ORGAN10 CHEMISTRY. Organic Chemistry. Formation of Tertiary Alcohols. By D. PAWLOW (Deut. Chem. Ges. Ber. ix 1311).-In the formation of these alcohols 2 mol. of the zinc-compound act on 1mol. of the acid chloride. At the same time condensation-products of acetones are formed because the latter are also a product of the reaction- /CH3 CH3.COC1 + Zn(CH& = CH3.C-C1 \0ZnCH3 /CH3 CH3.C-Cl + CH3COC1 = 2CO { EE + ZnClz. \OZnCHs ABSTRACTS OF CHEMICAL PAPERS. The acetone is then further acted upon by the zinc methide for on adding the latter body to acetone mesityl oxide is formed while among the products of the action of zinc methide on propiouyl chlo- ride the oxide C,H,,O boiling at 167-168' could be isolated. Ethylisopropyl ketone boils at 117-119' and is oxidised to acetone and propionic acid.By acting on butyryl chloride with zinc methide and ethide the tertiary alcohol C,H,( CH,) (C,H,) COH was obtained which boils at 135-138" and yields a heptylene boiling at 90-95'. Methylethyl-isopropyl carbinol which was obtained by an analogous reaction boils at 124-127" and its heptylene at 75-80". c. s. Conversion of Acid Chlorides into Alcohols. By D. DJA-KONOW (Deut. Chem. Ges. Ber. ix 1312).-A better yield is obtained by employing sodiixm instead of its amalgam which Saytzeff used. c. s. Cholesterin. By W. E. WALITZKY (Deut. Chem. Ges. Ber. ix 1310) .-Cholesterin from brain yields the chloride C,,H,,Cl. This chloride was heated with the acetates of potassium sodium and silver in presence of alcohol or acetic acid under varying conditions but Berhhelot's acetate was not formed the chloride remaining either un- changed or losing chlorine and being converted into a resin.Alkalis sodium sulphite potassium cyanate and cyanide mercuric cyanide and silver cyanide gave similar results. When the chloride is heated with sodium ethylate the hydrocarbon C,H, is formed which is sparingly soluble in alcohol more readily in ether and crystallises in transparent needles melting at 80'. On heating the chloride with alcoholic ammonia a resin is formed together with the compound (C26H42)2HCI. The iodides of potassium and aluminium do not convert the chloride into an iodide and aniline does not act on it whereas when sodium amalgam is added to its boiling alcoholic solution the hydrocarbon CZGH44 is formed crystallising from ether-alcohol in large pointed pyramids melting at about 90".Aqueous hydriodic acid and iodine and phosphorus convert cholesterin into impure CQ6H4,. According to Latschinoff cholesterin yields with potassium perman- ganate the acid C26H4207, which forms amorphous salts ; only those of the alkalis are soluble in water the others are insoluble in water alcohol and ether but dissolve in benzene. c. s. (C0172pt.rend., Action of Water on Glycols By M. NEVOLE lxxxiii 228-229) .-Bromide of isobutylene when heaked with water in a sealed tube is transformed into the corresponding aldehyde. The author explains this reaction by supposing that the glycol is first formed and then changed into aldehyde by elimination of the elements of water thus :-CHS CH CH CH \/ CBr + 2Hz0 = \C.<E + 2HBr; I 1 C'H2Br CH,OH 59 ORGANIC CHEMISTRY.CH CH CH CH \/ \/ COH = CH + HZO. I I CHZOH CHO For he found that when the glycol prepared from bromide of isobuty-lene was heated with water for some hours at 200," isobutyric aldehyde was in fact formed. The parallel reaction took place with ethylenic glycol at a somewhat higher temperature. R.R. Preparation of Trimethylene Bromide. By J. L E R M oN T o F F (Liebig's Aizrbalen clxxxii 358-362) .-The author prepares this sub-stance as follows:-Ally1 bromide is saturated at -10" to -15" with dry hydrogen bromide and afterwards heated to 165-170" in the same vessel for 24 hours.Nearly the whole of the product boiling at high temperatures is trimethylene bromide. About one-third of the ally1 bromide remains unaltered after this operat'ion but if the liquid be again saturated with hydrogen bromide and heated for 24 hours the whole enters into combination. The product is purified by distil- lation with steam. J. R. Preparation of Dichloracetic Acid. By 0. WA L LA c H (Deut. Cher12. Ges. Bey. ix 1212).