)2*NH2,HC1 is formed.N.H. M.Derivatives of Normethylnitropianic Acid. By K. ELBEL(Ber., 19,2306-2312) .-Normethylnitropianic acidCOH* C6H ( C 0 OH) (OH) ( OMe) *NO,,is best prepared by heating finely powdered nitropianic acid withfuming hydrochloric acid (10 parts) for 15 hours at loo", with a refluxcondenser, hydrogen chloride being passed in all the time. Theproduct is evaporated down, when the normethyl-compound sepa-rates ; the yield is 80 per cent.of the theoretical.Normethylorthanhyd~-lzmidohemipinic acid (normethylazo-opianicacid), OMe*C6H(OH)(COOH)<~~> [OMe: OH : COOH : CO : NH= 4 : 3 : 2 : I : 61, is obtained by treating a boiling saturated aqueousN,-0 Anhydrodiazohenzipinic acid, COOH*C6H(O~e)2< co >, iscoVOL. LII. 50 ABSTRACTS OF CHEMICAL PAPERS.fiolution of normethylnitropianic acid with tin and hydrochloric acid.It is dissolved in alcohol and precipitated with water. It crystallisesi n colourless, lustrous needles which melt at 174-175" with decom-position ; i t is readily soluble in alcohol, sparingly in benzene, andinsoluble in ether. When boiled with baryta, crystals of bariumnormet h ylamido hemi pinate are formed. The diacety I-d erivative,O&fe*C6H(OAc) (COOH)<NA:>, cooMe*C,H(oAc)(CooH)<,,>, co melting at 198'.is obtained by boiling normethyl-anhydramidohemipinic acid with sodium acetate and acetic anhydride(10 parts) for one hour.It melts a t 205", dissolves readily in ben-zene; the alcoholic solution has a fine blue fluorescence. It is veryunstable and changes when kept into the monacetyl compound,Normethy/nit?.opianic acid phenylh ydrazine crystallises in redneedles which melt a t 178-179" with decomposition. When boiledwith glacial acetic acid, it parts with the elements of water and yieldsnorrnethy Znitropiaxide, No2*C6H(0Me) (OH) < ca: : N->. Thelatter crystallises in lustrous, lemon-coloured, rhombic plates meltingat 191". I t dissolves unchanged in dilute potash solution.Thepotassium salt is very readily soluble in water, almost insoluble inabsolute alcohol. Normethy Zamido-opiaxide is obtained by boiling thenitro-compound suspended in ammonia with ferrous sulphate. Itcrystallises from alcohol in short, almost colourlesv prisms.CO*NPhNormethy1rritro~'anoximic acid,NO2*CsH(OMe) (OH)(COOH)*CH :NOH [ = 6 : 4 : 3 : 2 : 11,is formed b;j- mixing a boiling solution of normethylnitropianic acidin water (40 parts) with an aqueous solution of hydroxylamine hydro-chloride and sodium acetate. It crystallises from alcohol in lustrousyellow needles which become brown when warmed, and melt at 252".It has a slight reducing action on Fehling's solution. It dissolves inalkali with SL deep-red colour, and the solution gives off ammonia,when boiled, with formation of normethylnitrohemi~inic acid,NO,*C,H(OMe) (OH)(COOH), [ = 6 : 4 : 3 : 2 : 11.The latter crys-tallises from alcohol in almost white, silky needles, readily soluble inwater and alcohol; it melts at 220". The hydrogen potassium saltforms bright yellow prisms. The same acid is formed when nor-methylhemipinic acid is nitrated with dilute nitric acid,Normethylnitrohemipinimide, N02*C6H( OMe) (OH) <C CO.0- H)>, isobtained by boiling an alcoholic solution of normethylnitropianic acidwith hydroxylamine hydrochloride, or better by boiling normethyl-nitropianoximic acid with glacial acetic acid. It crystallises in brightyellow needles which melt a t 252" with decomposition.Homo-orthophthalimide. By S.GABEIEL (Ber., 19,2363-2367 ;compare Abstr., 1886, 812, and this vol., p. 61).-When a solutionof homo-orthophthalimide (2 grams) and potash (1 gram) in methylalcohol (15 c.c.) is digested with methyl iodide (4 grams) at loo",N. H. MORQANIC CHEMISTRY. 51dimethylhomo-orthophthalimide, CgH5Me2NO2. is formed. The lattercrystallises from water in flat needles melting at 119-120"; it isreadily soluble in the usual solvents and in alkali. When heatedwith potash and methyl iodide a t loo", it yields the trimethyl-derivative, CDHaMe3NO2 ; this cry stallises in long needles melting at102-103" : it is readilv soluble. Alkali does not dissolve it.CH G O Howio- ort hophthalmeth y limide, C&< .kMe > , is formed byevaporating a mixture of homo-orthophthalic acid and methylamine,arid distilling the residue.It forms long, colourless needles, whichmelt a t 123" and boil at 314-318". I t is readily soluble in the usualsolvents and dissolves in alkalis. When heated with methyl iodideand potash, it yields trimethylhomophthalimide melting at 102-103".In the latter compound, therefore, one of the methyl-groups isattached to nitrogen. Trimethylhomophthalimide is hardly attackedby fuming hydrochloric acid at 100", and so cannot contain methoxyl;when heated with the fuming acid a t 230-240", the anhydride of a co This crystallises in flatcrystals melting at, 82.5-83" ; the silver salt, Cl1HI6OkAg2, was pre..pared. The anhydride is also formed when dimethylhomophthalide(fi-om homophthalide, potash, and methyl iodide) is heated a t230" with fuming hydrochloric acid; ammonia is formed in thereaction.Tri- and di-methylhomophthalimide and the anhydride (m.p.82.5433") have probably the constitution expressed in the formula-, bibasic acid, C,H,Me,<CO>O, is obtained.Action of Amines on Phthalylacetic Acid. By E. MERTENS(Bey., 19, 2367--2373).--Pure phthalylacetic acid is stiriaed withwater and treated with a 33 per cent. solution of ethylamine until itis dissolved ; it is then filtered and saturated with hydrogen chloride,being kept cold the whole time. A white crystalline substancegradually separates with ,slight evolution of carbonic anhydride,Analyses show the compound to have the formula C~~&,O~NZ.Itmelts at 129", dissolves readily in warm alcohol, ether, and chloro-form, more sparingly in benzene ; boiling water decomposes it.2Methylei~eyphthalethimidine, CO< z g i > C CHz, is formed when thecompound C,H,,O,N, is heated above its melting point ; carboriioanhydride and water are evolved. It has a carrot-like odour, distilswith steam, and is readily soluble in alcohol, ether, and chloroform,&c. It strongly resembles Gabriel's methylenephthalomethimidine(Abstr., 1885, 1228).Phthalethimidylacetic acid, C@< %g(>C : CH-COOH, is obtainedby keeping a solution of the compound C,H24N205 in sulphuric acid(10 parts) for 24 hours, and then pouring it into water. The whitecrystalline precipitate is crystallised from dilute alcohol, from which iteC52 ABSTRACTS OF CHEMICAL PAPERS.separates in