ORGANIC CHEMISTRY. Organic Chemistry. Ethene Chlorhydrate. By A. LADENBURG and E. DEMOLE (Deut. Chem. Ges. Ber. vi 1023-1024). BYheating this compound with acetic anhydride in sealed tubes to 110' it is converted into ethene acetochlorhydrate which compound has already been obtained by Simpson and Lourenqo by a different reaction. c. s. New Derivatives of Propyl (continuation see this Journal [2] xi 871). By A. CAROURS (Compt. rend. lxxvii 745-750). Pro23yZ 0xaZate.-When anhydrous propyl alcohol is distilled wit11 dry oxalic acid mixed with one-third of its weight of sulphuric acid a colourless limpid liquid condenses in the receiver. Water separates this into two layers. The upper layer is washed first with sodium ABSTRACTS OF CHEMICAL PAPERS.carbonate solution and then with water and finally dried over calcium chloride. By rectification the product yields a very limpid colourless liquid having an aromatic odour recalling that of ethyl oxalate. Its sp. gr. at 22" = 1.018. It consists of p~qiyloaalate C,0z.(OC3H~)~. It boils at 209"-211". An aqueous solution of ammonia converts it into oxamide. Alcoholic ammonia if not in excess does not,give with it any precipitate of oxamide but on evaporating a crystalline body is obtained consisting of propyZ ommate C2O2(NHz) OC3H,. This sub- stance when heated in a tube melts to a colourless liquid and gives off vapours which condense in the form of slender prisms. P~opylCarboaate.-The action of sodium upon propyl oxalate is analogous to its action upon ethyl oxalate the product being yropyl carhowate CO(OC3H,)2 which is a colourlcss limpid liquid boiling at 156"-160" and having 8 specific gavity of 0.968 at 22".Its odour is somewhat like that of ethyl carbonate. Roiling concentrated potash- solution converts it into propyl alcohol. With an aqueous solution of ammonia or more rapidly with an alcoholic solution it is converted at ordinary temperatures into prop31 uretha'ize which crystallism in prisms. Propyl Xa;ZicyZate.-This compourzd is formed when a mixture of propyl alcohol salicylic acid and oil of vit)riol in the proportion of 2 parts of each of the first two to 1part of the third is submitted to distillation An oily liquid is condensed which is washed with water containing sodium carbonate to free it from a small quantity of sulphurous acid.It is then washed with water dried over calcium chloride and rectified. Propyl salicylate C7H6O2.OC3W7, thus formed is a colourless limpid liquid having a high refractive index. It has an aromatic taste and an odour resembling that of methyl saticylate. Its sp. gr. at 21" = 1.021. It boils at 238"-240. It is slightly soluble in water and freely soluble in alcohol and ether. Like its methyl and ethyl homologues propyl salicylate forms crystalline compounds with alkalies. It behaves also like its homologues when heated with anhy- drous baryta. Chlorine and bromine act energetically on propyl sali- cylate producing well-marked crystalline bodies. Fuming nitric acid added in small portions at a time elevation of temperature being avoided converts it into propyl witrosalicylate or indigotate which is a heavy yellow oil.If the nitric acid is added in excess and the whole is boiled crystals of picric acid are formed. An aqueous solution of ammonia converts prop91 salicylate into salicylamide. Prop$ Phenate.-Propyl iodide is heated for several hours at 100" -110" in a closed vessel with potassium phenate in alcoholic solution. Ou. adding water to the contents of the tubes when the reaction is over an oily liquid is separated which is to be washed first wit11 alkaline and then with pure water and rectified. Propyl phenate C6H,.0C3H, thus produced is a colourless very mobile liquid having the odour of ethyl phenate. Its sp.gr. at 20" = 0.968. It boils at 190"-191". It is attacked by bromine added in excess with the aid of heat colourless crystals being formed. Fuming nitric acid also acts upon it with energy producing at first an indigo and then a reddish-browu colour the liquid then becoming lieavy and oily on addition of water. If the acid is added in excess and heat is applied the oily liquid formed on ORGANIC CHEMISTRY. addition of water is of a yellow colour. Sulphuric acid converts propyl phenate intlo a sulpho-acid. P~opyl;Nitrite.-Wben nitrous acid formed by the action of nit'ric acid on starch is passed into propyl alcohol the whole being kept cool the vaponrs are immediately absorbed. On addition of water an oily liquid separates which after the process of purification employed with the compounds above described yields propyZ nitrite NO.OC,H7.This is a colourless very mobile liquid boiling at 43"-46". It burns with a yellowish flame. Like ethyl nitrite it has the odour of apples. Its sp. gr. at 21 = 0.935. B. J. G. Derivatives of Normal Propylic Alcohol. By H. ROEMER (Deut. Chem. Ges. Ber. vi 1101). TRIPROPYLAKIWE boils at 144Q-1460 and has a less powerful ammo- niacal odour than monopropylamine and is less soluble in water. Phosgene gas acts on propylic just as on ethylic alcohol ; the chZoro-carbonic propyZ-ethei- formed boils at 120"-130" ;when it is treated with water or aqueous ammonia pyopyl carboNate is formed but the best way of preparing this substance is to act on prop91 chlorocarbonate with sodium propylate.Propyl carbonate is a light liquid boiling at 160'-165". Aqueous ammonia acts on propyl chlorocarbonabe forming propyl carbamate ; t#his urethane is verv soluble in ether and alcohol less so in water. ' It melts at 50". " Similarly propyl; yhenyZ-c&rbarnate, { Z5sH5 CO is obtained by the action of aniline ; this compound melt; at 570-59". Attempts to prepare propylised aniline and propyl-sulphocarbimide met with little success. C. R.A. W. On the Sugar of Couch-grass Root and Triticin. By HERMANN MU LLER (Arch. Pharm. [3] ii 500). THEauthor concludes that the root of couch-grass (Friticum repens) contains no dextrose and no cane-sugar as the extracted sugar exhibited no tendency to crystallisation and gave a molecular rotation- [a]y = 54"to the left which was scarcely altered by heating with diluted sulphuric acid the value 53.9" to the 'left being thus obtained.In a former paper the author stated that by treatment with milk of lime a small quantity (0.437 gram) of a dextro-rotatory feebly-sweet tasting substance was isolated and this was then viewed as dextrose ; but he now finds on examination of larger quantities that this body consists of a small quantity of laevulose calcium chloride and calcium malate. Keither is lactic acid a normal constituent i.e. it is not present as such in the root but is formed by fermentative changes in the extract of the root on kecping. ABSTRACTS OF CHEMICAL PAPERS. The sugar present in the root is considered by the author to be solely fruit-sugar as when freed from gummy matters by treatment with lead acetate it gave the rotation- [a-Jy= -79.1" whilst the lzvulose separated by means of calcium hydroxide gave the rotation-[a],= -102.7" pure lzvulose giving -106".The quantity of sugar (estimated by a Fehling's solution 2 C.C. of which represented 0.010 gram of lEvulose) varies from 2.45 to 3.33 per cent. of root dried at loo' probably vary- ing in amount with the growth of the plant its development the time of year &c. &c. Triticin is best extracted from couch-grass roots by the following process. The dried and chopped root is treated with 25-30 per cent. alcohol drained in a displacement apparatus and well washed with water ; the dilute alcoholic extract is precipitated completely by lead acetate and the filtrate treated with sulphuretted hydrogen and con- centrated to a syrup on the water-bath.Several volumes of strong alcohol are then added and the gum washed with alcohol and dissolved in water. This treatment with lead acetate sulphuretted hydrogen alcohol &c. is repeated several times till lead acetate gives no further precipitate. The purified substance is then dissolved in a little water precipitated by strong alcohol and the precipitate decolorised by boiling its solution with freshly ignited well-washed animal charcoal ; the solution is concentrated and dialysed for 5-6 days the water in the water vessel being reneyed daily ; the gum is precipitated by alcohol washed with the same and dried in thin layers on a porcelain basin at 80"-100' and the pulverised residue is rubbed and dried at 100'-110'.A thousand grams of root will thus yield 15-20 of purified triticin tjhe quantity actually present being from 60 to 80 grams. The preparation requires 12 to 14 days. C. R A. W. Silico-acetic Acid. By A. LAD EN B UR G (Deut. Chem. Ges. Ber. vi 1029-1030). THE ethylic ether of this acid is produced together with zinc methyl- ethylate ZnCH3( OC2H,) and other bodies by heating ethyl silicate and zinc methide gradually to 12O0-3OO0 and opening the tubes from time to time for the escape of gases. Ethyl ortho-silico-acetate SiCH3(OC2H5)3,is a liquid boiling at 145O-15lo. It is soluble in alcohol and insoluble in water which however slowly decomposes it.Its specific gravity is 0.9283 at 0". By the actionof hydriodic acid it yields a solid insoluble body the composition of which agrees nearly with that of silico-acetic acid Si(CH,)OzH. It has the greatest resem- blance to silicopropionic acid and when heated takes fire yielding silica carbon dioxide and water. To prepare zinc methidc the author heats zinc-filings with methyl iodide sodium-amalgam (1 per cent. of Na) and a few drops of acetic ORGANIC CHERIISTRY. ether in a flask connected with a reversed condenser to the upper end of which is fitted a descending tube dipping into a column of mer-cury of 40 centimeters. The dry product is then distilled from an oil-bath. In this manner an excellent yield of zinc methide boiling at 47" is obtained.c. s. Ethylcrotonic Acid By W. P E :r n IE F F (Deut. Chem. Ges. Ber. vi 1098). THEorigin of ethylcrotonic acid leaves little doubt that its formula is When fused with potassium hydrate it forms acetic and butyric acids (Frankland and Duppa). From the examination of the calcium and silver salts the author finds that the butyric acid is the norma(; acid and not isobutyric acid. Normal butyric acid appears to give rise to a calcium salt containing a variable amount of water of crystallisation ; thus (CaH70J2Ca + H20,separates from a heated solution in small shining plates ; the salt with 4molecules of water of crystallisation separates from the mother- liquor on standing ; half of the water is lost by exposure to air for two or three days.Besides the two known isomerides ethylcrotonic acid and pyroterebic acid (the latter of which forms acetic and isobutyrio acids by the action of potash-W. C. Williams) four other six-carbon acrylic acids may possibly exist hydrosorbic acid may perhaps be one of these (Fittig and Barringer). C. R. A. W. Relations between the Molecular Rotatory Power of Tartaric Acid and of the Tartrates. By H. LANDOLT (Deut. Chem. Ges. Ber. vi 1073-1078). THEinvestigations of Biot Arndtsen and Krecke have demonstrated that the specific rotatory power of tartaric acid increases with the dilution of the solution and with the temperature ; and moreover that irregularities in dispersion occur when the solution contains more than 10 per cent.of acid. The salts of tartaric acid are now found to be less subject to these irregularities than the free acid. In order to determine the molecular rotatory power of the tartrates solutions of equivalent strength were employed the errors due to dilution being thus eliminated. In the case of the free acid the formula 15.06-0*131 C. gives the specific rotatory power of a solution having any degree of concentration C being the number of grams of acid contained in 100 C.C. The determinations were in all cases made with D light. Many experiments proved that the molecular rotatory power of acid ABSTRACTS OF CHEMICAL PAPERS. tartrates is approximately equal to twice that of tartaric acid while neut’ral tartrates possess nearly three times the rotatory power of the free acid.Small variations in the molecular rotatory power were observed in various salts the rotatory power being found to decrease as the metal contained in the salt is replaced by one having a greater atomic weight. It is also noticeable that the specific rotatoi-y power of a tsrtrate con- taining two metals is the mean of the specific rotatory powers of the tartrates of the metals entering into its composition-K,C,H,O Sp.rot. power. ....... 28.48 Mol. rot. power. 64.42 Na2C4H406.. ...... 30.85 39.85 Mean ............ 29.66 62.13 KNaC4H4o6. . . . 29.67 62.34 The salts (ASO)‘HC~H,~~, (As0)’KCIH4U6 K(C2H,)CaH40 and Ba&(C2H,)C4H406 were found to rotate in accordance with the law already stated but the numbers obtained were not quite so satisfactory as in the previous cases.On the other hand Ma(BoO)’C4HI06 and K(BoO)’C4H406 gave unsatisfactory results owing to the fact that the rotatory power increases largely with the dilution of the solutions. In the case of tartar-emetic this increase is remarkably great a 7.982 per cent. solqtion possessing a molecular rotatory power equal to about 22 times that of tartaric acid. Ethyl tartrate has a molecular rotatory power 2+ times as great as t>hat of tartaric acid and the specific rota- tory power of an alcoholic solution of tartaric acid is rather less than than of an aqueous solution ; but its rotatory power may be increased by heating in a sealed tube or by dilution with water.A solution of tartaric acid in methylic alcohol is inactive but dilution restores the rotatory powers of the acid. The author intends also to test the law of multiple rotatory powers by an examination of the malates and camphorates. T.B. Iron Tartrates and Citrates and their Amrnoniacal Com- pounds. By C. MEHU(J. Pharm. Chim. [4],xviii 85-92). FERROUS tart rate FeC4HP06 was obtained by boiling together equal parts of wire nails (pointesfines de Payis) or fragments of iron wire tartaric acid and water. Under these circumstances hydrogen is evolved and the ferrous tartmte is deposited as a white insoluble crystalline powder which after thorough washing with hot water undergoes no change on exposure to the air. If,however the washing has been imperfect the product gradually acquires a brownish tint on keeping.The acid liquor which has been filtered from the ferrous tartrate becomes yellow on exposure to the air but ebullition with iron decolorises it. Ferrous tartrate does not dissolve to any extent in aqueous tartaric ORGANIC CHEMISTRY. acid citric acid acetic acid or ammonium chloride but dilute mineral acids dissolve it readily and ttbe solutions undergo oxidation on expo-sure to the air. The solution in hydrochloric acid rotdtes the plane of polarisation to the right. Ammo?zio-ferr.ic tartrate 2(C4H606) .Fe2O3.2(NH,) .