-This substance may be prepared as follows :-Ethyl dichlora.cetate (obtained by the action of potassium cyanide on alcoholic chloral) is dissolved in alcohol and mixed with an equal number of molecules of potash. The cryst,als of sodium dichloracetate thereby produced are dried placed in a long combustion tube and submitted to the action of a current of hydrogen chloride so long as the gas is absorbed.The dichloracetic acid resulting from this operatiori is then distilled off in a slow stream of hydrogen chlo- ride. The acid boils at 189-191" solidifies at O" and yields a crys-talline poiassium salt. J. R. Action of Potash on Trichlorobutyric Acid. By K. GAR-ZAROLLI-THURNLAK (Deut. Chern. Ges. Ber. ix 1209).-The author has obtained by this reaction an acid having the same composition as Gottlieb's dichlorocro tonic acid but differing therefrom in properties. The investigation is not yet complete. J. R. A Simple Method of preparing Glycollic Acid. By RUDOLPH PITTIG (Deut. Chem. Ges Ber. ix 1198).-When chlwacetic acid in moderately strong aqueous solution is boiled for a few hours it is almost completely converted into glycollic and hydrochloric acids.On distilling the product and evaporating the residue over the water-bath there remains a syrupy liquid containing only a trace of chlorine from which it may be freed by again evaporating with water. The calcium salt obtained from the residue is pure glycollate. J. R. Action of Chloral and Bromal on Oxy-acids. By 0. WAL- ABSTRACTS OF CHEMTCAL PAPERS. LACH (Deut. Chem. Ges. Ber. ix 1214-1216).-The following bodies are obtained by heating chloral with the respective acids :-Chloralide of mandelic acid 10-7 C6H5CH/ )CHCC13 Snow-white crystals melting at 59" boiling at 305-310' with partial decomposition soluble in alcohol and ether insoluble in water.Chlornlide of tartaric acid /0-HC\ )CHCC13 HC<VOO)CHCC13 I coo 0-Small crystals melting at 122-124" insoluble in water soluble in warm alcohol and ether. Cldoralide of rnalic acid CHP.C00H I CH 1'0 ~OO)CHCC13. A monobasic acid forming fine crystals which melt at 137"and dissolve freely in hot water. The corresponding bromalides are obtained by precisely similar re- actions. J. R. Synthesis Of a-Oxybutyric Acid. By s.PRSCHIBITEPK (Deut. Chem. Ges. Ber. ix 1312).-This acid is formed by the action of hydrocyanic and hydrochloric acids on propionic aldehyde. C. S. Action of Ally1 Iodide and Zinc on Ethyl Oxalate. By E. YATERN~ (Guzzettn chimica italiana vi 38-39).-0n and P.SPICA gently heating a mixture of one molecular weight of ethyl oxalate and 4 of ally1 iodide with granulated zinc an energetic action is set up which must be moderated by affusion of cold water. On adding water tu the product and distilling an oil passes over which when sub-jected to fractionation may be separated into ally1 iodide and a com- pound boiling at 207-209'. This by analysis gave numbers corre-sponding with the formula CIOH1603, so that there can be no doubt the substance is ethyl-diallyloxalate H0.C(C3H,),.CO(OCzH5). From this ether the acid may be obtained by saponification but the authors have not yet examined it. They thought it probable that the acid CeH,oO might be obtained by Prankland and Duppa's method of treating the ether with phosphorus trichloride but the results were unsatisfactory.C. E. G. ORGANIC CHEMISTRY. 61 On so-called Non-saturated Compounds. By R UDOLPH PITTIG (Reut. Chem. Ges. Ber. ix 1191-1195).-This is a continua-tion of a previous paper on the same subject of which an abstract has already appeared in this Journal (1,976 i 897). 'It was stated before that maleic acid and its anhydride when dis- solved in fuming hydrobromic acid are converted into fumaric acid. Further exaxmination of this reaction has shown that monobromosuc- cinic acid is formed at the same time. The two products are formed in about equal numbers of molecules whatever the proportion of hydrobromic acid employed. Furnaric acid when heated to 100" with a sufficiently large excess of hydrobromic acid is rapidly and completely converted into mono- bromosuccinic acid identical with that obtained from maleic acid.A strong solution of monobromosuccinic acid prepared in the cold is almost completely decomposed by boiling for a few hours the praduct being pure fumaric acid. Citraconic acid and its anhydride dissolve in fuming hydi-obromic acid to a clear liquid which in the coiirse of a few days deposits small hard crystals of bromopyrotartaric acid. This acid when recrystallised from hot water forms large transparent monoclinic crystals melting at 148" with decomposition. It is resolved by prolonged boiling with water into methacrylic and hydrobromic acids and carbon dioxide and the same decomposition is brought about instantaneously by dissolving the acid in excess of