yellow needles melting a t 180" with effervescence.It isreadily soluble in hot water, alcohol, and ether, less soluble inbenzene. The silver salt forms a flaky crystalline precipitate; thebarium saZt crystallises in yellow lustroufi needles. Propylamine andphthalylacetic acid yield the compound C,,H,,O,N,. It forms largewell-formed prismatic crystals which melt with effervescence a t 103".It behaves similarly to the ethylamine compound.Acetophenone-orthocarboxa.,7iZideJ COMe*C6H4*CO*NHPh, is obtainedby warming phthalylacetic acid with aniline. After the evolutionof carbonic anhydride has ceased, the whole is left for 24 hours,when the substance separates in white crystals.It crystallisesfrom benzene in large, well-formed cubes which melt at 189-192", and dissolve readily in warm alcohol, ether, or chloroform.When heated a t 204" and afterwards a t 2.30". it is converted withevolution of aniline and water into rnethylene~hthal~~enimiLJine,CO<::~>C CH,. The latter crystallises in yellowish prismsreadily soluble in alcohol, ether, and chloroform; it melts at 100".When acetophenonecarboxanilide is kept dissolved in strong sol-sulphuric acid for 24 hours, it is converted into a compound, C16H11N0,isomeric with the compound just described. It is sparingly soluble inalcohol and ether, readily in benzene, chloroform, and light petroleum ;it melts at 265". N. H. M.Bromoterephthalic Acid. By M. FILETI (Gaxzetta, 16, 284-287).--Pischli (Abstr., 1879, 639) states that the monobromotere-phthalic acid obtained by the oxidation of bromotoluic acid retains1 mol.H,O, even after drying a t 120". As the same acid obtainedfrom bromocymene was found to be anhydrous, the author hasrepeated Pischli's experiments. The analytical results obtained forthe proportion of carbon and bromine show that this acid is alsoanhydrous. Itssilver salt is precipitated as a white, gelatinous mass, somewhatsoluble in water. The methyl saZt, C6H,Br(COOMe)2, obtained fromthe said chloride (Fischli), as also from the acid itself (Fileti), crystal-lises in acicular prisms, melting at 5 2 " ; it presents a well-markedchromatic polarisation. V. H. V.It melts a t 296", and at the same time sublimes.Curnidic Acids. By E.SCHNAPAUFF (Ber., 19, 2508--2511).-Theauthor prepared a-cumidic acid,C6H&fez(GOf)H,), [Me : Me : COOH : COOH = 1 : 3 : 4 : 61,by a modification .of Wurtz's process, by the action of efhyl chloro-carbonate and sodium amalgam on dibromometaxylene, This acidforms glittering prisms melting much above 320"' and subliming withonly slight decomposit,ion. It is easily soluble in boiling alcohol, verysparingly in boiling water. Its barium salt crystallises with 1+ mol.H,O, and is very soluble in water: the methyl salt forms long needlesor plates and melts a t 76".Cumidic acid, obtained as described by Jannasch (this Journal,18'71, 240) by the oxidation of durene, was converted into the methyORQANIC CHEMISTRY.53salt, and this by crystallisation from alcohol was separated into twoparts, the one melting a t 76" the other crystallising in needles and.melting at 114". The former was the methyl salt of the a-acid j u s tdescribed. The ether melting a t 114" yielded @-cur/lidic acid[Me : Me : COOH : COOH = 1 : 4 : 2 : 51 on hydrolysis. This acidis easily soluble in boiling alcohol, very sparingly in boiling water ; itrr\-stnllises in hexagonal prisms, and sublimes at high temperatureswithout previous fusion. Its barium salt crystallises with 24 mols.H20; its methyZ salt melts at 114" and boils at about 297" (corr.).When the barium salt is distilled with excess of lime, paraxylene isformed, so that the above formula may be regarded as established.Jannasch's acid is, therefore, a mixture of two isomeric cumidioacids.L. T. T.Reaction of Stilbene. By (3. ERRERA (Cazzetta, 16, 325).-Kade(Abstr., 1880, 46) states that stilbene in alcoholic solution gives a redcoloration when heated with a solution of ferric chloride. It is hereshown that this change is in reality due to the presence of water inthe alcohol, which causes a partial decomposition of the ferricchloride into hydrochloric acid and some stable form of ferrichydroxide. Stilbene is not even necessary for the reaction ; if absolutealcohol is used no colour-change ensues.By T. ZINCKE (Ber., 19, 2493-25Q2) .-Inthe hope of elucidating the constitution of the two compounds,C3,H,,N,0s and CB1HP2NCOG (Abstr., 1882, 736, and 1883, 210), ob-tained by the action of nitrous acid on P-naphthaquinone-anilide and-toluide respectively, the author has undertaken similar investigationswith phenanthraquinone.I n the present communication, the authordetails some preliminary experiments as to the action of alkalis onhalogen-derivatives of /I-naphthaquinone, which were made to deter-mine whether @-naphthaquinone-deriva tives undergo changes similart o the conversion, by the action of alkalis, of phenanthraquinone intodi phenyleneglycollic acid.theaction of bromine in acetic solution on p-naphthaquinone, and crystal-lising in red prisms melting at 177-178", dissolves readily in coldtlilute alkalis. From these solutions, acids precipitate hjdroxybromo-/3-naphthaquinone, described by Merz and Baltzer.Aniline and am-monia also act on bromo-/j-naphthaquinone, forming corn poundsanalogous to naphthaquinoneanilide. Dibrorno - /3 - naphthayuino,he,[0 : 0 : Br : Br = 1 : 2 : 3 : 41, could not be obtained directly fromnaphthaquinone, but was formed by the action of excess of bromineon an acetic solution of the monobromo-derivative. It is best ob-tained, however, by the action of bromine on a-amido-p-naphthol. Itcrystallises in red: rhombic scales or tables, sparingly soluble in;~lcohol and ether, and melts a t 172-174". With ammonia andaniline, it yields the same compounds as the monobromo-derivative.It dissolves in cold dilute alkalis, and from these solutions acidsIrecipitate a substance, crystallising in small white needles ; this hasnot beeu further investigated.V.H. T.p-Naphthaquinorre.Rro.rrLo-@-nuphthaqIcinone, [0 : 0 : Br = 1 : 2 : 31, obtaine54 ABSTRACTS OJ!' CHENICAL PAPERS.ChEoro-P-naphthaphone, [0 : 0 : C1 = 1 : 2 : 31, is formed whenchlorine is passed through a solution of p-naphthaquinoiie in tentimes its weight of glacial acetic acid, until a precipitate begins to beformed. It crystallises in red needles, soluble in alcohol, glacialacetic acid, and benzene, ahd melts a t 172". It gives an additiveproduct with hydrochloric