-Ferrous tartrate dissolves readily in ammonia and the solution absorbs oxygen from the air at the same time acquiring a brown tint. By evaporating this sdution on dishes heated to loo" greenish scales having the composi- tion represented above are obtained.This salt is insoluble in alcohol or ether easily soluble in water non-deliquescent in the air and when dried over vitriol retains 3H20. Ammonio-ferric tartrate prepared by dissolving gelatinous ferric hydrate in acid ammonium tartrate was found to be variabie in composition. Ferroz~s cit?-ate C6H,0,Fe.H,0 was prepared in the same manner as the tartrate citric acid being substituted for tartaric acid. Even when well washed it becomes coloured on drying unless extreme care is taken and on exposure to sunlight it acquires a reddish tint and undergoes partial oxidation. Hot water dissolves a small proportion of ferrous citrate but the salt is not deposited on cooling and the addi- tion of alcohol scarcely renders the solution turbid.Ammonz'o-ferric citrate 2(C6H807),Fe203 2(NH3).-When ferrous citrate is treated with liquid ammonia a solution is formed which becomes rapidly dark on exposure to the air ; and by evaporating this solution on flat dishes heated to lOO" greenish scales having the above composition are obtained. Ammonio-ferric citrate is insoluble in strong alcohol but water dissolves it in all proportions. One part of tlie salt dissolved in two parts of water yields a solution which is not syrupy. W-R Researches on Sorbic Acid. PART11. By E. KACHEL and R. FITTIG (Ann. Chem. Pharm. clxviii 2'76-294). Tetrabromocaproic Acid ; Xorhic Acid I%tmbromide.-T he authors have slightly modified the process formerly given by Fittig and Barringer for the preparation of this compound.Sorbic acid is mixed with about ten times its weight of carbon sulphide and the calculated quantity of bromine then added by degrees. Traces only of hydro-bi-ornic acid are evolved and the liquid remains clear and on standing a day or two deposits large well-formed crystals of the tetrabromide. These crystals are purified by recrystallisation from dilute alcohol. To gain some information as to the nature of the bye-products of which however only small qnantj ties are produced the mother-liquors were evaporated to dryness the residue dissolved in cold solution of sodium carbonate and a concentrated solution of the same salt added. The sodium salt of the tetrabromide which was thus thrown down was filtered off and hydrochloric acid added to the filtrate.A small yellowish precipitate was thus obtained and this distilled with water gave a very small quantity of a volatile organic acid. The wsidue on cooling deposited needles of a compound which was at first believed to be sorbic acid inasmuch as it had the appearance as well as the meltiug point of that body. Analysis however showed that it ABSTRACTS OF CHEXITCAL PAPERS. contained 41.65 per cent. of bromine or very nearly the amount 4l.88 required by the formula of ~nonobrom,osorbic acid C3H,Br02. The quantity of material was insufficient for its further examination. The properties of the tetrabromide have already been described pretty fully.The sodizcrn salt C6HJ3r402Na.2Hz0 forms magnificent silvery scales. It is easily soluble in water and in alcohol but quite insoluble in a concentrahed solution of sodium carbonate. The potassium salt is very soluble and difficult to obtain pure. It is not precipitated by the addition of potassium carbonate to its solution. The ainnzoitiurn salt separates in fine needles from the solution of the tetrabromide in excess of ammonia. The barium salt (CsH,BraOs)LBa.l~HzO, may be formed by mixing barium chloride and the sodium salt. The caZciwn salt (CsH,Br,O,),Ca. 7Hz0 is obtained in a similar manner. It crystallises with great facility in fine large silvery scales. It is much less soluble in cold water than the barium salt and makes its appearance even in somewhat dilute solutions.The zinc salt resembles the barium compound in appearance. Decompositioiz of the Salts by Heat.-When boiled with water the salts undergo decomposition regenerating the tetrabromide which separates in the form of a liquid becoming crystalline. A portion of the salt undergoes complete decomposition and the hydrobromic acid liberated assists the separation of the tetrabromide forming at the same time a corresponding quantity of bromide of sodium. When sodium hydrate or carbonate was added for the purpose of neutralising this hydxobromic acid as it was generated resinous pro- ducts only were obtained. By substituting barium carbonate for the alkaline salt a volatile highly irritating compound was produced which with ammoniacal nitrate of silver gave a reddish precipitate de- positing metallic silver on application of heat.The authors therefore believe this product of decomposition to have been acrolein but for want of material have not been able to examine the re$ction further. The residue contained only a small quantity of brown resinous matter but no organic acid could be detected. Action of Hydrogen on the !l'et.rabromide.-The action of sodium amalgam and water proceeds in two stages. The four atoms of bro-mine are first removed sorbic acid being regenerated and this by the assumption of two atoms of hydrogen is converted into hydrosorbic acid. Caproic acid is not formed. Sorbic Acid Dibrornide (Uibronzohydrosorbic Acid 1.-In the prepara- tion of the tetrabromide it was observed that the first two atoms of bromine are taken up more readily by the sorbic acid than the last.Proceeding in the manner already described but employing two instead of four atoms of bromine the dibromide C6H802Br2,corre-sponding with hydrosorbic acid was obtained. It forms small spark-ling scales meltiiig at 94'-95" ; dissolves easilF in ether alcohol carbon sulphide and hot benzene; is also slightly soluble in hot water. Simultaneously with the crystallised dibromide is formed a quantity of an oily fluid substance which the authors have not yet studied but ORGANIC CHENISTRY. which they consider may possibly be a compound isomeric with the dibromide. Eydrosoybic Acid-In the former paper it was stated that hydro- sorbic acid melted with potassium hydrate gave butyric acid.Further experiments show that acetic acid is formed at the same time. The butyric acid gives a calcium salt which crystallises with one molecule of water and the solution of which deposits nearly the whole of the salt on the application of heat. It is therefore normal butyric acid. Hydrosorbic acid therefore furnishes normal butyric acid and acetic acid when fused with potassium hydrate. The two isomeric com- pounds ethylcrotonic and pyroterebic acids suffer the sgtme deoom-position. Hydrosorbic acid is certainly different from the former but it is possible that it may be identical with pyroterebic acid. The difference in boiling point and specific gravity may arise from incorrect observations.The authors purpose making a careful comparison of the two acids. Some experiments upon the action of fused potash on sorbic acid led to no definite result. W. A. T. Oxpethane-sulphonic Acid and Oxymethane-disulphonic Acid. By MAX HULLER (Dent. Chem. Ges. Ber. vi 10511-1034). AFTERadverting to the attempts of Theilkul and Schwarz to prepare the methylic homologue of isethionic acid the author says that he found aIrnost the theoretical amount of isethionic acid could be obtained when alcohol is saturated with sulphuric anhydride so as to form a liquid which fumes in the air. The product diluted with water and boiled until the ethionic acid is decomposed is first treated with lead carbonate to remove the excess of sulphuric acid and the filtrate after precipitation with hydrosulphuric acid is neutralised with potassium carbonate and evaporated to dryness.The potassium isethionate thus obtained may be rendered absolutely pure by crystallisation from hot alcohol of 80-90 per cent. Methyl alcohol t.reated in a similar manner yields potassium oxymethane-disulphonate but the oxymethane-mono- sulphonate may be readily prepared by slowly adding sulphuric anhy- dride to a mixture of methyl alcohol or rnethylsulphuric acid with it considerable excess of sulphuric acid and subsequently treating the product in the manner above described. Both the free acid and its salts are very stable remaining unchanged even after long boiling with wster or with concentrated acids.The potassium salt forms large rhombic crystals which are t’olerably soluble in water but insoluble in alcohol. The ammonium compound forms small needles and the barium salt small transparent plates. The potassium oxymethane-disulphonate prepared from the product of the action of excess of sulphuric anhydride on methyl alcohol is contaminated with a dark coloured impurity which may be removed by treatment with alcohol of 40 per cent. The residue on being crystal- lised from boiling water yields the pure potassium compound in tufts ABSTRACTS OF CHE?/IICAL PAPERS. of needles. The barium salt obtained by precipitating the potassium compound with barium chloride crystallises in needles. Both the acid and its salts like those of oxymethane-sul phonic acid are very stable and can be boiled with water or concentrated acids without undergoing decomposition.EH3 The author assigns the graphic formula c-0 to methyl--SO2OH sulphuric acid and -OH to oxymethanesulphonic acid ; the CI:20Ef oxymethanedisdphonic acid he believes to be cSzEE its sta- bility being due to the direct union of the sulphur in the sulphur group with the carbon atom. He has also obtained indications of an acid bisulphomethylsulphuric acid -SO,OH corresponding with '-cl-" -SO,OK ethionic acid which he intends to investigate further C. E. G. The Compounds of Chloral with Sulphuric Acid. By J. GRAUOWSKI (Deut. Chem. Ges. Ber. vi 1070-1072). THE compound ~loHg~l~~S3~~6 formed by the action of sulphuric mhy- dride on chloral may likewise be obtained by washing the product of the action of sulphuric acid on chloral with cold water and crystallising the residue from ether the reaction being- SC2HCI,O + 3SO.&& -HZO = C1~HgC115X3016.This compound may with care be crystallised from warm alcohol. It melts at 70° undergoing decomposition at the same time. At 100' chloral distils over leaving a residue of sulphuric acid and chloralide. Tt decomposes by keeping into sulphuric acid and insoluble chloral ; with acetyl chloride it forms a new compound C8H12C112S3017, in small needles which melt at 92". The author has aleo obtained a compound CsH,4C1,2S2015 by the action of fuming sulphuric acid on chloral and likewise a crystalline compound C6H6c1503 melting at 129" by the treatment of dichloracetal with the fuming acid.C. E. G. A Polymeric Modification of Is0butyraldehyde. By G. A. BARBAGLIA (Deut. Chem. Ges. Ber. Ti 1064). TIIE author finds that the action of bromine and iodine on isobutyr-aldehyde produces a polymeride 3( C4HsO) = CI2HxO3,identical with that previously described by him (ibid. v 1052) as formed by the action ORGANIC CHEMISTRY. of chlorine on the aldehyde. It is readily prepared by psssing a current of air charged with bromine vapour through the liquid. The polymeride crystallises in slender needles melts at 60° and is un-changed even by long-continued exposure to a teniperature of 200". It reduces silver salts and is not acted upoii by dry chlorine bromine or iodine.Cyanogen does not cause the polymerisation of the aldehyde. C. E. G. Action of Ammonium Trisulphocarbohate and Sulphocarba- mate on Acetone and Aldehydes. Eiy E. MULDER(Ann. Cfhem. Pharm. clxviii, 228-241). ACETONINE is formed in small quantity only by the action of ammonia upon acetone. The base being unstable it appeared not improbat)le that a better result would be obtained by acting with acetone on a salt of ammonia. With carbonate or oxalate of ammonia t>his is not the case but the experiment is more successfiil when trisulphocarbonate of ammonis is is employed. Trisulphocarbonate of acetonine is then obtained. This body is very unstable even at ordinary temperatures evolving H,S and CS2. By treatment with hydrochloric acid it yields acetonine hydrochloride and with oxalic acid the oxalate.The author represents the constimtion of acetonine by the following formula :-NzxC~(CH,), N-C=( CH3) 2 / NILCIZ(CH,),. By heating trisulphocarbonate of acetonine with ferric chloride the sulphocyanide reaction is obtained. Sulphocarbamate of ammonium NH2.CS.HS.NH3 mixed with acetone yields after some days a beautifully crystallised yellowish body the analysis and reactions of which show that it is acetonine sul- phocarbamate. By the action of carbon bisulphide on aldehyde-ammonia Liebig and R?edtenbacher obtained a body which they considered as a kind of base and named car8oth;aZ&.ae C,Hl0N2S2. The author has prepared the same compound by bringing together aldehyde and sulphocarbamate of ammonia.He therefore considers carbothialdine as diethylidene-ammonium az~@hocnrbamate-LCH.CH3 NH2-C S-S-Ny \CH.C3H. Sulphocarbamate of ammonium and acrolein yield a similar com-pound NH,.CS. SN (C3H& or d~allylide.ne-anzmoizizcm.sulphocarbaw,ate. In like manner valeral and benzoic aldehyde furnish corresponding compoupds. ABSTRACTS OF CHEMICAL PAPERS. The product of the action of carbon oxysulphide on alcoholic ammo- nia is a colourless body probably NH,.CS.HO.NH,. When ammonium sulphide is substituted for ammonia a body, COS(NH4),S is formed which evolves H2S at ordinary temperatures leaving the same compound. This ammonium oxysulphocarbamate bebaveg with benzoic aldehyde like sulphocarbamate the resulting compound being NH2.CS.0N( C~HG)~.Heated witoh alcohol the filtrate deposits a colourless crystalline body which is not hydrobenzamide. Ammonium carbamate gives with benzoic aldehyde a solid mass NH,.CO.ON( C7H6), which after heating with alcohol yields crystals of hydrobenzamide. Acetone acts neither upon ammonium oxyaulphocarbamate nor upon the carbamate. W. A. T. Silver-Urea. By E. MULDER (Deut. Chem. Ges. Ber. vi 1019-1021). BYacting with freshly precipitated silver oxide on an aqueous solution of urea Liebig obtained a compound having the composition 2CH4N20 + 3Ag20. When a solution of silver nitrate and urea is precipitated with caustic soda a gelatinous yellow precipitate is formed having the composition CO(NHAg),.As Liebig did not make an ultimate analysis of his compound but only determined silver and wea it appears very probable that the two bodies are identical indeed they con- tain almost the same per centage of silver. c. s. Action of Ammonia on Bromacetyl-urea. By E. MULDER (Deut. Chem. Ges. Bey. vi 1015-1018). INa previous communication (last POL p. 382) it was shown that this reaction yields digly collamic diuramide together with another body which appears to be triglycollamic triuramide. The latter is always formed in small quantity only and differs from the diuramide by not yielding a platinum double salt and not melting below 230° whereas the diuramide melts at 195"-200". c. s. Derivatives of Uric Acid. By E. MULDER (Deut. Chem.Ges. Ber. 1010-1015). ON dissolving dialuric acid and urea in warm water and tilling with this solution a flask which is then well st?oppered urea dialurate crys- tallises out. It is sparingly