sodium carbonate aud heating the solution to the boiling point.The reaction affords a satisfactory means of preparing methacrylic acid. Itaconzic acid dissolves in fuming hydrobromic acid and forms with it a crystalline addition-product melting at 133" which is still under investigation. Crotonic and isocrofonic acids dissolve in hydrobromic and hydriodic acids forming solutions which deposit substituted bromobutyric acids after standing a few days. These products are completely converted into normal butyric acid by treatment with sodium-amalgam. Cinizanzic acid combines with hydrobromic and hydriodic acids in the cold. Bromhydrocinnamic and iodhydrocinnamic acids both form pearly laminq the former melting at 128" and the latter at 120",with decomposition.J. R. On the Isomeric Pyrotartaric Acids. By W. MARKOWNIKOFF (Liebig's AnnaZen clxxxii 324-346) .-The author's investigation of these acids has led to the following results :-1. Pyrotiwtnrzic Acid from Pvopylene Bvomide.-This acid was pre- pared by heating to 150" a mixture of propylene bromide with excess of potassium cyanide and alcohol and afterwards heating the propy- lene cyanide thus formed to 100" with fuming hydrochloric acid. The product, when purified by crystallisation melted at 112". The neutral ammonium saZt forms crystals very easily soluble in water arid sparingly soluble in alcohol. The caZciunz saZt forms small prismah crystals. The acid when heated to 200" gives off water and is converted into the anhydride C511603 which is a colourless oily liquid boiling at ABSTRAOTS OF CHEMICAL PAPERS.244.9" (cow.) tasting sweet and sour and combining but slowly with water. Pyrotartaric acid prepared from tartaric acid behaves in the same manner so that the two acids are identical. 2. Isopyrotartaric Acid from a-Bromobutyric Acid.-This acid termed by the author a-isopyrotartaric acid was prepared by acting on ethyl bromobutyrate diluted with alcohol with potassium and mercury cyanide at 130" and heating the ethyl cyanobutyrate thus formed to 100" with hydrochloric acid. It crystallises when pure in rhombic prisms which melt at 111.5" and dissolve easily in water alcohol and ether. At 160"it begins to decompose into carbon dioxide and butyric acid.The potassium salt forms small crystals easily soluble in water in- soluble in alcohol. The sodium salt crystallises in granular masses more freely soluble in cold than in hot water. The silver salt dissolves sparingly in boiling water. It does not blacken at 100". The zinc saZt formed by saturating the acid with zinc carbonate is sparingly soluble in cold and hot water. At 150" it begins to decom- pose into butyric acid carbon dioxide and water. The lead salt is a heavy white precipitate which is not affected by boiling. The ethyl-ether of this acid formed by the action of ethyl iodide on the silver salt is a colourless liquid of faint aromatic odour boiling at 199-201". 3. Isopyrotartaric Acid fyom Isobutyric Acid (fl-hopyrotartaric Acid) .-This acid crystallises in transparent four-sided prisms sparingly soluble in alcohol and moderately soluble in water.At 120" it sub- limes in white needles and at 170" begins to melt and decompose into carbon dioxide and isobutyric acid. The sodium saZt crystallises in small needles easily soluble in water. The barium salt is less easily soluble and crystallises in stellate groups of thin needles. The caZcium salt like that of the a-acid is moderately soluble in cold water and is deposited from the solution on warming. It crys-tallises in nodules. The magnesium snlt is crystalline and easily soluble in water. The zinc saZt C5H,04Zn.3H,0 obtained by saturating the acid with zinc carbonate dissolves in 106 parts of water.It resembles the zinc salt of the a-acid and decomposes in the same manner. The lead saZt produced on adding lead acetate to a hot solution of the sodium salt forms white scales insoluble in hot and cold water. The silver saZt crystallises in small needles insoluble in water and not affected by boiling. 4. Normal Pyyotartaric Acid.