acid which forms white cr,ystals. Itdissolves in dilute alkalis, and this solution when acidified yieldshydroxychloro-a-naphthaquinone. The unstable p- hydroxy-compoundundoubtedly first formed passes into the more stable a-derivative.When chloro-P-naphthzquinone is reduced with sulphurous acid i nacetic solution, chloro- p - naphthapuinol, C,H,Cl(OH),, is formed,and crystallises in long, colourless needles melting a t 116-117".The anilide and imide of chloro-p-naphthaquinone both crystnllisein dark-coloured scales having a metallic lustre, the former substancemelting a t 253", the latter at 260".Dichloro-p-naphthczpi~inzone, [0 : 0 : C1 : C1 = 1 : 2 : 3 : 41, may beobtained directly from the quinone, but is best prepared by the actionof chlorine on a-amido-p-naphthol.It crystallises i n red scales,needles, or tables, easily solnble in chloroform and boiling benzene,sparingly in alcohol, melts a t 184", and sublimes without decom-position.With ammonia or aniline, it forms the imide or aniliderespectively. When reduced with sulphurous acid in acetic solution,it yields dichloro-/3-naphthaquinone, crystallising in white needleswhich melt a t 125". Ik dissolves in cold dilute alkali, and thisEolution when heated becomes cloudy, and deposits a greyish-whiteprecipitate. If the cold alkaline solution be treated with excess ofacid, an acid of the formula C,H,Cl?03 is liberated. This acid crys-tallises with 1 mol. H20 in small white needles, melts a t 98-100",and is easily soluble in alcohol, sparingly so in water. Its methyZsmZt forms colourless scales or hexagonal plates melting a t 13'7-138".The action of the alkali on the dichloroquinone appears to take placeaccording to the equation C,oH4Cl,0, + H,O = CloH,Cl,O,.Theauthor considers the action to be similar to the action of alkalis onphenanthrsquinone, and the most probable constitution of the acid t ohe CCl<ccl:> C6 I3 C( OH)-COOH. The acid forms an ncety Z-dericative,melting at 75-76'. Boiling baryta-water or alkalis cause a separa-aion of carbonic anhydride. When a solution of the acid in glacialacetic acid is treated with concentrated sulphuric acid at 120", hydrogenchloride is evolved, and a yellow crystalline compound melting at224-226" is produced. The acid is decomposed on heating itsaqueous solution, a yellow compound of intense odour and volatile insteam being amongst the products of reaction.The experiments on the bromo-derivatives were carried out inconjunction with Weltner, those on the chloro-derivatives withC.Frolilich. L. T. T.Benzene- and Toluene-azonaphthols and their IsomericHydrazine-derivatives. By T. ZINCKE and I?. RATHGEN (Ber., 19,2482 - 2493). - W $en the two position-isomerides, benzeneazo-p-naphthol and P-napl -thaquinonehydrazide (see Zinckc and BindewaldORGANIC CHEJIlSTRY. 55Abstr., 1%35, 391), are reduced by means of stannous chloride, theformer yields a-amido-@-naphthol, the latter P-amido-a-naphthol.When a-amido-/I-naphthol is oxidised, P-naphthaquinone is formed,but the authors find that p-amido-a-naphthol yields under similarconditions P - diriaphthaquinone (/3 - dinaphthadiquinone). Bothquinones yield with bromine dibromo-p-naphthaquinone.When heated with nitric acid, benzeneszo-P-naphthol yields dinitro-P-naphthol, CloH5(OH)(N0,), [NO, : OH : NO, = 1 : 2 : 41, whilstp-naphthaquinonehydrazide yields dinitro-a-naphthol [OH : NOz : NO,= 1 : 2 : 41.Whenthe above isomeric hydraside and azo-compound are reduced in alkalinesolution, they are both decomposed into aniline and amido-naphthol.The author disputes the correctness of Denaro's assertion (Abstr.,1886, 246) that two isomeric benzeneazonaphthols can be obtainedfrom p-naphthol.The authors have also investigated the corresponding toluene-deriva-tives. Pitratolueneazo-a-naphthol, OH*CloH6*Nz*C7H7 [OH : N, = 1 : 41,was prepared like the similar benzene-compound. It crys tallises indark-red flakes having a metallic lustre, aud melts with decompositiona t 208".It is easily soluble in acetone, aniline, and alkalis, sparingly soin alcohol and acetic acid. No bromo-derivative could be obtained.Nitric acid yields dinitro-a-naphthol (b. p. 139"). The hydrochloridaand hydrobromide form bluish-green scales, which are slowly decom-posed by water, rapidly by alcohol. It also Eorms metallic derivatives.The ethoxide crystallises in red needles, which appear yellow bytransmitted light, and melt a t 126-127"; the methoxide melts a t103-104" ; the acetyl-derivative crystallises in yellow needles meltinga t 101-102". Orthotolueneazo-a-naphthol, [OH : N, = 1 : 41, formsred needles melting a t 144-146', soluble in alcohol, benzene, andncetic acid. It forms dinitro-a-naphthol with nitric acid, and yieldssalts resembling those of the para-compound. The sthoxide crys-tsllises in red scales melting at 94", the methoxide in reddish-brown needles melting a t 93".Para- and ortho-tolylhydrazides ofa-naphthaquinone are identical with the corresponding azo-com-pounds.Parato Zuene-@naphthol, ClOH~ON,H*C,H7, or C10H6 (0 H) *Nz*C7R7[0 : N, : : 2 : 11, forms red crystals with green flnorescence, is solublein alcohol, benzene, and acetone, and melts a t 134-135". It formsvery unstable salts with acids. The dibrorno-derivative forms intenselyred needles melting at 190". Nitric acid converts the azo-componndinto dinitro -P-napht hol (m. p. 194"). 0 rthotol ueneazo +-nap ht h ol,[O : N, = 2 : 11, crystalliscs in small red needles or scales which melta t 131".With nitric acid, it yields a dinitro-p-naphthol melting a t167". The tolylhydrazides of P-naphthaquinone are, like the similarphenylhydrazide, isomeric and not identical with the nzo-compounds.They resemble them, however, very closely, the chief difference beingtheir greater solubility i n alkalis. P-Naphfhaquinone-iuaratolylhydr-azide, CIOH60*N2H*C7H7 [0 : NP = 1 : 21, crystallises in small, red,glistening needles which melt at 145". The dibromo-dericative,CliH12B~-20, forms red, sparingly soluble needles melting at 236".B-NallhthapuinrJne-o~t~iotol~~li y draxide crystallises in red scales with aThe P-derivative melts at 1!34", the a- a t 138"56 ABSTRACTS OF CHEMICAL PAPERS.golden-yellow fluorescence. It is easily soluble i n the usual solventsand melts at 156".Its dibromo-derivative melts at 254". Besidesthese hydrazides, the product of the action of the tolylhydrazinc onthe p-naphthaq uinone always contained considerable quantities of di-naphthyldiquinol. L. T. T.New Diamidodinaphthyl. By P. JULIUS (Ber., 19,2549-2552).