soluble in water and forms crystals grouped in stars. It is not oxidised in the air like free dialuric acid its aqueous solution has an acid reaction and gives a fine blue colour by adding ferric chloride and ammonia. The free acid and alloxantin give the same reaction. When a solution of alloxan and urea is evaporated in an exsiccator ORGANIC CHEMISTRY. allzlranic acid C,H,N,O, is obtained foi*ming crystals which are grouped in stars. It is sparingly soluble in cold water more freely in hot water and has a slight acid reaction. It neither gives the reaction of alloxan nor does it yield mycomelic acid with cold ammonia.Its aqueous solution is precipitated by basic lead acetate mercuric nitrate and baryta-water. The lead salt yields on decomposing it with hydrogen sulphide and evaporating the filtrate a crystalline body pos- sessing the properties of alloxanic acid. On adding silver nitrate and a little ammonia silver alluranate C5H,AgN405 crystallises out. Hydriodic acid converts alluranic acid into hydantdin. Its solution in ammonia or dilute alkalis when freshly prepared gives with acids a precipitate of the acid but no longer after standing. It is interesting for the physiologist that alloxan and urea cannot exist together in solution. By adding silver nitrate and a little ammonia to an aqueous solution of alloxan a precipitate consisting apparently of C4AgrsN204 is formed.Hydriodic acid reduces alloxan at the common temperature to allox-antin but at 100" to dialuric acid. c. s. Hornologues of Oxaluric Acid. By W. H. PIEE (Chemical News xxviii 173). WHENone molecule of urea is fused with one molecule of succinic anhydride at a temperature of 120*-130" an oily liquid which solidifies to a crystalline mass is obtained. This was powdered, washed with alcohol and crystallised from water which deposited it in brilliant scales consisting of an acid melting with decomposition at 203"-204" and having the composition C5H1,N204. The new sub- stance is moderately soluble in hot water or acetic mid almost in- soluble in cold water or alcohol and insoluble in ether chloroform or carbon disulphide.Sulphuric acid diesolves it and the addition of water causes its precipitation in an unaltered state. With alkalis or alkaline earths it forms easily soluble salts but the lead salt and tbe silver salt C5HIAgN204 form white crystalline precipitates nearly in- soluble in boiling water. The author proposes to call the new acid 8ucchw-ca&a?nk acid and represents it by the following formula- CH~-CO-NH-CCO-NH~ 1 CH2-40OH. CE,-CO--NE-CS-NH~ Xuccino-sulphocarbamic acid I was pre-CH2-COOH pared and purified like the last-described body sulphurea being snb- stituted for urea and the fusion being conducted at about 150". It forms a yellowish crystalline powder which melts at 210*5°-211" is insoluble in cold water alcohol and ether and dissolves rather less readily than succino-carbamic acid in boiling water or acetic acid; snlphuric acid however dissolves it readily but without alteration VOL.XXVII. E ABSTWCTS OF CHXMICAL PAPERS. The alkaline salts of succino-sulphocarbamic acid are easily soluble but the lead salt and silver salt form white precipitates which blacken when heated. The fusion of citraconic anhydride with urea gave rise to the libe- ration of carbonic anhydride and the formation of citraconamide ; but when citraconic anhydride is fused with sulphurea combination takes CO-NH-CS-XHz, place and citraco-suljphocarba~~c acid C3H/ 'COOH is produced. It melts with decomposition at 222"-223" and yields easily soluble salts with alkalis.Its lead salt and silver salt form white precipitates which like the corresponding salts of succino-sulphocarbamic acid become black on heating. When lactide is heated with urea carbonic anhydride is evolved and B substance which is still under investigation is formed. The same substance is produced when lactide is heated wit'h sulphurea carbon .oxysulphide being evolved in this case. When succinic anhydride it heated with sulphocarbanilide phenyl- sulphocarbimide and aniline are liberated and the latter substance then reacts on the anhydride. The author intends to continue and to extend his researches. T. B. On Ethyl and Diethyl-allylamine. By ALBE RT RXNN E (Ann. Chem. Pharm. clxviii 261-266).has PIPERIDINEbeen proved by Cahours to be a secondary base. Whether it be amylene the two affinities of which are saturated by the bivalent group NH or ethyl-allylnmine or methylcrotonylsmine is open to question. The author has prepared ethyl-allylamine for the purpose of comparison. Allylamine was prepared from ally1 sulphocarbimide by the action of sulphuric acid; it was mixed with ethyl iodide in a tube which was sealed and gently warmed. After the action had ended the con- tents of the tube were distilled with potassium hydrate. Allylamine, ethyl-allylamine and diethyl-a1 lylamine came over. Ethyl-allylamine was separated by fractional distilladion. It came over between 83"-85". It is colourless mixes with water and has a strong ammoniacal smell.It is not identical with piperidine as its boiling point is 22"lower. Its salts also are entirely different. Diethyl- allylamine boils between 100' and 102'. It dissolves in twenty times its bulk of water of 18" and when gently warmed separates out producing a milky turbidity like that exhibited under similar circum- stances by conine. It is isomeric with ethyl-piperidine but has a boiling point 20" lower. W. R. Haloid Derivatives of Toluene. By E. WROBLEVSKY (Ann. Chern. Pharm, clxviii 147-213). MEPERstates that sodium has no action on a mixture of methyl iodide and the author's liquid bromotoluene correspondiug with oxybenzoic ORGANIC CHEMISTRY 51 acid but the author finds that an action takes place a hydrocarbon which is probably isoxylene being formed.Aee&ornetabromo~a,.atol~idine,C&&BP(CE3)NE(CzH30) was ob-tained by gradually adding bromine to acetoparatoluidine in presence of water. When crystajlised from spirit it forms beautiful needle- shaped crystals It melts at 117*5O,and is easily soluble in alcohol but slightly solrrblc in water. Alooholic potash converts it into meta-~romopa~~t~~uid~ne, a colourless liquid,.which solidifies at .+FJ0 boils at 240° has a specific gravity of 1.510 at 20° and is easily soluble in alcohol. The same hse was obtained by brominatim of the corr8- sponding toluidirme. The ?zitrate crystallises from water in lmge yellow leafy plates melting at 182". The hydrochloride is slightly soluble in water from which it separates in large white square prisms melting at 221" with partial decomposition.The acid oxalate C7H6BrNH2 CZH2O4 crystallises in large white needles which are slightly soluble in water. The acid sulphate C,H6BrNH2.H2S04-I-H,O is very soluble in water from which it separates in large roseate needles. When the amido-group of the above base was replaced by hydrogen according to the method of Griess metabromotoZziene boiling at 181"-182" and having a specific gravity of 1.4009 at 21" was obtained. This bromo- toluene does not solidify at -20° and when oxidised yields bromo- benzoic acid identical with that obtained by the action of bromine on benzoic acid. Hence this brornotoluene belongs to the rnet~a series. Metabromotoluene was afso obkained by heating diazometabromotoluene sulphate with water- iMetccbrom op ariodo tduene C6H31pBrWH3.-W hen diazometabromo- toluene prepared by the action of nitrous acid on bminotoluidine nitrate is dissolved in nitric acid and treated with hydriodic acid an oil separates which when purified forms a colourless liquid boiling at 265".It is easily soluble in alcohol and does not solidify at -14". Whennitratedit yields ne'troptr;riodornetabrornotoZu~~, CGLfiNOaIPBiJ"CH3 which separates from alcohol in needles and melts at 118O. When toluidine is digested for 16 hours with an equivalent quantity of glacial acetic acid and afterwards distilled the latter portion of the distillate consists principally of acetorthotoluidine and acetopara-toluidine and by treating the first portion of this with soda again digesting it with acetic acid and repeating these operations acutortho-toluidiy&ewas obtained in the pure state.AcetornetnbromorthoioZuidi?ze C6H3Brm( CH3)NH,(CzH30) was ob-tained by treating the last-named substance with bromine in presence of water. It crystallises in beautiful long needles which melt at 157" dissolve easily in alcohol and with less facility in boiling water. The action of acetyl chloride on metabromotoluidine also yields this sub- stance. Alcoholic potash converts it into metL~bro.morthotol~idine.This latter forms large octohedrons melts at 57" boils at 240" and is easily soluble in alcohol but not readily soluble in water. The hydrochloride crystallises from water in white prismatic crystals having a pearly lustre.Hydrochloric acid separates it from its solution and it sub-E2 ABSTRACTS OF CHEMICAL PAPERS. limes unchanged. The nitrate separates from water in long needles, and melts at 183" at the same time undergoing decomposition. The sulphate (C5H6BrNHz),.HzS0,+ l&H,O is deposited from water in white pearly tablets. When the sulphate of the diazo-derivative of metabromorthotoluidine is heated with alcohol metabromotoluene is obtained. ~etabrornort~iodotoluene, C7H6Brm10,was obtained by treating meta- brornorthodiazotoluene with hydriodic acid. It forms a colourless liquid smelling like bromotoluene and boiling at 260". Its specific gravity is 2.139 at 18O and on treatment with nitric acid it yields witrometnbromorthiodotoluene C,H5NO2Brm1O.This compound is easily soluble in alcohol and forms fine prismatic crystals. When meta- bromorthodiazotolueue sulphate is boiled with water metabromortho-cresol is formed as follows:- C7HsBrNZ.HS04 + HzO = C7Ef6Br(HO)+ Nz + HSSO,. It forms beautiful needles having a golden lustre and is almost in- soluble in water but more easily soluble in alcohol. It melts at 88*5O and its aqueous solution is coloured greeu by iron chloride. Its potas-sium salt C6H3Brm(CH3)(KO)o+ HzO forms shining red scales. Sulplto-Derivatives of Metabromotoluene.-When metabrornotoluene is treated with fuming sulphuric acid three sulpho-derivatives are formed and when a solution of their barium salts is evaporated a slightly soluble a-salt is first deposited and on further evaporation two other salts ,@ and y The a-barium salt forms small prismatic crystals.The a-potassium salt forms beautiful prismatic crystals and yields salicylic acid on fusion with potash. Hence the a-acid is meta-brbmotoluene-orthosulphonic acid. The P-barium salt 2[ (C7H6BrmS030)zBa]+ 3&0 forms fine lustrous crystals.-The P-lead salt [C7H6BP( S03)0]zPb + 3H@ separates from water in fine large needles.-The /3-calcium salt 2[ (C7H6BrmSOto)2Ca]+ 5Hz0,forms large rhomboidal leaflets. The $-potassium salt forms large shining leaflets and yields salicylic acid on fusion with potash consequently the p-acid is also a meta-bromotoluene-orthosulphonic acid the two acids having the positions 1 2 3 and 1 3 6 respectively..The y-barium salt 2[(c7H6BP S03)2Ba] + 5Hz0 crystallises in needles and the corresponding potas- sium salt yields on fusion with potash a small quantity of an acid which is not coloured by iron chloride and consequently cannot be salicylic acid but it mag. be either a paraoxybenzoic acid or oxybenzoic acid. p-Barium Nitrometabromotoluene-orthosulphonate 2[(C7HaN0J3rmS030)2Ba]+ 7Hs0 was obtained by nitrating the &barium salt just described. It forxne needle-shaped crystals which are easily soluble in hot water. The lead salt [C7H,Br"N0z.S03]2Pb + 3Hzo,forms prismatic crystals easily soluble in water. The calcium salt 2[ (C7H5Brm(NO2) S030)zCa] + ~EzO,separates from alcohol in large prismatic crystals which are easily soluble in water or alcohol ORGANIC CHEMISTRY.53 Metabromotoluene yields two nitro-derivatives one of which is solid the other liquid. The solid compound a-nitr~metabromotol~~ene cqstallises in prismatic crystals which melt at 55". It boils at 267" and is easily soluble in alcohol. The liquid compound 13-nitrometa-bromotolzcene is a colourless liquid smelling of bitter almond oil and boiling at 269". Its specific gravity is 1.612 at 20". Orthobromotoluene and its Derivatives.-Orthobromotoluene was ob-tained in a pure state by first converting Rosenstiehl's orthotoluidine into the corresponding diazo-derivative of toluene and afterwards con- verting this into the perbromide which when digested with alcohol yields orthobromotoluene in the pure state. It boils at 182" has a specific gravity of 1.401 at 18" and remains fluid at -20".Only resinous products were obtained on oxidising it but with bromine it yields a dibromotoluene boiling at 240". Ort7lobrorrzometato~zcidinewas obtained by converting Beilstein and Kuhlberg's metatoluidine into the aceto-derivatire and treating this aa described in the early part of the present paper. It boils at 240" and its nitrate crystallises in red prismatic crystals. When it is con- verted into the perbromide of the corresponding azo-derivative and heated with alcohol it bromotoluene identical with that last described is formed. Parabromotoluene yields two nitro-derivatives one of which is solid the other liquid. The solid modification a-parabromorthonitro-toluene, melts at 43" and boils at 256"-257".The liquid form P-parabromo-metanitro-toluene,remains fluid at -20° boils at 255"to 256" and has a specific gravity of 1.631 at 18". Reduction with tin and hydrochloric acid yielded the corresponding bases. a-parnbromortho-tolzcid~nesoli-difies at -2" and the P-parabronwmeta-tohidineform prismatic crystals melting at 67". The nitrate of the former crystallises in beautiful crystals having a pearly lustre while that of the latter forms prismatic crystals. Parametadibromo-toluene '1 3 4 was obtained by brominating solid toluidine and digesting the perbromide of the diazo-derivative obtained from this with alcohol. It has a specific gravity of 1.812 at No,boils at 238"-239" and remains fluid at -20°. Nitric acid transforms it into a nitro-dibromotoluene which melts at 86"-87" and separates from dilute alcohol in fine needles.Reduction by tin and hydrochloric acid transforms this compound into a dibromotoluidine which melts at 95" and does not unite with acids. Fittig's dibrorno-toluene probably has the positions 1 2 4 and the author did not succeed in obtaining its nitro-derivative in the pure state. Ortlzometa-dibroniotolzcene C6H3.BrmBro.CH3, 1 2 5,? was obtained by bromi- nating metahromotoluene. It boils at 236" has a specific gravity of 1.8127 at 19" and it remains liquid at -20". Its nitro-derivative corresponds with that last described but its amido-derivative melts at 83" and does not combine with acids This dibromotoluene was also obtained by digesting the perbromide of the diazo-derivative of metabromorthotoluidine with alcohol.OrthometadibromotoZue?ae 1 2 3 ? was obtained either by decomposing the perbromide of the diazo-derivative of orthobrornometatoluidine with alcohol or by brominating orthotoluidine and treating the dibromotoluidine ABSTRACTS OF CHEMICAL PAPERS. with alcoliol and nitrous acid. 