-This acid obtained by acting on pro- pylene bromide with potassium cyanide at loo" and then proceeding as in the preparation of cc-isopyrotartaric acid crystallises from water in large transparent four-sided prisms which melt at 97.5". It distils for the most part at 215" the distillate forming a white crystalline mass melting at 82". ORGANIC CL-TEMISTRY. The calcium salt which is more freely soluble in cold than in hot water crystallises in stellate groups of thin needles.The magnesium salt is crystalline and easily soluble in water. The zinc salt dissolves very sparingly in cold and still less freely in hot water. This acid appears to be identical with Dittmar's pyrotartaric acid obtained by the reduction of glutanic acid the salts of the two acids behaving in the same manner. The foregoing results set at rest the question of the isomerism of the dicarbon acids of the formula CjHS04. The four theoretically possible isomerides are now all known. Their structural formuh are as follows :-CHzCO2H CHZCOZH CH(COZH), I I I CH2 CHCO2H CH, I I I CHZCOZH CHs CH3 Normal Methylsuccinic acid Ethylmalonic acid pyrotartaric acid.(from tartaric acid). (from butyric acid). Dimethylmatonic acid (from isobutyric acid). J. R. On Normal Oxypyrotartaric Acid (Glutanic Acid) and its Isomerides. By w. MARRORNIKOFF (Liebig's AnnaZen clxxxii 347-358).-The author prepares glutanic acid by the action of nitrous acid on glutamic acid the best result being obtained by adding potassium nitrite in the required quantity to a dilute solution of glutamic acid mixed with hydrochloric acid. Glutanic acid being very soluble is obtained in crystals with difficulty. The crystals melt at 72-73' and solidify on cooling in a clear amorphous mass. The acid appears to form with bases two classes of neutral salts differing in solubility. The zinc salt obtained by saturating the acid with zinc carbonate crystallises from a syrupy solution on standing in transparent four- sided tables which when dissolved in hot water are transformed into a pulverulent sparingly soluble salt.It crystallises from a hot satu-rated solution in nodules agreeing in composition with the formula C5H,O5Zn+ 3Hzo. The mag?zesiz~wadt C5Hs0,Mg + 4H20 obtained in the same manner as the zinc salt is sparingly soluble in cold water and crys- tallises from hot solutions in tramparent microscopic rhombic tables. Glutanic acid when heated to 190" is converted into an anhydride which dissolves in water reproducing the acid Glutanic acid is converted by reduction into normal pyrotartaric acid. It is isomeric with Maxwell Simpson's oxypyrotartaric acid ABSTRACTS OF CHEMICAL P-4PERS.from dichlorhydrin. The structural formula of these bodies are as follows :-CH(OH)CO,E CH&O,H I I CH2 CH(OH) I I I CHzCOzH CE,CO,H Glutanic acid. Oxypyrotartaric acid. The aut,hor discusses also the probable formula of itamalic and citramalic acids two other isomerides of glutanic acid but as yet the constitution of these bodies cannot be determined with certainty. J. R. Conversion of Citraconic Anhydride into Xeronic Anhy- dride. By R. FITTIG (Deut. Chew. Ges. Ber. ix 1189).-The author formerly described as xeronic anhydride a body formed in the distilla- tion of citric acid. Further investigation of this body has shown that it is a product of the decomposition of citraconic anhydride (see this Journal 1876 i 898).When pure citraconic anhydride is gently heated in a ret,ort it begins to evolve carbon dioxide at 160" and on continuing the heating till the temperature gradually rises to 190" the contents of the retort become converted into a brown very viscid mass which when distilled yields first a small quantity of citraconic anhydride and afterwards at 220-270° a brown oil insoluble in water a carbonaceous residue being left in the retort. The brown oil when distilled with water yields a distillate of xeronic anhydride the amount of which is com-paratively small. J. K Product of the Oxidation of Glycogen with Bromine Silver Oxide and Water. By R. H. CH[TTE N DEN (Liebig's AnnaZen. clxxxii 206-213).-The author has obtained by the action of bro-mine on an aqueous solution of glycogen at loo" and subsequent treatment of the product with silver oxide an acid which he proposes to call glycogenic acid.It forms when pure an intensely sour syrupy liquid the aqueous solution of which dissolves carbonates forming salts having the general formuIa C6H,,M'O7 and mostly crystalline. The calcium barium cadmium cobalt manganese and lead salts have been analysed. In all but the last (C6H,Pb20,) the acid appears to be monobasic. The formation of the acid by the oxidation of gly-cogen may be represented as follows :-C6HI0O5 + H20 + Br2 = C6H1206Br,; C6H1206Brz+ Ag20 = C,HlZO7+ 2AgBr. J. R. Glycosamine Hydrochloride. By G. LEDDERHOSE (Deut. Chem. Ges Ber. ix 1200).