-am-Dinaphthyl is best prepared by distilling a-dinaphthol with zinc-dust (10-15 parts) : the distillate is re-distilled in a vacuum andrecrgstallised from glacial acetic acid.Mononitrodinaphthyl, C10H7*C10H6*N02, is obtained by adding nitricacid, of sp. gr. 1.3 (20 grams), to a solution of dinaphthyl (10 grams)in 150 C.C. of glacial acetic acid. It crystallises in lustrous, orange-coloured plates melting at 188". It dissolves easily in hot benzeneand glacial acetic acid, less readily in alcohol and ether.Dinitrodinaphthyl, N02*C10H6*C10~6*N01, is prepared by treating asolution of 10 grams of dinaphthyl in 150 C.C.of glacial acetic acidwith 80 grams of nitric acid, and then heating at 60". It crystallisesin bright yellow, volumiiious needles which melt at 280°, it dissolvesvery sparingly in benzene, xylene, and glacial acetic: acid, and ispractically insoluble in other solvents.Uiczmidodinaphthyl hydrochloride, ~H,*C,oH6~C,oH60NHz,2H~l, isprepared by treating 10 grams of the dinitro-compound, suspended in200 C.C. of glacial acetlic acid, with hydrochloric acid, and50 grams ofzinc-dust. It is readily soluble in water, sparingly in strong hydro-chloric acid ; when exposed to the air, it quickly becomes green.Thefree base could not be isolated. The diacety 1-derivatiue crystallisesin almost colourless needles which melt above 300" ; it is insoluble.When the hydrochloride is treated with ferric chloride, dark-brown,lustrous needles of diimidodinaphthyl h?ydrochloride, CZoH,,N,C1,, .areobtained ; this is reconverted by reducing agents into the diamido-compound. N. H. M.Tetrahydroxyanthraquinones. By E. NOAH (Ber., 19, 2337-2340) .-When metahydroxybenzoic and gallic acids (equal mols.)are heated with sulphuric acid (10 parts) for 20 hours at 170", twotetrahydroxyanthrapuinones, ClaHa( OH),O,, are formed, together withhexahydroxjanthraquinone. The product is extracted with alcohol,the solution evaporated to dryness, and the residue extracted withbenzene.The solution contains +now only one tetrahydroxyant hra-quinone. This crystallises in long, slender, red, lustrous needles,which do not melt at 350", and sublime with difficulty, becomingpartly carbonised. I t is readily soluble in alcohol, acetone, andglacial acetic acid, sparingly in benzene, xylene, &c. The solutionsin sulphuric acid and in caustic alkali are violet and emerald colouredrespectively. The tetracety 1-derivative crystallises in yellow micro-scopic needles, which melt with decomposition at 207-2U9". Thesecond tetrahydroxpnthraquinonc is extracted by means of dilutealcohol from the residue undissolved by benzene. It crystallises insmall, red needles which do not melt at 380" ; it sublimes in small,yeilow needles, but is mostly decomposed.It dissolves readily iORGANIC CHXMISTRT. 57alcohol, glacial acetic acid, and acetone, sparingly in ether and ~ a t e r .The solution in sulphuric acid is brownish-yellow; that in causticalkali emerald-coloured. The tetracetyl-compound crystallises in lemon-coloured prisms, which are very readily soluble in glacial acetic acid,alcohol, and chloroform ; it melts at 189". N. H. M.Methylanthragallols. By E. L. CAHN (Ber., 19, 2333-2336 ;compare Abstr., 1886, 556).-l-~Methylanthragallol,is prepared by heating orthotoiuic acid (3 parts) with gallic acid(2 parts) for 12 to 15 hours up to 130-135". It crystallises fromalcohol in gold-coloured flakes consisting of microscopic needles. Itsublimes in long, orange-coloured needles, and melts at 297-298"with decomposition.It is readily soluble in hot alcohol and glacialacetic acid, sparingly in benzene ; it also dissolves in hot water, yield-i n g a red solution. The triacety 1-derivative crystallises in sulphur-coloured microscopic plates melting at 208-210", readily soluble inchloroform, acetone, hot alcohol, &c. When methylanthragallol isdistilled with zinc-dust, a hydrocarbon, crystallising in white platesand melting at 197", is formed. When oxidised, it is converted intoa quirione melting at 278-2279".3-~etl~ylanthragallol is prepared in a manner similar to the abovecompound from paratoluylic acid. It melts at 275', and sublimes inorange-coloured needles. It resembles its isomeride.The triacetyl-derivative crystallises in well-formed, lustrous, golden prisms meltingat 203-208' with decomposition.2- Methyl- and 4-methy l-anthragallol are formed simultaneously frommetatoluylic and gallic acids. The separation of the isomerides isdifficult, and is best performed by converting the mixed product intothe acetyl-derivative and recrystallising repeatedly from glacial aceticacid. The one methylanthragallol has a slight golden lustre, andmelts at 31 2-313" ; the other crystallises in small, well-formedprisms melting at 235-5240". The acetyl-derivatives melt at 188-190"and at 217-218" respectively.The four methylanthragallols closely resemble one another andanthragallol. They are readily soluble in alcohol, and dissolve instrong and in dilute alkalis, yielding green and violet solutions respec-tively.The solution in hot ammonia has a fine blue colonr, in sul-phuric acid it is red; the latter changes to green on addition of atrace of nitric acid. The absorption-spectra of the red solutions ofanthragallol and of the methylanthragallols in sulphuric acid arealmost the same. N. H. M.Acid from Santonin : Isophotosantonic Acid. By S. CANNIZ-ZARO and G. FABRIS (Ber., 19, 2260-2265) .-Isophotosantonic acid,C15H3206, is obtained by exposing 1 kilo. of santonin dissolved in 52litres of acetic acid to the action of light for several months ; one-ninthof the acetic acid is then boiled off under diminished pressure, and th58 ABSTRACTS OF CHEMICAL PAPERS.residue filtered from the photosantonic acid which separates on cool-ing.A further quantity of photosantonic acid is precipitated byadding water. The solution is then nearly free from photosantonicacid and still contains almost the whole of the isorneride. It is treatedwith sodium carbonate (which dissolves the photosantonic acid alone)and extracted with ether. It separates from its alcoholic solution inthick, triclinic crystals, rather soluble in ether, and sparingly in water.When heated a t loo", it is converted into the lactone, C,,H,,O*. It isdextrorotatory, [a]= = f 3 24" 17'. Photosantonic acid has nearlythe same specific rotatory power, but is lsevorotatory. Isophotosan-tonic acid dissolves in alkalis and in warm solutions of alkalinecarbonates ; the solutions are orange-red.The barium salt,(C15H,106)2Ra + H,O, is an amorphous powder, readily soluble i nalcohol and in water. The monacetyl-compoimd crystallises fromalcohol in transparent needles which melt a t 183" ; it is dextrorotatory,[ a ] D = + 58" 16'. The diacetyl-cowpound is very sparingly soluble ;it melts a t 163-166". It is very unstable, and when often recrys-tallised changes to the monacetyl-derivative.The results ahove described point to the following constitutionalformule for the lactones of isophotosantonic and photosantonic acidsrespectively :-CH : CH*CH-CHMe*C(OH)zCH 1 CH*CH*CHMe*CH*CH<;?