'It crystallises in long needles melts at 42*5" and boils at 239". Its dro-derivative is easily soluble in alcohol from which it separates in fine needles melting at 59". The dibromotoluidine C7H5BPBFNH2,referred to above as being formed by the bromination of orthotoluidine forms fine pearly needles easily soluble in alcohol and melting at 50". eta-metadibromotoluene 1 3 :5 was obtained from dibromo-paratoluidine by substituting H for NH,.It separates from alcohol in long needles which melt at 60" and boil at 241". Its nitro-derivative is easily soluble in alcohol from which it separates in prismatic crystals melting at 1%". When the sulphate of the azo-compound derived from this nitro-dibromotoluene is heated with water no cresol is formed but dibromotofuene 1 3 5 is repro-duced; when however hydriodic acid is used in place of water d~bro~~~odotoZuene, C7H5Br2mIP,is formed. This compound crystallises in long needles which melt at 86" and boil at 270'. The ortho-ortho-dibromotoluene 1 2 6 WM obtained by converting metatoluidine into a dibromo-derivative and replacing its NH by H. It boils at 246" has a specific gravity of 1.812 and doefi not solidify at -20".Its ?zitro-derivative separabs from benzene in beautiful prismatic crystals which melt at 79". Aeeto-dibromotoluuidine C7H5Br&H(C2H,0), was obtained by adding bromine to acetometabromotoluidine in pre- sence of water. It crystallises from water in fine flat needles melting at 154". Alcoholic potash converts it into a-dibromotoluidine which forms pearly crystals melting at 92.5". It does not combine with acids and plcoholic nitrous acid converts it into the last described dibromo toluene Zeta -metaparatr~bro?n,otol~en~, P 3 4 5. The solid met% dibromoparatoluidine was first converted into the corresponding diazo-derivative and this was afterwards converted into the perbro- mide which on digestion with alcohol yielded the above-mentioned tribromotoluene.It forms a colourless liquid which boils at 260" and remains fluid at -20". OrtPco-ortho~tr?'bro~~~~oZ~e~. -When an acid solution of metatoluidine hydrochloride is brominated a tribromotoluidine C7Ha3r02BrXNH2m is obtained. It is slightly soluble in alcohol from which it crystallises in needles melting at 97". When this base is decomposed by alcoholic nitrous acid the above tribromotoluene is formed It separates from benzene in long silky needles is slightly soluble in alcohol melts at 70" and boils at 290". Its nitroderivative €orms leafy crystals slightly soluble in alcohol easily soluble in benzene and melting at 215". Aceto~netachZorotoluidiire CsH[3(;lm.CH3.NHp(C2H,0),was obtained by passing chlorine into acttoparatoluidine in presence of water and crystallising the Product from water.It forms fine large leafy crystals which melt at 99 ,and dissolve easily in alcohol but sparingly in water Alcoholic potash converts itl into a chlorotoluidine C7H6ClmCH3NH2p. This compound boils at 222" and has at specific gravity of 1.151 at 20". The in'trate separates from water in large shining yelIowish prisms which melt at 189" ; 100 parts of water dissolve 2.593 parts of it at 19". The kydroch2oride is slightly soluble in water from which it separates in large white quad1 angular prisms having a pearly lustre and subliming above 210". The acid omdate C,H6C1.NH,.C2H201,is ORGANIC CHEMISTRY. slightly soluble in water and it crystallises in large needles.The acid sulphate C7H&1.NH,.HzSOa dissolves readily in water and crystallises in large needles. This chlorotoluidine was also obt'ained by the action of chlorine on a solution of a toluidine salt. Metachlorotolzcene C6&Clm. CHS was obtained by replacing the NH2 of the last-described base by H. It boils at 156" and yields metachlorobenzoic on oxidation. Isomeric deriuatiives of Parachloroto1zcene.-The products of the nitrs- tion of parachlorotoluene were separated by fractionation into two isomerides. a-chloronitrotokuenzs boils at 243O has a specific gravity of 1.307 at 18" and remains fluid at -18". l.3-chloronitrotoluene boils at 253" has a specific gravity of 1.3259 at 18" and remains fluid at -13". These chloronitrotoluenes were converted into sulpho-acids and the barium salts were prepared.The a-salt (C7H5CINO2SO3)2Ba +4H20 is slightly soluble in water and crystallises in fine needles while the @salt is very soluble in water. Liquid a-chlorotoluidine was ob-tained by the reduction of a-chloronitrotoluene. It forms a colourless liquid which boils at 238" has a specific gravity of 1.1855 at 20" and remains fluid at -20". Its hjdTochEoride CTH6C1.NH2HC1 +H20 forms prismatic crystals easily soluble in water and subliming like sal-ammoniac. The nitrate forms white prismatic crystals melting with decomposition at 179". 100 parts of water dissolve 2.853 parts of it at 17. Solid p-chlorotoluidine was obtained by the reduction of p-chloronitrotoluene. This substance forms large white tables having a pearly lustre.It melts at 83" boils at 241" and dissolves easily in alcohol but with difficulty in water. The hydrochZorid6 forms pearly elongated leaflets which sublime like sal-ammoniac and are more soluble in water than the corresponding salt of the liquid a-cblorotolui- dine. The nitrate forms large white pearly tables melting with decomposition at 165". 100 parts of water at 17" dissolve 5.014 parts. Isomeric Metlzylclilorophenetob from the above Chloroto1uidines.-The mixture of chloronitrotoluenes obtained by nitrating paracblorotoluene was amidised and the isomeric chlorotoluidines were separated by crystallising their hydrochlorides (the @-salt being as stated above more soluble than the a-salt). Each base was then converted into the sulphate of its diazo-derivative and on heating these with alcohol no chlorotoluenes were obtained but isomeric methylchlorophenetols a-methyZchloroy,henetol forms an aromatic liquid almost insoluble in water but easily soluble in alcohol.It boils at 210"-220" and has a specific gravity of 1.127 at 19.5. ~-~nethylchlorophsnetol bas an odour like that af its isomeride boils at 210°-220" and has a specific gravity of 1.131at 18'. By heating the sulphates of the azo-derivatives just referred to with hydriodic acid two isomeric iodochlorotoluenes are obtained. C7H6C1N2,HS0,+HI =H&Oa +N2+CTE&1I. a-chlo-riodotohene is a colourless liquid smelling like iodotoluene boiling at 242" and having a specific gravity of 1.716 at 17" It is easily soluble in alcohol insoluble in water and it does not solidify at -14".P-clzloriodotoluene boils at 240" has a specific gravity of 1.770 at 19*5" aud it solidifies at +10". ABE3TRACTS OF CHEMIUAL PAPEXS. Nitro-d~chZorotoZzcenewas obtained by nitrating the dichlorotoluene produced by the action of chlorine on toluene in the presence of iodine. It is a colourless liquid which boils with partial decomposition at 274" solidifies when cooled to -14" and possesses a specific gravity of 1.455 at 17". Alcohol or ether dissolves it readily and it possesses an odonr resembling that of bitter almond oil. Its reduction results in the formation of a dicldorotolzcidine which crystallised from dilute alcohol in leafy crystals melting at 88" and boiling at 259".Acids do not combine with it. As dichlorotoluene yields only one amido-derivative it follows that in the preparation of parachlorotoluene no isomeride is formed. I',B. Bromotolnenes. By H. HGBNEE and J. POST (Ann. Chem. Pharm. clxix 1-69). THISelaborate paper eontains fhe results of a research which the authors in conjunction of some of their pupils carried out with the object of examining the derivatives of the two isomeric bromotoluenes which are formed simultaneously by the direct action of bromine on toluene. Some of the results have already been published separately (see this Journal ix 120,1055 ; x 696 1005 1094; xi 886). (1.) ParabromotoZzceize.-This compound was obtained in a perfectly pure state by repeated crystallisation fkom alcohol and pressing the crystals between paper.It forms splendid colourless crystals melting at 28"-29" solidifying again at 28" and boiling at 185.2". By oxida-tion it yields parabromobenzoic acid melting at 245". When it is dissolved in fuming sulphuric acid either at a temperature not exceed- ing 80" or at 160°-180" it yields two monosulphonic acids which may be separated by recrystallising the barium salts ; that of the a-acid being much more soluble than the B-compound. a-Series. a~Purabromotolzcene-su223horticacid CJ3,Br(CH3) SO,H is a very soluble orystalline laminated mass. a [C6H3Br(CH3)SOJ2Ba + 7HzO forms colourless well-defined long and compact rhombic needles. a [C6H3Br(CH3)S03]2Pb+ 3H20 is obtained from a concentrated solution in loug needles which when re-crystallised from a dilute solu- tion are converted into small light yellow compact rhombic plates.u [C16H3Br(CH3)S03],Sr + 7H20 crystallises in hard four-sided pyramids. u C6H3Br(CH~)SO2.NH2 was obtained by treating the impure chlo- ride of the acid with solid ammonium carbonafie and then adding con- enhated ammonia. It dissolves sparingly in cold water freely in alcohol ether and hot water and crystallises in long soft silky needles melting at 151"-152". a C6HzBr(N01)(CH,)SO,H was produced by adding the anhydrous barium salt to warm fuming nitric acid ; it crystallises in small pale- yellow deliquescent needlw arid forms very soluble salts. u [CGHzBr(N02)(CH,)SOs]J%i t HzO separates by slow evapora- ORGANIC CHEMISTRY.57 tion in thin yellow needles and from a concentrated solution in crys-tals resembling sal-ammoniac. a [C6H2Br(N02)(CH,) SO,],Pb + 2+H20 forms colourless .glisten- ing octohedrons; sometimes it was obtained in needles which also contain water but are more soluble in alcohol than the octohedrons. a [C6&Br(No2) (GH,) SO3lzSr + $H20 crystallises in thin fan- shaped needles. a C6HzBr(N02) (CH3)S03Na forms long and very thin needles. a ParaZtromoszc~hobenzoicacid was prepared by boiling barium a-pa.rabromotoluene-sulphonate with a ohromic acid solution. On con-centrating the solution C6H3Br(CO2H) S03K + K20crystallises out in thin needles. a C3H3Br{ gg Ba + iH,O crystallises in thin glistening plates ; a C6H3Br{ iz } Ca and ac C6H,Br { :g } Pb + 2H20 form small needles.0 Series. P-ParabromotolzLenesulrphonic acid is readily soluble in water and alcohol sparingly in ether and forms a crystalline laminated mass. It is not converted into an isomeric modification by heating it to 210". p [C6H3Br(CH3)S03]zBa+ E20crystallises when a dilute solution is slowly evaporated in hard compact plates and from a concentrated solution in very thin and brilliant plates. If it be mixed with one of the isomeric salts or with the calcium salt it separates from a concen-trated solution as a white powder. 13 [C6H3Br(CR,)s03]2Pb + 3H20 crystallises in silky stellar needles. p [C6H3Br(CH3)S03]2Ca+ 4H20 is a very soluble salt and forms either thin long rhombic needles or compact plates.p C6H3Br(CH,) SO,Na + H20crystallises in thin transparent four-sided prisms. 0 [C6H3Br(CH3)S03]21Mg+ 8$H20(?)forms softy silky tufts and p [C6H3Br(C1E-f3)SO,],Sr + H20thin plates. 0 [C6]EI,Br( CH3)S0,]2Cu + 7H20 crjstallises in large pale-blue plates. p C6H3Br(CH3)S02C1 was obtained by the action of phosphorus pentachloride on the acid or its sodium salt. It crystallises from chlo- roform in plates melting at about 35" and possessing a peculiar smell. 0 C6H3Br(CH,) SOz.NH3crystallises from water in long slender glistening needles melting at 166"-167'. /3 ~6HzBr(N02>(CH3)SOzH is formed by adding dry p parabromo-tolueuesulphonic acid to warm fuming nitric acid. It crystallises from ether in deliquescent scales possessing a very bitter taste.P [C6H2Br(N02) (CH,) SOal2Ba 3-2H2O crystallises in warty needles. ,d [C6H2Br(NO2) (CH,)SO,],Pb + 3H~oseparat6s from a solution in ether-alcohol in thin colourless needles. [C6H2Br(N0,)(CH,) so3]2cu + 6H20 forms microscopic four-sided green prisms. 58 ABSTRACTS OF CHEMICAL PAPERS /3 C6H2Br(N02)(CH3)S0,A.g is a precipitate consisting of glistening scales. /3 [C6H,Br(NO2) (CH3)S03],Sr + 7HzO dissolves freely in water and alcohol and forms small yellow needles. The sodium salt is very soluble and could not be obtained in distinct crystals p Parabromos.u~hobenxoicacid C6H3Br( so3H) COzH. Wheu p-parabi-omotoluene-sulphonic acid is boiled with the chromic acid mix. ture a large portion is completely destroyed while another is slowly oxidised to the corresponding benzoic acid which forms a deliquescent mass and yields very soluble salts.The barium and calcium salts consist of microscopic plates. j3 Ortl~otol~.2ce~zeesz~l~hoolzic acid is obtained by the action of water and sodium-amalgam on the /? brorno-acid. Its salts are all very soluble. p [C6Hd(CH)SOs]J?b + 4H20crystallises in needles. (3 [CBH4(CH3)S03]zBa+ HZO ahd ,G C,H*(CH3)SO3K + H,O form monoclinic plates and the anhydrous sodium salt forms needles. The chloride of this acid is an oily liquid and the amide which is freely soluble in water alcohol and ether crystallises in monoclinic prisms melting at 152"-153*. ,i3 z'olyl sulphydrate C6H4( CH3) SH was prepared by treating the chlo- ride of the brominated acid with tin and hydrochloric acid and acting on the bromotolyl sulphydrate thus formed with sodium-amalgam and alcohol.It forms soft glistening plates and is insoluble in water j3 [C,Hd(CH3) S],Pb is a bright brick-red precipitate which readily absorbs oxygen and becomes white. (2.) 0rtkobromotoluerze.-To obtain a pure compound the liquid portion which was separated from the solid bromotoluens was cooled down to -2O" and zt few pieces of calcium chloride were added 011 which soon some solid bromotoluene was deposited. The liquid was %lien twice cooled down to -21" when a few more cr stals separated out. After being further purified by fractional distisation nnt,il it distilled at 183*2",it was boiled for ten hours with a mixture of manga-nese dioxide sulphurjc acid and glacial acetic acid and the sgme operation repeated twice.Thus all the para-compound which W~S still present was oxidised to parabromobenzoic acid while a large por- tion of orthotoluene was completely destroyed and not oxidised to an acid resembling in that respect other similar ortho-compounds. To remove every trace of parabromobenzoic acid the liquid was first sub-nlitted to fractional distillation and then left in contact with pieces of sodiurn. PLlre orthobromotoluene is a very refractive liquid possessing aromatic odour and boiling at 181°-1820. When heated gently with Nordhausen sulphuric acid it yields ody one sulphonic acid forming salts which are tolerably soluble crystallise well and lose their water of crystallisation only above looo,and in most cases none over sulphuric acid.