-When purified chitin is heated for half an hour with pure strong hydrochloric acid it dissolves completely forming a blackish-brown solution which when evaporated leaves a large quantity of brilliant crystals mixed with a black amorphous mass If chitin be similarly treated with addition of metallic tin ORGASIC CHEMISTRY.the solution formed has only a slight yellowish-brown colour and the formation of the amorphous substance is entirely avoided. The crys- tals amount to about 40 per cent. of the chitin employed. Their composition agrees with that of a carbohydrate in which HO is re-placed by NH2 combined with hydrogen chloride. COH.(CH,OH) . CHZ . NHZ + HC1. The crystals which have a decidedly sweet taste dissolve freely in water sparingly in alcohol forming acid solutions.They give with soda-ley and copper sulphate a dark-blue solution which deposits cuprous oxide on warming. The substance is being further examined. J. R. New Derivatives of Mucic Acid. By R,UDOLPH (Deqct. PITTIG Chem. Ges. Ber. ix 1198).-Muciu acid is decomposed by fuming hydrobromic acid when heated therewith for some days in the water- bath. The chief product of the reaction is an acid crystallising from water in long silky needles and from alcohol in lamin= and agreeing in composition with the formula C6H405. Its formation may be repre- sented by the equation- in accordance with which the author calls it deRydromucic acid. The bnriumsalt C6H20,Ba + 2+Hz0,crystallises in tufts of needles sparingly soluble in cold water. The calcium salt C6H205Ca + 3HL0 forms colourless laminae or small transparent needles.The silver salt CsHz05Ag,,is a white precipitate insoluble in water. The eth?y7 ether C6Hz05( C2H5)z crystallises from alcohol in colour- less rhombic prisms dissolving easily in alcohol aud ether and melting at 46-47'. It is not affected by heating with acetic anhydride. The acid is converted by the action of sodium-amalgam into a new acid which is crystallisable and easily soluble and melts at about 140'. Dehydromucic acid when carefully heated distils for the most part undecomposed without melting ; but when distilled in a bent tube it breaks up almost entirely into carbon dioxide and pyromucic acid. Cs?&05 = C5H50 + C02. J. R. On the Preparation of Levulinic Acid and on Caragheen-sugar.By F. B ENTE (Deut. Cl~em. Ges. Ber. ix 1157-1158).- This acid is formed not only by boiling cane-sugar or inulin with dilute sulphuric acid but is also obtained from filter-paper wood Caragheen-moss and left-handed gum-arabic. The latter yields att the same bime a small quantity of Scheibler's arabinose and caragbeeii an kactive sugar which reduces copper and silver salts and is oxidised by nitric acid to oxalic acid. The isomeric silver levulinate whicn the author formerly described does not exist being only the impure ordinary salt (see this Jouriial 1875 1005). c. s. Spontaneous Alteration of Anhydrous Hydrocyanic Acid ; VOL. xxxr. F ABSTRACTS OF CHEMICAL PAPERS. and a New Case of the Complete Transformation of that Acid.By J. DE GIRARD (Compt. red. lxxxiii 344).-It is kno\\-n that anhydrous hydrocyanic acid sometimes suffers decomposition in a very short time whereas at other times it may be kept for moiitlis without change. This difference arises from the calcium chloride used in drying the acid. If tlie calcium chloride is neutral the acid obtained will be pure ; but if the chloride is alkaline as it is when ignited in the open air the acid rapidly decomposes spontaneously. The expla- nation is that on the contact of the acid with the lime contained in the ignited calcium chloride calcium cyanide is formed ; this with the water contained in the hydrocymic acid gives rise to the for- matmion of calcium formste and animonia arid it is known that a trace of ammonia is sufficient to determine ihe decouiposition of the anhy- drous hydrocyanic acid.If some pure anliydrons acid be heated in a sealed tube for four or five hours the liquid solidifies to a compact bli:ck mass. On opening the tube there is no evolution of gas and the black substance has the total weight of the acid employed and the same centesimal coni- position. 011 heating it in a tube open at one end ammonium cyanide is at first formed then cyanogen and a carbonaceous residue is left ; but it niay be lieated to 50" without alteration. 011 treating the black substance with ether a crystallisable body is obtained upon which further experiments are in progress. C. IS. P. Decomposition of Potassium Cyanide Zinc Cyanide and Potassium Formcte in Carbonic Acid Air and Pure Hydro-and F.DE MONTIIOLON gen. By L. NAUDIN (Cowpt. reid. lxxxiii 345) .