>CO I I andCH : CH*CH*CHMe*COOHCH CH* C H*C HMe*CH2*CH < :?> C 0.N. H. M.I ICinchol. By 0. HESSE (Annulen, 234, 375--379).-A furthercomparison of i he properties of cinchol and Liebcrmann's oxyquino-terpene or cliolestole (Abstr., 1885, 1075) confirms the author's pre-viously expressed opinion (Abstr., 1885, 1076) that these twosubstances are identical.They both melt at 115", and are identicalin crystalline form. The acetates melt at 1 2 4 O , and also exhibitidentical crystalline forms. w. c. w.Alkaloids. By 0. DE CONINCK (Contpt. rend., 103, 640-641.)-Piperidine methiodide gives no colour reaction with potassium hydr-oxide (Abstr., 1886, 897), and this difference furnishes a means ofdistinguishing between a pyridic base and its hexhydyide.Cicutine methiodide also gives no colour reaction, but the solutionacquires an amber tint. The reaction is always obtained with colli-dines, and therefore will most probably be given by conyrine, thecollidine of which cicutine is the hexhrdride.No similar colour reaction is obtained with the methiodides ofaniline, orthotoluidine, or metaxylidine.When methiodides of pyridicbases are mixed with a fragment of solid potassium hydroxidORGANIC CHEMISTRT. 59and sn6cient water to form a paste, and then heated, a peculiar odouris developed owing to the formation of pyridic dihydrides.No similar reaction is given by methiodides of pyridic hexhydrides,nor by the methiodides of aniline and its homologues. C. H. 33.Extraction of Pyrroline from Animal Oil. By G. L. CIAMICIANand M. DENNSTEDT (Gazzetfa, 16,356) .-Pyrroline may be extracted asthe potassium-derivative by using caustic potash instead of the metalas heretofore practised.The reaction is probably CIH,NH + KOH =C,H,NK + H,O; the excess of potash serving as a dehydratingagent. The fraction of the oil, freed previously from nitriles, whichpasses over at 125-140", is heated in an oil-bath with an excess offused pofash, using a reflux apparatus. At the conclusion of thercaction, the liquid separates into three layers, the heaviest of whichis the excess of potash, the next the potassium compound, and thelightest the unaltered hydrocarbons. On cooling, the potassium com-pound solidifies, and is washed with anhydrous ether. The substancethus obtained, distilled in a current of steam, yields pyrroline of boil-ing point 130-138' ; with chloroform, it yields chloropyridine(Abstr., 1881, 820).V. H. V.Pyridine Bases. By A. LADENBURG (Compt. rend., 103? 692-695 ; see also Abstr., 1884 and 1885).--a-MetlzyZ~yridine (picoline),C6NH7, is obtained in the form of hydriodide by heating p-j-ridinemethiodide at 300". The base boils at 138-129", and is miscible withalcohol and water ; sp. gr. a t 0' = 0.9656. It forms a characteristicmercuriochloride, C,NH7,HCI,HgC12, by means of which i t can beisolated in a state of purity; this compound is very soluble in hutwater, but only slightly soluble in cold water. p-MethyZpyridine isbest prepared by Zanoni's method of heating glycerol and acetamidewith phosphoric anhydride. I t boils a t 142" ; sp. gr. at 0" = 0.9771.The platinochloride crystallises with 1 mol.H,O and melts at 214" ;the aurochloride is anhydi-ous and melts a t 183" ; the mercuriochlorideis also anhydrous, melts a t 143", and forms slender needles which canbe crystallised from water. .y-iWethy@yridi?~e is formed only in smallquantity by the action of heat on pyridine mdhiodide; it boils a t144-145" ; sp. gr. at 0" = 0.9708. The platinochloride is anhydrous,melts a t 225", and is only slightly soluble in water. aa'-Dimethyl-pyridiite is isolated from the fraction of animal oil boiling a t 138-145" by means of the mercuriochloride, C7NH9,HCI,HgCl2, which canhe crystallised from water, and melts a t 183". When decomposed, ityields lutidine boiling at 142-143"; .sp. gr. at 0" = 0.9924. Theaurochloride forms yellow needles which melt at 124" ; the platino-chloride crptalliees in large monoclinic crystals isomorphous with/3-picoline platinochloride, although the former is anhydrous, whilstthe latter contains 1 mol.H,O. The picrate is only slightly soluble inwater and melts a t 159". When the base is oxidised, it yields a bibasicacid, C5NH3( COOH),, crystallising in beautiful needles which melt a t226", and at the same time decompose into pyridine and carbonicttnbjdride. oc-y-Dimefk$pyridine exists in large quantity in Dippel'60 ABSTkACTS OF CHEMICAL PAPERS,oil, and can be isolated from the fraction which boils at 1S5--160" byacidifying with hydrochloric acid and adding mercuric chloride. Theprecipitated mercuriochloride, 2(C,NHg,HC1,2HgC12) + HzO, is re-peatedly recrystallised, and forms beautiful needles which melt at129'.When decomposed, it, yields the base ; this boils at 157", and isonly slightly soluble in cold water, still less soluble in hot water.The platinochloride is somewhat solnble, crystallises readily, andmelts at 219-220'. The aurochioride, C7HgN,HL4uC11, is less solubleand does not crystallise so well. Thislu tidine is identical with the lutidine prepared synthetically byHantzsch. When oxidised, it yields lutidinic acid, which crystallisesin plates which melt at 235".a-Ethy7pyridine is the principal product of the action of a, hightemperature on pyridine ethiodide ; it boils at 150", is miscible withalcohol, but is only slightly soluble in water. The platinochloride issomewhat soluble in water, and melts at 168-170" ; the aurochloridemelts at 120" and crystallises readily from hot water; the picratemelts at 110".When the base is oxidised, it yields picolinic acid only.y-Ethykym'dine is also formed in smaller quantity by the action of heaton pyridine ethiodide, and is separated from its isomeride by takingadvantage of the comparative insolubility of its