[C6H3Rr(CH,) So3l2Ba+ 2H20 forms rhomboydal plates ; the stron-tium salt is a very similar body. [C6H3Br(CH,)SO3],Ca + 2HZ0crystallises very slowly from a con-centrated solution in compact rhombic six-sided plates. ORGANIC CHEMISTRY. [C,H,Br( CH3)S03]2P1-,+ 2H20 separates fi*om a wry concentrated solution in very thin small plates and from a dilute in tufts of needle-shaped plates. C6H,Br( CH,) SOBNa + &H20 forms well-defined brilliant rhomboidal plates. C6H3Br(CH,)S0,K. + $H20crystallises in plates or in short fhick white needles. The copper salt. is very soluble and crystallises in very thin and light- coloured plates while the zinc salt forms small glistenirig plates and the magnesium salt small scales.C6~,Br(CH3)S02Clwas prepared by freating the dry sodium salt with phosphorus pentachloride. It foyms a ci-ystalline mass consisting of needle-shaped crystals and possessing a pungent smell. It crystd-lises from ether in large plates melting at 52'-53". It is but slowly acted upon by caustic soda or boiling water and dissolves sparingly in concentrated sulphuric acid and without change in fuming nitric acid. At 250" it begins to boil and at 260" it is decomposed into charcoal sulphur dioxide and C6H3BrCl( CH,). When heated with water to 200" for several days ih is reconverted into orthobromotoluene-sulpho-nic acid no isomeric modification being formed. C,K,Br( CH,) S02.NH2is sparingly soluble in cold water more freely in boiling water and very readily in alcohol and ether ; it crystallises in long glistening needles melting at 133O-134" and boiling with decomposition at about 290".Ortkobromotolyl sulphydyate C6H3Br(CH,)SH,is formed by boiling the chloride with tin and hydrochloric acid. It is a refractive limpid liquid having a peculiar smell and boiling with decomposition but volatilising with steam. The 1-ead salt is a bright yellow precipitate. On heating the sulphydrate with dilute nitric acid or acting on the sodiiim salt with alcoholic iodine the disulphide (C6H3Br(CH3)S)2 is formed crystallising from alcohol in small needles and from a mixture of xylene and alcohol in long needles melting at 56"-58". Ort7Lob1'0112012ity0tolue.i.les.li~hoiiic acid is a deliquescent mass readily soluble in alcohol and ether.The free acid as well as its salts has a very bitter taste. The following four salts crystallise from water in microscopic but well defined crjbtals :-[C6H2Br(NC),)(CH,)sO312Ba+ 2H20 [C,H2Br(N0,) (CH,) SOd]Pb + 2H20 [C6H2Br(N02)((33,)S03J2Ca [C6H&r(N02) (CH,) SO,]K. C6H2Br(N02)S03Na+ HzO crystallises in tufts of long needles and is less soluble in water than the preceding salts.. Orf7~obromosu~hoben%o~c cr cicl C,H,Br( SOyH)C02H was prepared by oxidising the barium salt of the corresponding toluenesulphonic acid with chromic acid solution. C,II,Br(CC),H)sO,K 3. $E120crystallises from water in thin plates resembling naphthalene. ABSTRACTS OF CHEMICAL PAPERS.C6H3Br{ gg:} Ba + 2Hz0 separates on adding alcohol to the con- centrated solution in tufts of glistening and very thin needles. C6H3Br{~~~} Pb + 2H20 forms small white glistening needles ; the calcium salt is very soluble and forms long silky needles. Metatoluenesulphonic acid was obtained by the action of sodium amalgam on a solution of barium orthobromotoluene sulphonate. [C6H4(CH3)S03]oBa+ 2Hz0 is very soluble in water and alcohol and forms a crystalline powder. [c6H4( CH,) S03JzPbf 2Hz0ciytallises from a concentrated aqueous solution in thin plates grouped in rosettes and from absolute alcohol in long needles. [C6H4(CH3)S03],Cais very soluble in water. On heating a con-centrated alcoholic solution the salt separates in small glistening plates which redissolve on cooling.C6H4(CH3)S03Na+ iHzOis very soluble in water and crystallises from absolute alcohol in large shining plates. C6&( CH,) So3K + iHzO is a similar compound crystallking from alcohol in plates resembling naphthalene. Metatohenesulphonic chloride C,H,( CH,) SOaCl is a limpid pale- yellow liquid having a penetrating smell. It does not solidify at -lo" and is not decomposed by water even at 130'. Ammonia con- verts it into C6H4(CH3)SO2.N&,crystallising from water at 40" in large plates and at 20" in thin needles melting at 90"-91". Metatolyl sulphydrate c6H4(CH3)SH,is formed by acting with th and hydrochloric acid on the chloride. It is a heavyrefractive liquid having a powerful smell and attacking the skin.Boiling dilute nitric acid converts it into the disulphide (C6H4(CH3)S)2, an oily liquid boil- ing at about 150". Crystallised bromotoluene being a para-compound can yield only two sulphonic acids and both have been here described. ' Of these the @-compound formed by replacing the bromine with hydrogen and treating the resultbg toluene with sulphuric acid is converted by fusion with potash into salicylic acid. The two sulphonic acids derived from the solid bromotoluene have therefore the following constitution :-Br The liquid bromotoluene is most probably an ortho-compound because bromine acts on the aromatic hydrocarbons in a similar waz ORGANIC CHEMISTRY. to that of sulphuric acid and nitric acid which latter always produce simultaneously a para-compound and an ortho-compound.By re-placing the bromine in the sulphonic acid with hydrogen metatoluene- sulphonic acid is produced and therefore the constitution of ortho-bromotoluene-sulphonic acid is expressed by one of the two following formulse :-In the last part of the paper Huebner discusses therelations existing between the composition of salts and their water of crystallisation and points out that all the acids derived from orthobromotoluene form with the dyad metals salts most of which contain two molecules of water, whilst those of the alkali-metals contain generally half a molecnle. The conclusion consists of a discussion on molecular compounds and quantivalence. . c. s. Action of Potash on the Monochlorophenol boiling at 218O By A.FAUST (Deut. Chem. Ges. Ber. vi 1022-1023). THISreaction according to Petersen and Baehr-Predari yields hydro- quinone. This the author cannot confirm ; he obtained only resorcin and consequently this monochlorophenol as well as paraphenolsulphonic acid and the non-volatile nitrophenol belong to the 1 4series. c. s. Researches on the Isomeric Cresols and their Occurrence in Coal-tar. By M. S. SOUTHWORTH (Ann. Chem. Pharm. clxviii 267-276). FROXthe ease with which thymol is converted by oxidation into a quinone it was thought probable that the cresol which is obtained from that body by removal of propylene would under similar treatment furnish the unknown toluquinone. Experiment however did not con- firm this idea.But although toluquinone has not been obtained certain substit;ution-derivatives of it are known. Borgmann has prepared tri- chloro-toluquinone by acting with hydrochloric acid and potassium chlorate upon the cresol from coal-tar. This cresoi however is un-doubtedly a mixture of at least two isomeric compounds and the expe- riments of Borgmann give no clue as to which of the three cresols is the parent of this trichlorinated derivative. The author’s experiments were undertaken partly in order to clear up this point and partly to gain further knowledge of the chemical constitution and properties of these bodies. MetacresoZ.-This is the cresol from thymol. By treating it with hydrochloric acid and potassium chlorate the author obtained dichloro- ABSTRACTS OF CHENICN; PAPERS.tolumetaquinone but by protracted action of the reagents he did not succeed in getting a body containing a larger proportion of chlorine. This compound crystallises fmm alcohol in yellow transparent tables which become brown on exposure to liglst It is slightly soluble in water but dissolves in alcohol and ether. It may be sublimed but at the same time undergoes partial decomposition. Solution of sulphurous acid converts it very readily into the corresponding hydroquinone CsHC12.CHs(OH) a colourless body which when crystallised from water retaius water of crystallisation pfoloably 2K20.It melts between 167" and 169" and may be sublimed without decomposition. By treat-ment with acetyl chloyide it furnishes an acetyl derivative which crys- tallises from alcohol in small clustering needles melting between 12'2" and 124".Dichlorotolumetaquinone acted upon by sodium amalgam did not yield toluhydroquinone. Paracresol.-This componnd subjected to the action of hydrochloric acid and potassium chlorate gave dark-coloured uncrystallisable pro- ducts from which no definite result could be obtained and which in the opinion of the author contain no chlorinated quinone. Orthowesol.-A fraction boiling at about 190" was employed. This undoubtedly contained a little paracresol but as just stated the para- modification furnishes no quinone and therefore any body of that nature produced must be an ortho-derivative. Treatment with hydrochloric acid and potassium chlorate resulted in this case in the formation of st.yellow body crystallising in shining transparent lamina which proved to be a mixture of di- and trichIoro- toluorthoquinone. Borgmann obtained precisely the same result in operating upon the cresol from coal-tar. When this mixture of chloroqixinone was reduced by sulphurous acid a mixture of the corresponding di- and tiichlorohy droquinones was formed and by distillation with water their separation was effected without difliculty the former being easily volatilised in vapour of water the latter remaining in the residue. Dichlorotoluorthohydroquinone C6HC1,.CH3.(OH), melts at 119"-121" sublimes easily and crystallises from hot water in feathery needles. Trichlorotoluorthohydroquinone crystallises from the solution left after distillation in long needle-shaped crystals.It melts at 211"-212". This was the melting point found by Borpann for his trichlo- rotoiuhydroquinone obtained from coal-tar cresol which also agrees with this compound in the rest of its properties. It would therefore appear that the two compounds are identical and hence that orthocresol is a constituent of the cresol from coal-tar. W. A. T. Pentabromoresorcin and Pentabromorcin. By C. LIEB E RMAN N and A. DITTLER (Ann. Chem. Pharm. clxix 252-269). A CONSIDERABLE portion of this paper is occupied with a detailed account of experiments on bromoresorcin the results of which have been already published (Deut. Chem.Ges.Ber.,v 1100,and this Journal [2] xi p. 502) ORBAXE CHEXISTRY.63 stating in addition that all their attempts to convert the tribromoreaor- quinone into tribromoresorcin or pentabromoresorcin have been unsuc- cessful. Pentabromorcin nndergoes a decomposition similar to that of the resorcin compound both when treated with a solution of silver nitrate and when snbrnitted to the action of heat; in the latter case however the reaction is more difficult of control than with thexsorcin derivative the molecule of bromine liberated attacking the tribromor- ciquinone. This new substance crystallises from chloroform in minute needles of a bright yellow colour. Pentachlororesorcin,. when heated sublimes unclianged. C. E. G. Synthesis of Anthracone and Dimethylanthracene. By W. A.VAN UORP(Ann. Chem. Pharm. clxix 207-5220). WHEX xylyl chloride prepared by the method of Lauth and Grirnaux (Atziz. Chem.Pharm.,cxlv 115) is heated to 210" with twice its voliime of water for twelve hours a thick oily liquid of aromatic odour is obtained. This when submitted to fractional distillation may be separated into a yellow volatile oil and ~~~et~~lan~~rae~~ze which passes over as a semisolid mass towards the close of the operation ; the proportion of the latter is but small and considerable loss is experienced in purifying it from the repeated pressings sublimations in a current of carbonic anhydride and crystallisations from glacial acetic acid necessary for that purpose. It forms large glistening scales very similar to anthracene in appearance which melt about 200'.By oxidation with chromic anhydride in a glacial acetic acid solution it forms two quinones one of which is yetidily soluble in glacial acetic acid melts at 153",and sublimes in thin scales ; the other is soluble wit,h difficulty in the acid and sublimes at a high temperature in yellow needles ; these quinones do not yield compounds analogous to alizarin. The oil previously mentioned gives more dimethylanthracene by re-peated fractional distillation but could not itself be obtained in t.he pure state ; it is probably however xylyl-zylene as when passed through a red-hot tube filled with pumice it splits up into dimethylanthracene and hydrogen in the same manner t.hat the hydrocarbon benzylbenzene Cl,Hl, obtained by the action of water on benzyl chloride yields anthracene.Dibl.onzodimetlzyZaiithl.ncene isprepared by adding a solution CI6Hl2Br2 of bromine in carbon sulphide to one of dimethylanthracene in the same solvent; on evaporation a yellow crystalline mass is left which is easily soluble in benzol ether and absolute alcohol. It is best recrys- trtllised from glacial acetic acid when it forms yellow needles melting at 154'. These are decomposed by red-hot lime with formation of dimethylanthracene. The second and third sections of this paper "The Action of Water at 64 dRSTRACTS OF CHEMICAL PAPERS. 200"on B;enzyl Chloride," and "The Behavionr of Benzyltoluene at a Red-heat," have been already noticed (last volume p. 500). The author concludes by observing that the formula of anthracene CsH4-CH 11 ,is inadmissible as it cannot be derived from benzyltoluene CJ%-CH C6&-CHz-C,H*-CH3 by the elimination of H4; the formula 1 C6H4/cH\C8H(',is however compatible with that of benzyltoluene 'CH' just given namely c6&<g2\c6a6 The methods employed for the synthesis of anthracene and dimethylanthracene point out the way by which the higher homologues of anthracene may possibly be obtained.C. E. G. Chlorination and Iodination of' Anthracene. By T. BOLAS (Chemical News xxviii 167). WHENanthracene was digested for some days with antimony pent% chloride a current of chlorine being at the same time passed into the mixture the greater part of the anthracene was carbonised but on subjecting the product to distillation it was found to yield a crystalline mblimate.A portion of this sublimate dissolved in hot benzene from which it separated in crystalline crusts which melted at 236* 247" and 252' after one two and three crystallisations. That portion of the sublimate which was insoluble in benzene yielded on sublimation beautiful needles which melted above 330° and contained an amount of chlorine nearly corresponding with that required by the formula C&LH4. It is however probable that this substance is either derived from some impurity in the anthracene employed or from a hydrocarbon formed by the polymerisation of anthracene and that the true hexa- chloranthracene is to be found in the portion soluble in benzene. When anthmcene is fused with iodine hydriodic acid is evolved even if the temperature does not rise above 155" and the greater part of the anthraceue is carbonised but a small portion of matter soluble in benzene or acetic acid is produced.When a solution of iodine in phenol is boiled with anthracene hydriodic acid is evolved. By moderating the violence of the above reactions and assisting the action of iodine with an oxidising agent the author hopes to obtain more definite results. T.B. The Aotion of Pyromellitic Acid on cc-Naphthol. By J. GRABOWSKI (Deut. Chem. Ges. Ber. vi 1065-1069). OF the numerous compounds which may be produced by the action of pyromellitic acid on a-naphthol the most important from its analogy with the phthalic acid and carbonic acid compounds is yyromelZitei7a-tetrGa-naphtholanhydride C6H,(COOH)r + BC,oH,OH 7-6HzO = C,H3,O6.ORUANIC CHEMISTRY. 