-Carbonic acid completely decomposes potassium cyanide in aqueous solution. With a solution containing abont 3 per cent. of the salt and a regular cui-rent of carbonic acid the quantities of cyanide decomposed were found to be equal for equal intervals of time. Deconipositio~~ of Potassium Cyaiiicle iiz Pure Hylroge?~,and iv Air Deprived of Cadhzic Acid.-A solution containing 2.1'7 per cent. of the salt as HCy was employed through which hydrogen was passed. After 36 hours the loss of HCy amounted to 5.8per cent. The decomposition still proceeded but so slowly that tlie loss of hydro- cyanic acid was undeterminable.The limit of 5.8per cent. was attained more rapidly in proportion as the current of hydrogen was itself more rapid. At a temperature of 15" no formic acid was pro-duced ; biLt at 60-80" a notable quantity of potassium formate was obtained but as this body decomposes at that temperature the pro- gress of the reaction could not be followed. Air gave identical results. The decomposition of potassium cyanide in an inert gas is limited only by the alkalinity of the remainder due to the potash liberated ; with carbonic acid there is no limit because the alkali is iieutralised as rapidly as it is produced. Decouiposition oj' ZirLc CyawXe aiid Potc~ssiwibFomnclte in Ci~rbo?iic Acid Pure Hyclrogeiz t~ndPure Air.-Zinc cyanide suspended in dis- ORGANIC CHEMISTRY.tilled water suffered slow decomposition by a rapid current of car-bonic anhydride. With air deprived of carbonic anhydride a very slight but noticeable decomposition occurred. No trace of decom-position was noticed in the cases of uranium and nickel cyanides even by the prolonged action of carbonic anhydride; but that gas decomposes potassium formate as also do pure hydrogen and air though in a less degree. C. H. P. The Structure of Cyanic and Cyanuric Acids. By A. C~aus (Dent. C'heliL. Ges. Bw.,ix 1165-1167) .-The author maintains against Nencki and Fleischer that these acids are hj-droxyl-compounds. c. s. Chloral Cyanide-cyanate and its Derivatives. By C. 0.CE c H (Deut. Chem Ges. Ber. ix. 1253-1255).-The formation of this sub- stance has been described by the author in a previous paper (see this Journal 1876 i 376; also ii 66).It dissolves sparingiy in cold and easily in hot water being completely decomposed thereby with formation of hydrocyanic and formic acids. On heating it with water in sealed tubes hydrocyanic acid is eliminated and the liquid yields ammonium chloride on evaporation. The substance dissolves in dilute acids and cry stallises therefrom unaltered but when heated with dilute hydrochloric acid it yields ammonium chloride. When dis- tilled with water it is resolved into hydrocyanic arid hydrochloric acids carbon dioxide and formic acid. Heated pel. se in a closed tube it sublimes partially in long needles at loo" and carbonises at i9no In the reaction of chloral potassiunz cyanide and potassium cyanate there is formed together with the foregoing compound a body having the formula C1H2C12NZ02, and therefore differing from it by the elements of 1mol.of hydrogen chloride. This substance previously described by Wallach (see this Journal 1876 i 376) forms small yellow needles soluble in alcohol ether and water. The author has found that it is formed whenever chloral cyanide-cyanate remains suspended in a solution of potassium cyanide. It dissolves in soda- ley and is precipitated unaltered by acids. When heated with alkalis it evolves animonia. Heated with dilute hydrochloric acid it is con-verted into fine lamixm of a substance which dissolves in water alcohol and ether and crystallises therefrom in yellow needles agree- ing in composition with the formula C4H,C1,NOa.The formation of this substance may be represented thus C,H,CIJV,@ +HC1 +2HZO =CaH,Cl,NO* +NHACI. The needles melt at 154" sublime partially in beautiful rhonibic tables dissolve in ammonia and dilute acids and crystallise from the latter unchanged. J. R. Action of Bromine on Phenyl Sulphocyanate. By B. PROS-KAUER aiid EUG.SELL(Deut. Chem. Ges. Ber. iv 1262-1266).