salts, especially theplatinochloride or ferrocyanide. The base boils at 163'; sp. gr. at0" = 0.9522. The plstinochloridie melts at 208", the picrate at 163",the aurochloride at 138". The ferrocyanide is precipitated even fromvery dilute solutions. When the base is oxidised, it yields isonico-tinic acid. a-y-DietkyZpyridine is also obtained in small quantity bythe action of heat on pyridine ethiodide ; it boils at 187-188", has a,disagreeable odour, and is only slightly soluble in water.When care-f u l ! ~ oxidised, it yields lutidinic acid which melts at 235".a-lsopropylpyridine, obtained by heating pyridine with propyl orisopropyl iodide at SOO", boils at 158-159", is slightly soluble inwater, and has a very disagreeable odour ; sp. gr. at 0" = 0.9342.The platinochloride, (C8Hl,N),,HZPtCI6, is somewhat soluble andmelts at 168" ; the aurochloride crystallises from dilute solutions inyellow plates which melt at 9l"and are only slightly soluble in water;the picrate forms yellow needles which melt at 116". When the baseis oxidised by potassium permanganate, it yields picolinic acid. y l s o -propyZppidipLe is obtained in smaller quantity by the same reaction,arid is separated by means of the platinochloride, which is only slightlysoluble in water, and melts at 203".The base boils at 177-178";sp. gr. at 0" = 0.9439.The picrate melts at 180".When oxidised, it yields isonicotinic acid.C. H. B.Quinoline. By A. CLAUS and F. COLTJSCHONN (Bey., 19, 2502-2508).-The authors describe a number of halogen additive productsof the propio-haloid compounds of quinoline. Quinoline propio-bromide is easily formed when its constituents are heated alone, orbetter, with alcohol, at 90-100". It is easily soluble in alcohol andwater, and crystallises from water in colourless plates containing2 mols. H,O, and melting at 66" ; from absolute alcohol, it separatesin anhjdrous crystals melting at 148".It is easily soluble in chloro-form, and horn this solutiou crystallises with 1 mol. CHC1, in quadratiORGANIC CHEMISTRY. 61prisms which cradually lose chloroform and become opaque, soften at65", and melt with evolution of chloroform a t 128-129". Quinolinepropiodide forms yellow anhydrous ctptals me1 ting at 145", andbecoming rapidly discoloured in the light. This also crystallises with1 mol. CHCI, in quadratic prisms which begin to evoke chloroform at92". Quinoline propiochloride cannot be easily prepared directlyfrom its constituents, but is best obtained by acting on the corre-sponding bromide with silver chloride. It is very soluble in water,and crystnllises in colourless prisms or plates containing 1 mol.H,Oand melting a t 95". The hygroscopic anhydrous salt melts at 135" ; italso crystallises with 1 mol. CHCI, in quadratic prisms melting a t 79".The additive products were obtained by treating a chloroform solu-tion of the propiohaloid salt with the halogen.Quinoline propiobroinide dibromide, CgNH,*PrBr?, forms glistening,red, triclinic crystals melting at 93". The di-iodide forms brownmetallic needles melting a t 60". The dichloride forms yellow scalesmelting at 60". The tetriodide, CgH,N*PrBrId, yields small, almostblack needles having a green fluorescence and melting at 49".Quinoline propiodide dibromide forms orange triclinic crystals melt-ing a t 77". The di-iodide forms thin, bronze-coloured scaleq meltingat 62".The dichloride forms yellow needles melting a t 87". Thetetrabromide, C9NH7*PrIBr4, is a very unstable orange-red powderwhich evolves bromine a t the ordinary temperature, and gave no con-stant malting point (48-58"). The tetriodide forms iodine-colouredplates melting a t 50'. The tetrachloridp crystallises in needles whichshow the high melting point 1 4 ~ 1 4 . 5 " . It is also formed whenquinoline propiochloride is treated with iodine trichloride, and maytherefore really he quinoline propiochloride iodide trichloride. Whenboiled with water, it is gradually decomposed into quinoline propio-chloride. Similar migmtion of the halogen-atoms may also verylikely take place in others of the mixed halo'id compounds.Qziinoline propiochloride dibromide forms orange crystals melting at84-85'.The &iodide melts a t 61-W. The dichloride is veryunstable and could not be obtained in a pure state. A tetriodideis easily formed, but could not be obtained in a pure state.All these additive compounds decompose when heated a t 250-200",prop91 haloid salts, quinoline haloid salts, and halogenispd andalkglated quinolines being amonget the products of decomposition.These decompositions are being studied. All the above temperaturesare uncorrected. L. T. T.Isoquinoline and its Derivatives. By S . GABRIEL (Ber., 19,2354--2363 ; compare Abstr., 1886, 812) .-Dichlorisopuinoline,CH: CC1C"""&y: N 2,is prepared by heating homo-orthophthalimide (8 grams) with phos-phorus oxychloride (24 grams) for three hours a t 150-170".Theproduct is poured into alcohol ( 5 vols.), the mass of crystals soobtained treated with soda until alkaline, filtered. and recrystallisedfrom alcohol. It is readily soluble i n hot alcohol, cold chloroform62 ABSTRACTS OF CHEMICAL PAPERS.ether, and benzene; it boils at 305-307". The alkaline mother-liquor obtained in the preparation of this compound, when treatedCCl : N >' with hydrochloric acid, yielded the cldoro-derivutive C6H4< CH,*COor C6H4<~CH1_C"0H'> ; this crystallises from boiling alcohol in longneedles melting at 195-197" with evolution of gas. It is rathersoluble in hot alcohol, sparingly in hot benzene and in chloroform ;it dissolves in alcohol, but not in ammonia. The methyl-cornpoun,d,C,H5MeClN0, is obtained by dissolving half a gram of the substancein methylalcohol (10 c.c.), adding methyl iodide (2 grams), and heat-i n g a t 100".It forms slender, white crystals, readily soluble inalcohol, ether, benzene, &c., insoluble in alkali. It melts at 66-67',and has an odour of fruit.Chlorisopuinoline, C6H1< CH CH:N ' '">, - is obtained by reducing thedichloro-compound with phosphorus and hydriodic acid at 150-170", or with tin and hydrochloric acid. It melts at 47-48', andboils at 280-281" under 753 mm. pressure, and is readily soluble.Methoxy pheiilJlclzloriso quinoline, C"H4<C(oMe) : N>, is formedwhen phenyldichlorisoquinoline (1 gram) and sodium methoxide areheated for three hours at 100". I t crystallises from alcohol in needlesmelting a t 76", readily soluble in ether, benzene, &c.It dissolvesalso in strong hydrochloric acid, but is precipitated by water. Whenheated with fuming hydrochloric acid at loo', it is conyerted, withevolution of methyl chloride, into the compound C16H&1N0, probablych!orisobenzuZ phthliinidine, C6HH'<Co.