65 This is formed when one molecule of pyromellitic acid is heated with four molecules of a-naphthol in an oil-bath to 300". The product after being exhausted with boiling acetone and purified by fractional crystallisation from phenol yields microscopic crystals which have the composition C,H,Os + C6H,0H[,and lose their phenol when heated to 260". Frorn the mother-liquors the compounds a-and 6-pyornellitein-tetra-a-nap htholhemianhy dride are obtained the first 2C50H2807, C6H50H in thin plates the second in very slender needles they lose their phenol when dried at 260" and are reduced to C50H2807.In the acetone solution the compound .I-pyromellitein-tet,.a-a-~~(~p htholhemianhydride is found.It melts at 265" and when dried at 150" has the composition C50H2807.On heating one molecule of pyromellitic.acid with three of a-naphthol to 250" as long as water escapes and removing the excess of naphthol by distillation in a current of aqueous vapour a brownish- black mass is left This when purified by repeated solution in potash precipitation by acid and solution in ether forms a brown powder tri-a-napktho~2/ro~~~~Zl~t~i~ acid which has the composition C40H2408 and is readily soluble in alcohol ether and acetone. It dissolves in alkalis with a deep green colour. T?.i-a-na~litholiiei?,ianh2/dro~~?.o?nellitAic acid C4,H2,07,is produced together with the last mentioned compound when a mixture of one molecule of pyromellitic acid and three of a-naphthol is heated to 280"-300".It is a yellowish brown powder soluble with difficulty in cold alcohol or ether. It yields a fine blue solution with alkalis. C. E. G. Carvol and Carvacrol By A. KEKULEI and E. FLEISCHER (Deut. Chem. Ges. Ber. vi 1087). CARTTOL is obtainable from oil of carraway (Carurw carvi) by fractional distillation and boils at 224.5"to 225". It can however be more readily obtained pure by converting it into the crystalline sulphuretted hydro- gen compound discovered by Varrentrapp and decomposing this by potash care being taken to allow the alcoholic potash to act for a short time only and at the ordinary temperature. On treating it with crystallised orthophosphoric acid much heat is evolved and the carvol becomes converted into its isomeride carvacrol (which as shown in a former paper is identical with campho-cresol or oxycymene derived from cymene-sulphonic acid j.So great indeed is the heat evolved during this intramolecular interchange (wzolecu-Zare Umlageru?zg) that the action becomes explosive unless the carvol is diluted with carvene. For this purpose the crude oil of carraway can be used; 5 parts of acid to 50 of carvol suffice. The result- ing carvacrol is obtained pure by solution in potash precipitation by an acid and distillation. It boils at 232"-232.5" (236.5" to 237" when the whole mercury column is in the vapour). Phosphorus trisulphide converts carvacrol almost wholly into cymene.The pentasulphide also forms thiocymene. The same results are obtained with carvol only little or no cymene is thus obtained with the pentasulphide. Both cymenes give on oxidation ordinary toluic acid (melting point 1~5"--176") and terephthalic acid. The thiocy- YOL. XXVIT. F ABSTRACTS OF CHEMlCAL PAPERS. mene in each case appears to be identical with that from camphor giving the same characteristic metallic compounds the crystalline mercury salt melting at 108~5"-109"in each case. Hence oxycymene (carvacrol) is isomeric with thymol these two bodies representing the only two theoretically possible modifications of hydroxylated cymene (this hydrocarbon being 1:4 propyl methyl-benzene). Just as thymol gives propylene and y-cresol when treated wikh phosphoric anhydride so carvacrol yields propylene (yielding a bromide which distils perfect,ly at 142")and a cresol not yet investigated.Similarly thymol gives thymotic acid melting at 120",on treatment vith sodium and carbon dioxide. Carvacrol gives by the same process camacrolic crcid melting at 133"-134". Both acids are indicated by t.he formula C6H2 gz {L and give (like salicylic acid and all acids prepared synthetically by Kolbe's reactiou) a blue coloration with ferric chloride. The action of oxidising agents on cayvol 'and carvamol has not as yet given any definite results excepting the production of oxalic acid. When car- vacrol is fused with caustic potash two acids are produced resembling those obtained by acting in the same way on the sulphotoluic acid corresponding with thiocymene.Possibly these are oxytoluic and oxyterephthalic acids. Phosphorus pentachloride acts on carvacrol as on all phenols a chlorocymene being formed together with a solid crystalline tertiary phosphoro-cymene ether volalile with partial decomposition. The chlorocymene boiled at 214' and gave by oxidation monochlorot oluic acid melting at l84"-186". Researches on these and tlie corresponding bromo-derivatives are contemplated SO as to throw light on the positions of the hydroxyl group in the two isomerides thymol and carvacrol respectively. The sulpho-acid of carvacrol is solid and crystalline and gives crystalline salts when oxidised by manganese dioxide or potassium dichromate and dilute sulphuric acid.Considerable quantities oE thymo;l are produced idslzticnl with that obtaiwed f~o~n tlzynol melting at 46" giving a hydroyuinone melting at 139"-140° and so on. The identity of the quinone thus obtained from each of the two isomerides necessarily follows from the ascription of the formula?- CH3 IC /\CH CH 1 IfCH CH and I I1CH C.OH \/c I I C3& C3H7 to the two isomerides and it also follows that the 1:3 position cannot OROAXIC CI3EMIrjTRP. be that occupied by the hydroxyls in a hydroquinoiie or the oxygen in quinone (the 1:4 position of the hydrocarbon radicals in cymene being granted Le. toluic and terephthalic acids being taken as 1:4 benzene derivatives). A quinone must therefore be either a 1:2 or a 3 :4 derivative and the latter alternative is excluded if it be assumed as is usual that resorcin is a 1 4 derivative.Attempts to convert thpd iuto its isorneride carvamol or vim vemd are contemplated. These may probably be realised by means of carvol which have not impossibly an intermediate formula analogous to that of ethylene oxide. C R. A. W. Note by Abstractor.-It would be of great interest to determine the “heat of combustion ” of the three isomerides carvol carvacrol and thymol. The evolution of heat during the transformation of carvol into its isomeride of higher boiling point carvacrol would indicate that the heat of combustion of the latker is less than that of the former just as the heat of combustion of hesperidene boiling at 178” is pro- bably less than that of the terpene of nutmeg-oil boiling at 163” (this Journal [el xi 694).Favre and Silbermann have shown that acids of the acetic series develop less heat on combustion than their respective isomerides of the conipound-ether series these latter boiling at 70” to 90” lower than the former; also that the higher members of the olefine family (possessing higher boiling points) have smaller heah of combustion than the lower members of that family so that it is not impossibly a general rule that of a series of isomedes that o”iLe has the 11ighest boiling poiizt which has the leust heat of combustion Ls. which possesses the least of what is often called “potential energy,” but which may perhaps be more conveniently termed intriiuic chemical etwrgy; or in other words the formation of an isomel-ide of higher boiling point from its constituent elements is attended with the evolu- tion of more heat during combination i.e.there is greater “affinity ” between its constituent elements than is the case with an isomeride of lower boiling point. As pointed out (7oc. &A),* this result is not the same as that which might be expected from Thornsen’s recent investigations nor is it in accordance with the relative degrees of stability of the dibromides of certain terpenes when heated. On the other hand Favre and Silber- mann’s experiments lead to the conclusion that in the case of certain terpenes the higher the boiling point the greater the heat of combus-tion.From the abstractor’s results however together with the recent ones of Riban it appears probable that the substances examined by Fane and Silbermann were not pure terpenes but contained cyineue. C. It. A. W. * In the paper referred to (this Journal 1873 p. 694) by an unfortunate erratum the sense is wholly inverted. On line 7 for “ a result q&e in harmoily with Julius Thomsen’s results,” read “ 8 result lzot quite in harmony with Julius Thomsen’s results.” ABSTRACTS OF CHEMICAL PAPERS. New Method of Forming Orthotoluic Acid. By RUDOLPH FITTIG RAMSAY and W~LLIAM (Ann. Chem. Pharm. clxviii 202-253). THATsalicylic acid belongs to the " ortho " group has been indirectly proved by V. Meyer ; for the ordinary bromo- and sulpho-benzoic acids may be resolved on the one hand into oxybenzoic acid and on the other into isophthalic acid.As all attempts to derive phthalic acid from salicylic acid were fruitless the indirect proof furnished by Meyer has been questioned. It was with the view of confirming the indirect proof of &$eyer and of connecting salicylic and phthalic acids directly with each other that the authors undertook their investi- gation. By the action of sulphuric acid on toluene two different toluene- sulphonic acids were formed ; one which exists in larger quantity is undoubtedly " para-;" the other has been termed by Anna Wolkow metatoluene sulphonic acid. This so-called meta-acid when treated with fused potassium hydrate has been converted first into a cresol and finally into salicylic acid.Could it be converted into a toluic acid and oxidised the position of the lateral groups in salicylic acid would be determined. The two acids were separated as much as possible by crystallisation of their potassium salts from water. The more soluble of these pre- sumably ortho was distilled with potassium cyanide and the cyano- toluene produced was oxidised to toluic acid. As a mixture of two salts was employed two toluic acids were obtained. These were sepa- rated by crystallisation of their calcium salts from alcohol of 0.83 sp. gr. after most of the para-salt had been removed by crystallisation from water in which it is less soluble than the ortho-salt. The calcium orthotoluate crystallises from alcohol in feathery tufts.The acid melts at 102". A nitrotoluic acid melting at 143"was formed by treatment witb concentrated nitric acid. The sole products of oxida-tion of orthotoluic acid were carbonic anhydride and water. Before how- ever concluding that metatoluic acid was not present it was necessary to oxidke the residue ; if it were there isophthalic acid would be found as one of the products of oxidation. But no trace of this acid was actually found terephthalic acid alone separating out on oxidation with potassium dichromate and sulphuric acid. As the three toluic acids correspond with the three phthalic acids these results aEord direct proof that the lateral groups in Ralicylic acid occupy the relative positions 1 2. Nifroparatoluic acid was also prepared.It melts at 188"-189" and is deposited from alcohol in monoclinic crystals. The barium salt crystallises with four molecules of water. It appears to be pecu- liar to ortho-compounds or at least to many of them that they can be distilled with water vapour. Salicylic and phthalic acids and ortho- nitrophenol are all volatile whereas the corresponding metn- and para-compounds cannot be distilled. This may prove a convenient means of separating ortho- from meta-compounds. W. R. ORGANIC CHEXISTRY. 69 Metatoluic Acid. By CARLBOTTINGER RAMSAY and WILLIAM (Ann. Chem. Pharm. clxviii 253-261). THEdescriptions of metatoluic acid by Ahrens Tawildarow Wurtz and von Richter differ widely from each other. Could COZ be with- drawn from uvitic acid a toluic acid would be obtained the position of whose lateral chains would admit of no doubt for uvitic acid is derived from mesitylene.Bottinger heated calcium uvitate mixed with half its weight of calcium hydrate for 8-10 hours in a bath of molten lead whereby a toluic acid was obtained which after sublimation fused between 109"-110" and confirmed the observations of von Richter. The barium salt after drying in the air was found to crystallise with !7+ molecules of water. On oxidatioii it yielded isophthalic acid almost quantitatively. Ramsay treated xylene with bromine to form bromoxylene and oxidised it with potassium dichromate and sulphuric acid. The greatest difficulty was experienced in decomposing the insoluble chromium compound which resulted but by repeated alternate boiling with hydrochloric acid and potassium carbonate the salt was decom-posed.The mixture of acids was separated as far as possible by crystallisation of the calcium salt. The less soluble of these salts which crystallised in long needles gave an acid fusing between 205" and 207". It was treated with sodium-amalgam to remove the bromine and the residue was acidified and distilled with water-vapour. From the metatoluic acid which came over the calcium and barium salts were made ;the former resembles calcium benzoate very closely in appearance and crystallises with three molecules of water ;the latter crystallises in small glittering scales and contains two molecules of water. The acid from these salts fused at 9lo-92O corresponding with the observations of Ahrens.It was found however that on crystallisation from alcohol a mixture of well formed monoclinic crystals and warty clusters was deposited which could easily be separated mechanically. The former melted at 106" the latter at 176" showing that a mixture of meta- and para-toluic acids had been the means of leading Ahrens to false con- clusions as to the melting point of metatoluic aoid. W. R. Benzylated and Di-benzylated Acetic Acid. By LYDIASESEMANN (Deut. Chern. Ges. Rer. vi 1086). WHEN the product of the action of sodium on acetic ether was treated with benzyl chloride in an oil-bath for sevei-al hours at 200" and water a,dded to the product a red-brown oil separated which by fractional distillaf,ion yielded unaltered benzyl chloride a liquid boiling at 200" -300" and a heavy viscid oil boiling above 300".The middle portion boiled for the most part at 240"-260" and gave ttn oily precipitate becoming crystalline on standing after saponification with potash and addition of hydrochloric acid. After recrystallisation this substance melted at 47" boiled at about 280" and had the composition C9HI0O2 giving a barium salt C,H,Sa60~. Hence this substance was