-When a solution of bromine in chloroform is added to phenyl sulpho-cyanate diluted with chloroform an orange-red crystalline sub-F'i ABSTRACTS OF CHEMICAL PAPERS. stance is formed the composition of which agrees with the formula C14Hl,NzS3Br2.At the same time some phenyl isocyanide is formed. The reaction is probably represented by the equation- 3(C6H5NCS)+ Br = CIaHloN,S,Br2+ C6H,NC.The former product dissolves quietly in water in the cold but at looo a riolent reaction occurs in which large quantities of carbon dioxide and hydrogen sulphide are evolved and aniline hydrobromide and the hydrobromide of another base C6H5N0,are formed. The reaction is as follows :-The base C6H5N02,crystallises in white needles which dissolve sparingly in water and easily in alcohol. It forms with platinum tetrachloride a crystallisable double salt. Its melting point is 156'. With alcohol the orange-red body behaves quite differently. At the boiling heat a violent react'ion takes place in which ethyl bromide and hydrobromic acid are formed and part of the alcohol is oxidised.The liquid on cooling deposits beautiful sulphur-yellow needles agreeing when purified with the formula ClaH,,N2S3,melting a.t 152" and dissolving freely in hot alcohol but not in water. The same product is formed by the action of glacial acetic acid on the orange-red body. Its constitution is not yet determined. The authors are continuing t,heir investigation. J. R. Action of Alcoholic Potash on the Mustard Oils (Sulpho- carbimides). By R. SCHIFF (Deut. Chem. Ges. Ber. ix 1316).-By this reaction the same sulphocarbamic ethers are formed that Hofmann obtained by heating the sulpliocarbimides with absolute alcohol to 110". Thus a mixture of phenylic sulphocarbimide and alcoholic potash becomes hot and then the compound CS { :E:Hs separates out.Allylic sulphocarbimide is even more readily acted upon by alcoholic potash. c. s. Action of Phosphorus Pentabromide on Amides. Fy 0. WALLACH (Deut. Chem. Ges. Ber. ix 1213). -Diethyloxamide reacts with phosphorus pentabromide at a gentle heat to form two crystalline bodies which may be represented by the formule. CBr2NHC2H CBrNC2H I and I C:Br2NH C,H CBrNC2H These substances are decomposed by water and react with ammonia to form diethyloxamide. When heated they give off hydrogen bromide 3nd yield a brown mass from which potash liberates the base broiri-oxaZ&hyZin. This last is a solid body,-which distils with difficulty. J. R. ORGANIC CHEMISTHY. On Salts of Hydroxylurea and Double Salts of other Hy- droxarnates.Ry N. D. C. HOD GE s (Liebiy's L4nnalen clxxxii 214-220).-Dresler and Stein who first investigated hydroxylurea were unable to obtain compoands of that substance with acids. Derivatives of hydroxylamine corresponding with smides having since been shown to possess acid properties it is improbable that hydroxylurea is capable of combining with acids it might rather be expected to contain hydrogen replaceable by metals and the results of experiments made by the author seem to show that such is the case. Sodium ard Potassium Salts of Hydr.oxylurea.-When a solution of hydroxylurea in absolute alcohol is mixed with a sollition of potassium hydrate or of metallic sodium in absolute alcohol a colourless pre- cipitate is thrown down which rapidly becomes pasty and absorbs moisture greedily from the air.On one occasion the potassium com- pound was obtained as a crystalline powder which after careful drying in a current of air was found to contain 17.94 per cent. of potassium. By analogy with other hydroxamates the formula of the potassium salt should be NzCH3K02+ N2CH402 which requires 20.56 per cent. of potassium. Lead Salt of Hydroxylurea and Acetic Acid.-When to an aqueous solution of the sodium salt obtained as above an excess of neutral lead acetate is added the solution deposits on standing small colourless crystals agreeing in composition with the formula (CJ&02)J'b + (N&H,02)J'b + NzCH402 or Lend Acetate awd A.nishydrnxamn,ate.-Acid potassium anishydrox- amate added to excess of a strong solution of neutral lead acetate throws down a dense white precipitate the composition of which after drying agrees with the formula.CZH302 b<N( c,H,o,)Ho' Lead Acetate and Benzhydroxamate.-Obtained in the same manner as the preceding compouiid. A dense white precipitate agreeing in composition with the formula. N(C,H,O)HO + Pb' 'N(C,H,O)HO 'N(C,H,O)HO' J. R. Decomposition of Uroxanic Acid. By L. MEDICUS (Deut. Chem. Ges. Ber. ix 1162-1164).-0n boiling this acid witlh water no allanto'ic acid is formed as Mulder has stated the products consisting of urea carbon-dioxide and glyoxalyl-urea. C,H,N,O = CONZH + CO + C3H43,Os. ABSTRACTS OF CHEMICAL PAPERS. This decomposition confirms the views which the author held as to the constitution of uric and uroxanic acids.Uric acid. Uroxanic acid. Glyoxaljl- urea. OH I /NH-C-CO-NH \NH-CO I OH c. s. Two new Thiocarbamides (Sulphureas). By PSI.DE CLER-MONT and E. WEHRLIN (C0777pt. red. lxxxiii 347).