~H->. It crystallises fromalcohol in slender, lustrous needles, melting at 211-212", moderatelysoluble in ether and cold alcohol, readily in glacial acetic acid, ben-ztae, &c. The formation of this compound is analogous to that ofisobenzslphthalimidine from phenylethoxyisoquinoline (Abstr., 1886,631).Ethozychlorisoquiil.oline, CeH4<g$YgCk>, is prepared by heatingdichloroisoquinoline with alcoholic soda at 100".It forms readilysoluble needles melting at 37-37.5".The methoxy-derivative, CloH8XOC1, is prepared in a, similar manner.It melts a t 73-74", and is isomeric with the methyl-compoundobtained from chloroxy quinoline. When heated at 150" in a currentof dry hydrogen chloride, it is converted into oxychlorisoguinoline,C,H4<gt.&!!>. This crystallises from dilute alcohol in slenderneedles melting at 218-220' ; i t dissolves rather readily in ether,easily in alcohol and chloroform ; it is also readily soluble in diluteaqueous soda. The methylderivative, c6H4<gg.&z:>, crydxdlisesin long, broad needles which melt at 111-112" ; it is readily solnble.c)xy chlorisoquinoline is formed in small quantities in the preparationof ethoxychlorisoquinolhe.CC1: CPh -CC1' CPORGANIC CHEMISTRY.63Isoquinoline is conveniently prepared by heating dichlorisoquinoline(3 grams), and hydriodic acid, sp. gr. 1.96 (18 c.c.) for five hours at230". The product is treated with alkali, and steam distilled ; thedistillate being treated with hydrochloric acid and again steam dis-tilled to remove the unchanged chloro-base. Isoquinoline melts at20-22", and boils at 236-236.5". The ethiodide crystallises in gold-coloured plates melting at 147-148", readily soluble in water and inwarm alcohol. N. H. M.Synthesis of Hydroxyquinolinecarboxylic Acid. By E. ,LIPP-MANN and F. FLEISSNER (Ber., 19, 2467-2471) .-Unlike ordinaryphenol-derivatives, the potassium compound of orthohydroxyquinolineis not acted on by carbonic anhydride even at 300".When, however,nascent carbonic anhydride (obtained by the action of potash oncarbon tetrachloride) is employed, action takes place. Orthohydroxy-quinoline, carbou tetrachloride, and caustic potash are mixed in alco-holic solution in the proportions necessary for the equation C9NH7U + CCI, + 6KHO = 4KC1 + C9NH5(OK)*COOK + 4H20, and the~ h o l e boiled for 12 hours. The product contains hydroxyquinoZine-ccirboxylic acid, OH.C,NH,*COOH, which when purified crystallisesin yellow prisms melting at 280". ?'his acid agrees in its salts and inall its properties, save melting point and oxidatiou products, with thea-hydroxycinchonic acid (m. p. 254-256") obtained by Weidel andCobenzl from sulphocinchonic acid (Abstr., 1881, 742). The acid issparingly soluble in the ordinary solvents. It dissolves in dilutehydrochloric acid to form a hydrochloride, which is precipitated on theaddition of concentrated hydrochloric acid in the form of glisteningneedles. The platinochloride forms unstable, bright yellow needles.The acid forms a normal barium salt, the pale yellow solution ofwhich, on the addition of baryta-water, yields white needles of thebask barium salt CloNH,BaO3 + H,O ; these only part with their waterof crystallisation at 140-150". The silver salt is precipitated in theform of pale lemon-yellow flocks, which soon change to microscopicneedles. The aqueous solution of the acid gives a green colorationwith ferric chloride, but none with ferrous sulphate. When subjectedt o dry distillation, the acid yields orthohydroxyquinoline.When oxidised by potassium permanganate in alkaline solution, theacid yields a pyridinedicarboxylic acid, C,NEIQ04, forming brightyellow crystals melting at 234-235". With ferrous sulphate, it give8a blood-red coloration, and forms a silver salt which is gelatinous whenfirst precipitated, but soon becomes crystalline. This acid is probablyidentical with Bottinger's pyridiuedicarboxylic acid, and isomeric withWeidel's isocinchomeronic acid.Weidel and Cobenzl's a-hydroxyvcinchonic acid, when similarlyoxidised, yields a-pyridinetricarboxylic acid. The authors are furtherinvestigating this subject.By 0. FISCHER andH. VAN Loo (Ber., 19, 2471--2476).--This is a continuation of theauthors' previous work (Abstr., 1884, 1372). When P-diquinoline isheated with ethyl iodide in closed tubes at 90-loo", P-diquinolirbeL. T. T.Peculiar Formation of 6-Diquinoline64 ABSTRACTS OF CHEMICAL PAPERS.ethiodide, Cl,N2H12EtI, is formed in long, ruby-red crystals. It is veryunstable, and is decomposed by water and by boiling alcohol. Rodiethiodide could be obtained. When bromine is allowed t o act onP-diqiiinoline in chloroform solution, a tetrabromc-additive product,CI,N2H,,Br4, is produced. This crystallises in pale yellow needlesmelting at 192", and is decomposed at once by sulphurous acid,diquinoline sulphnte being formed. /3- DiquinolinedisuZphonic acid,ClsN2H,,(S03H)2, is produced when P-diquinoline is heated with alarge excess of fuming sulphuric acid. It is very soluble in water,and is precipitated from this solution by a mixture of alcohol andether in yellowish flocks. Its potassium salt crystallises from 50 percent. alcohol in glistening white prisms containing 3 mols. HzO. Theanaquinolinecarboxylic acid described in the former paper (loc. cit.),as obtained by the oxidation of the base by chromic acid in aceticsolution, is undoubtedly identical with that lately obtained by Skraupand Brunner (m. p. 247"). The melting. point previously given bythe authors was obtained from a sample crystallised from benzene ;when crystallised from water, it melts at 248-249". The author con-siders this acid to be metaquinolinecarboxylic acid, and that thename anaquinolinecarboxylic acid should be transferred to the acidmelting at 357O, and hitherto designated metaquinolinecarboxylic acid.If chromic acid is dissolved in sulphuric acid in place of aceticacid, the oxidation takes place in quite a different way. Under thesecircumstances p yridy 7quinolinecarbon: y Zic acid, C,NH,*C,NH,.C OOH,i8 formed. This crystallises in glistening needles, which melt withdecomposition at 271-273". It is sparingly soluble in water, easilyin alcohol, and forms salts both with acids and bases. The silver saIt,when heated, yields a p y r i d y lqzcinohe, C14N2H10, which crystaliises inwhite needles melting at 104", and gives a reddish-yellow crystallineplatinoch lorid e.Piperidine Bases. By A. LADENBURG (Compt. rend., 103, 747-74{9).