beiixyhtcc;! acetic acid formed by the reaction- 70 ABSTRACTS OF CHEM[CAL PAPERS. C€I-I,.Na CH,.C,H, + C7H7.Cl= NaCl + I I CO.0.CPHS CO.O.C,H,. Rydrocinnamic acid (benaylacetic acid) has this formula and boils at 2180" ; its melting point being 47". The viscid oil above mentioned when treated with potash and then with hydrochloric acid gave a bulky white precipitate which cohered together and became resinous ; this was distilled in a current of carbon dioxide mid crystallised from ligroin ; white prisms were thus obtained insoluble in water but readily soluble in alcohol and ether and melting at 85O.011 analysis these were found to have the com-position C16H1602, the barium and silver salts being respect'ively Cl6HI5BahO2, and Cl6Hl5AgOZ. Hence this body was dibewzylated acetic acid formed by the reaction- CHKa2 CH (C7&), I + 2C7H7Cl= 2NaC1 + I GO.0.C2H GO.0.C2H3. Further researches on the derivatives of this substance are in pro-gress. C. R. A. W. Bromo-Cmphocarbonic Acid. By J DE SANTOS E f3rLt.a (Deut.Chem. Ges. Ber. vi 1092). CAMPHOCARBONIC acid is obtained together with the comparatively un-stable borneol-carbonic acid by acting with carbon dioxide on the mixture of the sodium derivatives of camphor and borneol obtained by acting with sodium on camphor ; it can be extracted by ether from its aqueous solutions and separates from the solutions of its salts on addition of hydrochloric acid either at once or on standing according to the concentration of the liquor. It melts at 118°-1190. Bromine acts on camphocarbonic acid .energetically evolving hydrobromic acid and forming nzonobrcrmocamphocarbo~2~cacid CloHl4Br0.CO.0H.; rise of temperature during the action must be avoided otherwise carbon dioxide is aalso evolved. The acid is readily sduble in alcohol and ether and but little soluble in water ; it melts at 109"-110" being partially decomposed into bromocamphor and carbon dioxide at 65' ; on boiling its alcoholic solution the same result ensues the bromocamphor produoed melting at 76'.Its salts also are easily decomposed; the barium and silver salts have respectively the formule (CllHl4BrO3),Ba and C11EIilBr03.Ag. C. R.A. W. Terebic and Pyroterebic Acids. By W. CAR, L E T ON WIL I I AM s (Deut. Chem. Ges. Ber. vi 1094). 200 GRAMS of turpentine oil purified by repeated distillation are oxidised by 800 grams of nibric acid sp. gr. 1-25 the mixture being heated to 80" ;when the reaction has ceased the whole is heated for 24 hours on ORGANIC CHEMISTRY the water-bath nitric acid of sp.gr. 1.4being added from time to time until the resinous matter first formed disappears on further oxidation ; no terephthalic acid was found in the products. After evaporation the liquor deposits on standing crystals of terebic acid and of acid ammo- nium oxalate. The terebic acid thus obtained melted at 175" (Caillot found 168" as the melting point). The author confirms Swanberg and Eckmann's results viz. that terebic acid forms two classes of salts tsrebutes C1H9M04,and the so-called din-terebates C,HloM20,; the silver salts of these formulm are anhydrons the barium salts being (C7H9O4),Ba + 2H20 and C7H,,Ba05 + 5H20 the former being non-crystalline; a silver salt C7HgAgOl.C7H,20,was also obtained which lost no water at 110".By dry distillation terebic acid forms pyroferebic acid carbon dioxide being evolved ; almost the calculated yield is obtained. The pure acid boils at 210"; the silver salt CGHyAgOz,and the readily soluble crystallisable barium salt (CGH902),Ba+ 5Hz0have been obtained. Bromine unites with pyroterebic acid forming a dibronzocaproic acid C6Hl0BrZO2, which is reduced again to pyroterebic acid by sodium-amal- gam. Attempts to form caproic acid by the action of sodium amalgam on pyroterebic acid gave no result but strong hydriodic acid formed a vola-tile acid possessing the odour Gf caprio acid and giving a silver sdt containing the same percentage of silver (fouud 48736 ; calculated 48.43). On fusion with caustic potash pyroterebic acid forms acetic and butyric acids (Chautard).The author him verified this statement and shows moreover from the properties of the calcium and silver buty- rates obtained that isobictyric acid is produced and not the ordinary butyric acid. Dilute nitric acid dso yields isobutyrio acid together with oxalic acid. From this the following formula is attributed to pyroterebic acid :-CH3 )CH-CH=CH-CH-CO-OH. CH3 whence the formula CH3 \CH-C-CH-CO.OH CR3' II I CH OH (sic) for terebic acid would appear the most probable were it not alto- gether without analogy. CH [Query yCH-C-CH-CO.OH ? 1 CE3' II I CO OH Nothing but acetic acid has been obtained by the action of oxidisillg agents on terebic acid ; nitric and chromic acids have no action on it nor has oxide of silver ;melting caustic potash gives hydrogen and an ABSTRACTS OF CHEMICAL PAPERS.acetate whilst hydrogenising agents have no action on it. Phosphorus pentachloride is reduced to the trichloride substitution of hydrogen by chlorine taking place ; chloroterebic acid C7H,C10a,is t.hus formed melting at 189*5"-190" and giving salts analogous to the terebates and diaterebates ;sodium amalgam reconverts it into terebic acid. C R.A. W. Podocarpic Acid. By A. C. OUDEMANS, Jun. (Deut. Chem. Ges. Ber. vi 1122-li24). A RESINOUSexcrescence which was found on a Javanese tree Podocnrpus cupresfiina was found to consist of a resinous acid which separates fiom dilute alcohol in rhonibic crystals or when water is added to the alcoholic solution in small white needles.It is insoluble in water almost insoluble in benzene chloroform or carbon sulphide but easily soluble in ether alcohol or strong acebic acid. It melts at 187"-188° and is decomposed at about 320". Its specific rotatory power is /* 136" at 1'7') and its analysis led to the formula c,;H&. The author considers podocarpic acid to be monobasic and to yield salts formed on the following types :-I. C17H21Mf03. 11. Ci,H2oM'203 111. C17H21M03 + ClpH2203. The sodium sakt C17H2,Na03 + H20,forms slender needles soluble in about three parts of watw. The copper salt C17H20Cu03, was obtained by adding a solution of the sodium salt to copper sulphate. Ammonia dissolves podocarpic acid and tbe solution deposits a very soluble salt which is considered by the author to belong to the first class ;but on standing the solution deposits slightly soluble crystals of an acid salt which gradually loses its ammonia on exposure to the air podocarpic acid being left behind.Mononitropodoca,yic acid and diizitropodocmyic acid were obtained by warming podocarpic acid with dilute nitric acid. The former is a yellow crystalline substance slightly soluble in alcohol. Its salts are red or yellow and have a metallic reflex. The salts containing 2M are easy to prepare but those containing M are difficult to obtain. The barizcm salt C17Hl,?3a(N02)03+ 7Hz0,has a beautiful dark-red colour and metallic lustre. The dinitro-derivative is moderately soluble in alcohol and forms crystals which resemble those of potassium femocyanide but appear to belong to the rhombic system.The barium salt C17H1,Ba(N0z)203+ 4H20 forms reddish brown plates which polarise light. The following derivatives of podocarpic acid have been obtained and will shortly be described in the Annalen der Chemie I'.€3. ORGANIC CHEMISTRY. The Constitution of Podocarpic Acid. By A. C. OUUEXIANS Jun. (Deut. Chem. Ges. Ber. vi 1125-1128). BYdistilling the calcium salt of podocarpic acid a tar was obtained which when distilled with water yielded paracresol and a hydrocarbon having the composition C9Tll*; this the author calls carpene. The portion which did not volatilise with water was distilled im vacuo when it yielded hydrocarpot C16H200,a yellowish viscid aromatic liquid boiling at 220"-230" in a vacuum; and methanthrol C15Hi20,a solid sub- stance melting at about 122°C.This substance is probably a secondary product as when hydrocarpol is digested at t'he ordinary pressure carpene paracresol methanthrol and probably marsh- gas are formed. Carpene C9Hl4,resembles the terpenes and becomes resinified on exposure to the air the product having the composition C18H,0,. Carpene boils at 155"-157" has an odour recalling that of turpentine and that of storax and yields a bromo-derivative C9Hz5Br. The author considers that the formula OH c6HZ {:gH GH15 expresses the constitution of podocarpic acid. When podocarpic acid is heated with zinc-dust a hydrocarbon, Ci5HI2,is produced which the author calls metlzanthrene.It is a fluor-escent body melting at 117" and boiling above 360". It combines with picric acid and yields a quinone on treatment with chromic acid. Further details will be published in the Annaten der Chernie. T. B. Ortholuidinesulphonic Acid. By H. LI M P R I cH T (Deut. Chem. Ges. Ber. vi 1008-1010). WREN pseudotoluidine is heated with fuming sulphuric acid it yields two isomeric sulphonic acids C7HsN(S0,H). OrtlLotoZuidineszcl-phonic acid is sparingly soluble in cold water and crystallises in yellowish oblique rhombic plates or prisms containing one molecule of water C,&N( S0,K) -f-&H,O ; it forms silky crystals and dissolves readily in water. C7H,N(S03Na) + H,O forms feathery crystals. [C,H,N( SO,)],Ba + 3H,O crystallises in six-sided prisms which are freely soluble.2[C7H,N( SO,)]Pb + I&H,O (?) forms compact six- sided prisms. C7H8N( S0,Ag) is sparingly soluble and crystallises ixi small white plates. By fusing the acid with potash it yields pseudo- toluidine and on adding bromine to the aqueous solutiop tribromo-toluidine is precipitated and dibro??zotol~idi?2eSu~77L0~z;2.iC acid remains in solution. Tribromotoluidine crystallises in long white needles melting at 112O while the same compound prepared by the direct action of bromine on pseudotoluidine was found to melt at 105°-106". The dibrominated sulphonic acid is readily soluble in hot water and alcohol and crystallises in long whit'c needles with one molecule of water. [C,H,Br,N( SO3)IzBa + 4H2O crystallises in long white needles.ABSTRACTS OF CHE';\IICAL PAPERS. [C7H6Br2H(SO,)],Pb + 3H20forms prisms and does not freely dis-solve. The silver salt is a precipitate consisting of needles and darkens when boiled with water. On suspending the acid in strong alcohol cooled to 0" and passing nitrous acid into the liquid the diazo-compound C7H,N2S03,is obtained as a white explosive powder which readily dissolves iu water. By heating it with absolute alcohol under pressure a tolueneszdphonic acd is formed which on evaporation is obtained in form of a syrup ; its ehloricZe does not crystallise but the ninide forms prisms melting at 148". By acting with hydrobromic acid on the diazo-compound it is converted into b~omotol?cen estslphonic acid which does not! crystallise.[C7H6Br(SO,) J2Ba+ 3H,O forms white warty crystals. The chloride is a syrupy liquid amd the cctuide forms microscopic crystals melting at 156"-15 7". Cresolsulpho~zicacid was produced by heating the diazo-compound with water ; it forms vcry deliquescent crystals. [C7H70(SO3)IIBa+ 2$H20 is readily soluble and forms tnfts of needles. [C)7H70(SO3)],Pb+ 2$H,O is a similar body. These sul- phonic acids are isomeric with those already known. The second pseudotoluidine-sulphonic acid is very soluble and forms indistinct crystals. c. s. Action of Sodium-amalgam on Acetophenone. By A. EMM E E-LING and c. ENGLER (Deut. Chem. Ges. Ber. vi 1005-1006). BYacting with sodium-amalgam on a solution of acetophenone in dilute alcohol secondary phenylethyl alcohol is formed together with the cor- responding pinacone.The alcohol CsH,.CR(OH)CH, is a colourless very refractive liquid boiling at 202*-203" and having a very dis- agreeable smell. The pinacone (C,H,.COH. CHS)O has already been described by the authors,' who then believed it to be the secondary alcohol. It crystallises from dilute alcohol in long pointed crystals and from secondary phenylethyl alcohol in short quadratic prisms. c. s. Propiophenone. By T. I). BARRY (Deut. Chem. Ges. Ber. vi 1006-1008). Yropiopheno.ne (ethyl-phenyl ketone) was prepared by distilling a mixture of calcium benzoate and propionete as a yellowish very refrac-tive liquid boiling at 208"-210" ; it does not combine with the acid sulphites of the alkali-metals.By adding it in small portions to well-cooled fuming nitric acid it is converted into a solid mononitro-compound C6H4(N02) C0.CzH5,crystallising from absolute alcohol in small but well-defined prisms melting at 100". A syrupy modification of this compound is obtained by using nitric acid which has been gently heated AiiZido27ro~iophcnone,CsH,(NH,) C0.CH3,is formed by acting wit,h tin and hydrochloric acid on a solution of the solid nitro- compound in absolute alcohol; it is a syrupy liquid smelling like strawberries and forming a crystalline hydrochloride which yields with platinic chloric the crystalline compound [C,H4(NH2)C0.C2H3,HCl]2. PtCI,. ORGANIC CHEJIISTRY. Recolzdtzry Plientjl-propyZ dZcol/,ol C6H5.CH(OH)C,H,,is produced together with its pinacone by adding sodium-amalgam to a solution of the ketone in dilute aicohol it is a liquid boiling at 210"-211 with partial decomposition.c. s. Propyl-phenyl Ketone. By E. SCHMIDT and E. FIEBERG (Deut. Chem. Ges. Ber. vi 498). KETONE, PROPYL-PBENYL C6H5] CO is obtjainable by the distillation of C3H7 an intimate mixture of benzoate and butpate of calcium ; the crude pro- duct contains also benzene butyrone benzophenone and other substances of high boiling point. By fractional distillation a slightly yellow fluid of pleasant aromatic odour and blxrning taste is obtained boiling at 220"-222" and having the specific gravity 0.990 at 15"; at -20' it is still fluid. A regular increase in boiling point is thus noticeable in ketones of the aromatic family ; thus-Methyl-phenyl ketone boils at 199" Ethyl-phenyl ketone , 210" Propyl-phenyl ketone , 220"-222" whence the difference for CH appears to be about 11".Alkaline bisulphites do not combine with propyl-phenyl ketone ; on oxidation with sulphuric acid and potassium dichrornate it yields benzoic and propionic acids with small quantities of acetic acid and carbon dioxide ; sodium amalgam converts it into the corresponding pinacone-CGH.+2H-C3H7 0 I 0 CGH+.2H-C,H,,* which crystallises from alcohol or better from acetone in needles melting at 64" ; simultaneously with this product pseudobutyl phenyl alcohol is formed (phenyl-propyl-carbinol CH C3H7? C. R. A. W.). { 2 Bromine acts on propyl-phenyl ketone giving a combination-product which yields hydrogen bromide on distillation and another product not yet fully investigated.C. R,. A. W. C(C6HB) (C3H;) (OH) a Que1.y ? I C(CGHj) (CSH;) (OH).-C. K.A. W. ABSTRACTS OF CHEMICAL PAPERS. Coerulignone and its Derivatives. By C. LIEB E R 3% A x N (Ann. Chem. Pharm. clxix 221-251). THIS memoir is principally a summary of the papers already published by the author on this subject (see last volume pp. 70 and 1033) con-taining however some additional particulars. Coerulignone is readily changed by reducing agents into hydro-coerulignone yielding a colourless solution with zinc-dust and alkalis or with sodium-amalgam and with tin and hydrochloric acid a white powder ; with zinc-dust at a red heat an oily hydrocarbon is produced wliich solidifies partly on standing.The author prefers hydrochloric acid and ziuc-dust for preparing large quantities of hydrocoerulignone The latter is slightly soluble in ether and almost insoluble in carbon bisulphide ; when heated it yields a distillate which crystallises but at t,he same time the greater part of the substance becomes carbonised. When coerulignone is dissolved in warm concentrated potash-solution a yellow potassium-salt insoluble in the alkaline solution is deposited in a short time ; this decomposed by hydrochloric acid yields a preci- pitate consisting chiefly of hydrocoerulignone. The author also describes two compounds intermediate between coerulignone and hexoxydiphenyl formed by the action of sulphuric acid on coerulignone or hydrocoerulignone ; the former when treated with concentrated sulphuric acid becomes warm and the blue colour at first produced passes into brown.The product washed with cold water and crystallised from spirit in which it is very soluble forms yellow needles ; these dissolve in concentrated sulphuric acid with a brownish red colour and their aqueous and alcoholic solutions give a deep brownish red with ferric chloride. This compound is very difficult to purify ; its composition is represented by the formula C15Hld06, or coerulignone in which one atoni of methyl is replaced by hydrogen ; (0CH3)3 the acetyl-derivative has the formula C,,H { (OC&&O),' By the 'On-tinued action of sulphuric acid on the new compound and also on coerulignone or hydrocoerdignone especially when aided by a gentle heat, the mixture acquires an intense magenta colour ; on adding a large quantity of water a red precipitate IS obtained which speedily becomes brown.It is an amorphous orange-coloured powder having the composition CI1HI2Os or coerulignone in which 2 at. methyl are replaced by hydrogen. These compounds howet-er have not yet been converted into hexoxydiphenyl. C. E. G. Anilidacetonitril. By C. E li G I E R (Deut. Chem. Ges. Ber. vi 1003-1005). THJS compound is readily formed by the action of aniline on mono-chloracetonitril which was prepared by distilling chloracetamide with phosphorus pentoxide and rectifying the product twice over the same substance.Monochloracetonitril boils at 126"-12 7" not however without decomposition as Bisschopixick has stated some hydrochlorje acid being always formed. On heating it with an ethereal solutioil of ORGANIC CHENISTRY. aniline in sealed tubes to 80°-900 and evaporating the ether impure anilacetonitril is left behind as a brown syrup. It is freed from aniline by shaking the ethereal solution with dilute acetic acid evaporating the ether and dissolving the residue in strong hydrochloric acid. By adding sodium carbonate to the solution first a brown resin is preci-pitated and then the base which is again treated with acetic acid &c Anilidacetonitril NC.CK,NH( C6H5),is a thick yellow liquid wliich is decomposed by heat ; it is insoluble in water and dilute acids but dissolves in alcohol ether and concentrated acids.The hydrochloride is a white crystalline mass which is decomposed by water; the sulphate nitrate and oxalate do not crystallise. On heating the base with potsash ammonia is given off and a compound is formed crystal- lising in fine needles and consisting probably of phenylglycocine. c. s. Dinitrosulphocarbanilide. By A. B rtG c KN E R (Deut. Chem. Ges. Ber. vi 1103). WHEN paranitranihe is digested for a long time with the corresponding amount of carbon disulphide sulphuretted hydrogen is evolved and YHCH NO dinitrosulphocarbanilide CS { ~H:C-,R~NO~ is formed. This com-pound crystallises in needles melting at 160"-161° soluble in alcohol and ether almost insoluble in water.The corresponding mononitro-compound pears to result when phenyl-sulphocarbimide and nitran iline act on one another but is difficult to obtain in a suBciently pure state for ana- lysis. C. R. A. W. Oxethenaniline. By E. D EM o LE (Deut. Chem. Ges. Ber. vi. 1024-1026). Tim compound which Ladenburg obtained by heating oxethenepara- midobenzoic acid is also produced by the direct combination of ethene oxide and aniline taking place slowly at the commoii temperature and more quickly at 50". Oxethenaniline N C6H5 ,is a colourless some- { :€&.OH what viscid liquid which dissolves sparingly in water alcohol and ether freely in chloroform. Its aqueous solution is coloured green by bleaching powder.It boils at 280° and has at 0" the sp. gr. 1-11. Its salts are very soluble and deliquescent. [NH( C6H5) (C,H*.OH)ClH] + PtCl forms reddish brown granular crystals which are soluble in absolute alcohol and insoluble in ether Waber decomposes it platinum separating out and a green solution being formed. c. s. ABSTRACTS OF CHEMICAL PAPERS. A New Base from Nitrobenzanilide. By H. H~~BPITER and G. RETSCHY (Deut. Chem. Ges. Ber. vi 1128). THIScommunication refers to a base having the composition Cl3Hl0N2 and already alluded to by the authors (Deut. t%e???. Ges. Ber. vi 798 ; Chem. SOC. J.,xxvi 1147). The double tin-salt obtained by the action of tin and hydrochloric acid on monobenxolated diamido-benzene forms small almost colourless needles ; and by treating this salt with hydro- sulphuric acid the 7cydrocI~Zoride,C1,HlJV2,HCl is obtained in colour-less needles.It must he crys tsllised from dilute hydrochloric acid otherwise it becomes basic on recrystallisation. The free base obtained by adding ammonia to a solution of one of its salts forms colourless needles almost insoluble in water slightly soluble in benzene or chlo-roform and easily soluble in alcohol. It melts above 240". The plntimm suM (C,,Hl,N,),(HCI),PtC1, forms yellow needles. The O,, nitrate C1,HE0N2,HN forms colourless needles. The sdpphate (C,3H,oN2),H2S04, forms tufts of colourless needles. The nitration of the base has been effected. T. B. Nitro-and Amido-benzylarnlde. By J. STRA KO sc H (Deut.Chem Ges. Ber. vi 1056-1063). THEauthor obtains the nitrobenzyl chloride employed in the preparation of these compounds by gradually adding benzyl chloride to fuming nitric acid cooled to -15" until the mixture has a dark brown colour ; it is then poured into cold water and the precipitate after being washed and pressed is crystaflised from alcohol. The attempt to pre- pare nitrobenzylnmine by the action of alcoholic ammonia on this sub- stance wa8 unsuccessfd but more favourable results were obtained by the substitution of aqueous ammonia ; the brown mass resulting from their action on one a3other at 100" is in great part soluble in hydro- chloric acid yielding the hydrochloride of th; seco&h-y nitrobe?axyldmi,m, g:zggjgz> NIH.HC1. It crystallises in lustrous yellow prisms which melt at 'LI2" and are difficultly soluble in water alcohol and hot hydrochloric acid.With platinic cbloridc it forms a double salt (C14H13N304HCI).LPt~l~, crystallising in pale yellow needles almost insoluble in alcohol and in hot water. The free base obtained by pre- cipitating the hydrochloride with soda crystallises from alcohol in large shining plates of a yellow colour. These melt at !No,and are soluble in hot alcohol but insoluble in water and in ether. It seems to be capable of being distilled without decomposition. After the secondary nitrobeiizylamine has crystallised out from the solution obtained by treating the original product with hydrochloric acid a small quantity of an isomeric base may be precipitated from the mother-liquors by soda.Its hydrochloride crystallises in-white nodules which melt at about 1'73" and are moderately soluble in alcohol hot water and hot hydrochloric acid. The free base likewise crystallises in yellow nodules which arc insoluble in water. The portion of the original producc insoluble in hydrochloric acid ORGANIC CIIEXISTR'17. C,H,NO 1CH2\ consists of tertiary mitrobemyZarnine C,H,NO 1CHI,-N and may be C,H,NO,) CH2/ purified by crystallising it first from nitrobenzene and subsequently from glacial acetic acid. It forms white lustrous needles which melt at 163" and are insoluble in water or in ether and only very slightly soluble in hot alcohol. It is also formed by digesting secondary nitro- benzylamine with an alcoholic solution of nitrobenzyl chloride at 100" for about four hours.As the action of aminonia on benzyl chloride yields all three amines it was to be expected that the primary nitrobenzylamine would be found along with the other bases. This however was not the case neither could it be procured from the secondary nitrobenzylamine by treating it with hydrochloric acid at a high temperature. Se'econcJaq a~)z~~~)~en~la??z~~e is produced when the corresponding nitrobenzylamine is reduced by tin and hydrochloric acid. The hydro- CGHANH ]CH?\ chloride C,H,NH,) CH, NH,3HCI obtained by decomposing the tin double salt with sulphuretted hydrogen crystallises in white lustrous scales which are insoluble in alcohol and ether easily soluble in water less so in hydrochloric acid.The platinum double salt, 1c7H6NE2)2} N.3HCl.PtC14 crystallises in large reddish yellow needles easily soluble in hot water but insoluble in alcohol. The free base precipitated from an aqueous sollition of the hydrochloride by soda ci*ystdlises in glistening needles or plates which melt at 106" and are soluble in hot water alcohol and ether. It may be distilled without! decomposition and becomes colourecl by exposure to the air. The sulphate and nitrate form easily soluble needles. C,H,NI-I,] CH,\ Tertiary amz'dobenxylmti?~e,C,,H,$T = C6H,NH2] CH,-\N. The pro-C,H,NH ) CH,/ longed action of tin and hydrochloric acid on tertiary nitrobeiizylamine cause the tertiary amido-compound at first formed to split up into secondary amidobeuzylamine and toluidine ; but if the action of the reducing agent be continued only until the nitrobenzylainirie has dissolved and the tin be at once precipitated by snlphuretted hydrogen a solution is obtained from which soda precipitates the white crystai-line tertiary rt;widobeneylamine.It forms brill :ant octohedrons ~hich melt at 136",and are insoluble in water but readily soluble in hot alco- hol or ether ; it distils unchaiiged. The hydrochloride crystallises in yellow needles which are exceedingly soluble in water hydrochloric acid and alcohol. The platinum-compound is an amorphous yellow compound. The author was unable to obtain primary amidobenzylamine either by treating nitrobenzyl chloride with ammonia and aiumouium sulphide or by the nitration of acetobeiizylarnide ; but by the action of nitro-benzyl chloride on excess of aniline he succeeded in preparing nitro- benzylphenylamine.The product of the reaction when treated wit11 ftydrochloric acid solidifies to a crystalline pulp from which the aniline hydrochloride is removed by means of warm dilate hy drochluric wid ABSTRACTS OF CHEMICAL PAPERS. leaving the hydrochloride of the new base. Nitrobenyl.plLen~Za~~ai?~e hydrochloride CsH4N02)CH2-NEH,HC1 crptallises from hot con-ccntrated hydrochloric acid in white shining scales which are soluble in absolute alcohol but are decomposed by water into hydrochloric acid and the free base The platinum compound forms brown shining scales which are soluble in water and in hydrochloric acid.The free base crystallises in golden-yellow needles which melt at 68" and are soluble in hot alcohol ether and benzol but insoluble in water. Amidobenxy~phelnylnmi~ze.-This base cannot be prepared by re-duction of the nitro-compound with tin and hydrochloric acid the reaction proceeding much further ;but by digesting nitrobenzylplienyl- amine with ammonium sulphide at 100"for a short time distilling off the excess of sulphide and repeatedly crystaflising the product from con- centrated hydrochloric acid arnidobenzylphenylamine hydrochloride C,H4NH2) CH -NHC,H 2HC1 may be obtained in brilliant needles which are easily soluble in alcohol and in water less so in hydrochloric acid. The platinum salt is dark yellow and anzorphous.The free base is precipitated by soda from n solution of the hydrochloride in glistening scales which melt at 88" and are readily soluble in ether alcohol and benzene. c. E. G. The Oxidation-Products of Caryophyllin. By E. MYL I u s (Deut,. Chem. Ges. Ber. vi 1053-1056). THEauthor finds that the properties of pure caryophyllin are those usually assigned to it except that it is completely insoluble in alkaline solutions. Moreover he proposes to double the original formula making it C20H3202, as the temperature at which it sublimes 285" is much higher than that at which its isomeride camphor ClOH,,O,distils namely 285"-250". On adding caryophyllin in suflticient quantity to fuming nitric acid it dissolves with evolution of heat and after a short time the mixture solidifies to a pulp of microscopic white needles.When it is purified, first by solution in ammonia and reprecipitation by an acid and then by repeated precipitation of its alcoholic solution by water a new acid is obtained in ari amorphous condition. Cnryophyllic acid C20H3206, dis-solves in water with difficulty readily in alcohol ether and glacial acetic acid from all of which it separates in an amorphous state. It may however be crystallised from fuming nitric acid. ,Sod.C:.um caryoyhyllate CzoH,,~a~~6.-Caryophyllic acid decomposes sodium carbonate and on evaporating the solution to dryness and extracting with alcohol an amorphous sodium-compound of the new acid is obtained. Xilver caryophyllate CzoH3oAg2O6, is obtained as a yellow amorphous powder on precipitating a solution of the sodium salt with silver nitrate PHYSIOLOGICAL CHEMISTRY.Barium caryophyZtate C20H30Ba06+ 1$H20,is a yellowish precipi- tate insoluble in alcohol diHLicultly soluble in water. The author concludes by observing that although caryophyllin differs in its physical properties from camphor yet there is a certain resemblance since both substances yield acids by oxidation with nitric acid. C. E. G. The Composition of Cascarillin. By C. and E. MYLIIJS (Deut. Chem. Ges. Ber. vi 1051). CAscArtnxA bark contains a crystallisable bitter matter named by its discoverer (Duval) cascarillin. Tuson in his account of ricinine a base obtained from Ricinus comwzunis says that it is very similar to casca- rillin.The authors deny this for in the first place cascarillin contains no nitrogen ; in the second ricinine is a well characterised base while cascarillin is a neutral body and behaves itself indifferently both to acids and bases. The empirical formula of cascarillin is C6H,02. A rational formula has not yet been found. Bromine acts energetically on cascarillin but the resinous product of the reaction was not obtained pure. A nitro-product gave unsatisfactory numbers on analysis. On boiling cascarillin with dilute acids no splitting up takes place it is therefore not a glucoside. G.T. A. The Constitution of Saffranin. By S. E. PHTLLIPS (Chemical News xxviii 30).