-The bases are obtained by treating boiling alcoholic solutionsof the corresponding pyridine bases with a large excess of sodium.Piperidine obtained in thh way is identical with the base preparedfrom piperine. a-Methylpiperidine or a-pipecoliqe boils at 118-119",has the same odour as piperidine, and dissolves readily in water;sp. gr. at 0" = 0.860. The hydrochloride is very soluble, but notdeliquescent, and melts at 189". The hydrobromide is less soluble,and forms confused needles which melt at 182" ; the platinochloride isvery soluble. With carbon bisulphide, the base yields a thiocarbamate,CS2,'2C6HI3N, which crystallises readily, melts at 118", and is analogousto that! formed from piperidine. p-Methylpiperidine or P-pipecolineboils at 125", and dissolves readily in water; sp. gr. at 0" = 0.8684.The hydriodidc crystallises in beautiful, non-deliquescent needles,which melt at 131". It combines with cadmium iodide, forming thecompound Cd12,2C6H13NHI, a wbite precipitate soluble in warm water,from which it crystallises in white tables melting at 145". Theplatinochloride is somewhat soluble, and forms orange prisms meltingat 192" ; the aurochloride is very soluble, and melts at 231" ; the picratenielts at 136". aoc'-Dimethy~~peridinR or aa'-lupetidine boils at 128-L. T. TORGANIC CHE_1IISiTlZI'. 6 5130", and is very soluble in water and alcohol ; sp. gr. at 0" = 0.8492,The hydrochloride and hydrobromide crystallise in non-deliquescentneedles ; the platinochloride forms large orange crystals which melta t 212". ay-Dirnethypip~ridz'ne boils at 141", has an odour of piperi-dine, and dir,solves readily in water, though not in all proportions :sp. gr. a t 0" = 0.8615. The hydrochloride crystallises in beautifulneedles which melt a t 235" ; the hydrobromide is even more soluble ;the platinochloride is not very soluble, and crystallises in nodules ;the aurochloride is an oil. a-Ethylpiperidine boils at 143", and dis-solves slightly in water, but separates from the solution on heating,and has an odour resembling that of piperidjne and coniciiie ; sp. gr.a t 0" = 0.8674. The hydrochloride forms non-deliqiiescent crystals ;the platinochloride cryst,aliises in large tablea which melt a t 178".The methyl-derivative boils at 143-152"; sp. gr. at 0" = 0.8495.~,-.E&yZpiperitline boils at 1 -57", has a disagreeable odour, is onlys,lghtly soluble in cold water, and still less soluble in warm water ;sp. gr. a t 0" = 0.8795. The hydrochloride is deliquescent ; the platino-chloride forms yellow tables which meltl at 170-173" ; the auro-chloride crystallises from warm water in lamella which melt a t 105".a- IsopropyZpiperiditLe boils at 160-162", and is slightly soluble inwater, but separates from the solution when gently heated ; sp. gr. a t0" = 0.8676. Its odour and its properties generally resemble those of itsisomeric-le, conicine, but it is much less poisonous. The platinochlorideis much less soluble in water. and is not soluble in alcohol or ether ; i tmelts a t 193" ; the hydrochloride melts a t 240", the hydrobromide a t230", the hydriodide at 24 Lo. All these derivatives crgstallise readily.The iodide combines with cadmium iodide, forming a slightly solubledouble salt, which crystallises readily and melts at 132". The picrateand aurochloride crystaUise readily, and are only slightly soluble.With carbon bisulphide, the base yields a crystalline compound,CS (C,H,,N)SH,C,H1,N, which melts a t 105", dissolves readily inalcohol, but is only slightly soluble i n water. The methrl-dvivativeof or-isopropy~piperidine boils a t 166" ; sp. gr. at 0" = 0 85P3. Itshydrochloride is extremely soluble in water ; the aurochloride formsshining lamellae, and is also very soliihle in water ; the platinochlorideis somewhat soluble, and melts a t 100" ; the picrate crystallises readily,and nielts a t 149". ry-Isop,.opyZpiperi~~//e boils at 168-171", dissolvesslightly in water, and has a very disagreeable odour. The hydro-chloride crystallises, but is not stable in moist air ; the platinochlorideis crystalline, and is only slightly soluble in water, but dissolves inalcohol and ether, arid melts at 172"; the aurochloride is also crgstal-line, and only slightly soluble.Method of Preparing Extracts of Pepsin. By W. PODWYSSOZKI( P J ~ g p r ' . c A T C ~ L ~ U , 39, 62-74). -If the gastric mucous membrane ofcarnivora and herbivora be placed in glycerol almost immediatelyafter death, very little pepsin is extracted.Ebstein and Grutzner state that glycerol dissolves pepsin only, butthe author finds that a certain amonut of pepsin precursor, or as het,c.rmq it " propepsin," is dissolved also.Mucous membrane exhausted with glycerol still yields an importantC. H. B.VOL. 1.11 66 ABSTRACTS OF CHEMICAL PAPERS.amount of pepsin when treated with hydrochloric acid or hydrochloricacid and glycerol. It appears, therefore, that gastric mucous mem-brane contains two propepsins, one soluble in glycerol, the otherinsoluble.I f the mucous membrane is kept in a warm place for 24 hoursbefore it is extracted, a much larger yield of pepsin is obtained,provided no putrefaction has set in.Hydrogen and carbonic anhydride have no influence on the forma-tion of pepsin, but oxygen, on the other hand, appears to favour itsdevelopment ; more pepsin is formed when the mucous membrane isallowed to remain in contact with oxygen than when it is in contactwith air.Chlorine gas passed through any extract entirely destroys theferment. J. P. L.Comparative Estimation of Preparations of Pepsin. By .A.A. LIPSKI (Russlcayrc Medifsiiza, 35,583-584).-The powdered pepsinswere examined by digesting 0.2 gram of the preparation with 10grams of white of egg and 100 C.C. of hydrochloric acid (0.25 percent.) for four hours at 40". The undissolved albumin being thendetermined, the weight of this in grams was :-Perret acidifih 8.756,Marquart 8 577, Lamatch 8.557, Merck 7.213, Boudault neutre (No. 4)2 62, Witte 2.195, Boudault acidifit5 1.2, Russicum solubile (of theRussian Ph.) 0.721, do. do. recent 0.47, do. do. without the sugarcontained in the official preparation 0.157. The Russian pepsin is,therefore, far more active than any of the German or French pre-parations tested. The same holds good for the pepsin wines