-These were produced by a reaction similar to that signalised by one of the authors for the preparation of phenylthiocarbamide which consisted in heating aniline hydrochloride with ammonium suiphocyanidc. C'resyZthiocarbnniide CS.NH2.NH.C7H7.-Hydrochloride of paratolui-dine is heated with ammonium thiocyanide on the water-bath in presence of water. After a brief space an insoluble substance sepa- rates. This is washed on a filter until the washings afford no reaction with a ferric solution and then dissolved in boiling alcohol which on cooling deposits the cresylthiocarbamide in crystals.These crys- tals are colonrless plates which melt at 188",have a persistent bitter taste and are scarcely soluble in water or ether. Ncl;whtyZfl~iocnr0lnmz'cle.-Prepared in the same manner as the last substituting naphtylamine for the toluidine. It crystallises in small prisms with rhombic base which melt at 198" are slightly soluble in water and ether and very soluble in boiling alcohol. They have a bitter flavour and become brown on exposure to the air. Heated with lead oxide in boiling alcohol the substance is completely desulphurised and a crystalline body is produced which is under examination. If to a solution of napht~lthiocarbamide in sulphuric acid a little nitric acid is added nitrous vapours are evolved and a flocculent yellow substance produced which is slightly soluble in water but very soluble in alcohol.It has an intense tinctorial power and dyes silk a beautiful yellow. The formula of naphtylthiocarbamide is CS.NH2.N€I.CloH7. C. H. P. On Fluorene and Pyrogenic Hydrocarbons. By PII r L I P P E BARBIER (Ann. Chim. Yhys. [5] vii 472-546).-The author com-mences by briefly referring to the results of various chemists who have isolated or otherwise examined the hydrocarbons fluorene anthracene phenanthrene and tolane the last-named three isomerides may all be formed sjdhetically from toluene and may legitimately be considered as derived by dehydrogenation from the hydrocavbons C14H,,.Fluorene isolated some years ago by Bertlielot f'rom the heavy oils of coal tar boiling between 280 and 340",has been prepared in some qiiantity by the author and carefully examined. It is best prepared .horn the heavy oils from which anthracene and naphthalene have ORGANIC CHERTISTRY. 71 separated by first submitting them to fractional distillation and col- lecting. the portion passing at 290-340" (the distillate at 270-290 contains milch acenaphthene) ; by a further series of fractionations a portion passing at 300-320" is isolated. To obtain a good result enough oil should have been originally employed to allow of 15 or 20 liters of this distillate being collected. By the action of cold this fraction becomes nearly solid ; the mass is pump-filtered and the solid residue pressed in blotting paper and then again distilled collecting what passes at 290-310".Above this temperature little but phenan- threne passes over this hydrocasbon being thus obtained in an almost pure state ; it constitutes about one-half of the pressed crystals. On again distilling and collecting at 295-305" a yellowish-white mass is obtained containiiig a little oxidized substance and some acenaphthene ; these are eliminated by successively crystallising from a mixture of benzene and alcohol alcohol alone and glacial acctic acid. The last-named solvent removes the oxidized substance. but the same result can also be obtained by exposing to sunlight a solution of the crude fluorene in benzene. Absolutely pure fluorene may be prepared from the nearly pure substance thus obtained by dissolving it in ether.and adding the re-quisite quantity of picric acid. On slow evaporation fine red needles of the picric acid compound of the hydrocarbon separate melting at 80-82" ; by treating these with ammonia the hydrocarbon is set free ; and by repeating the combination with picric acid and regeneration sereral times a perfectly pure body melting at 113" is obtained Fluorene thus olhined boils at about 305O ; it sublimes with difficulty in very small white plates agglomerated so as to look like small white granules. It is very soluble in ether benzene carbon disulphide and hot alcohol; in cold alcoliol it is onlj sparingly soluble. The crystallised product has a beautiful violet fluorescence.On analysis it gives numbers leading to the formula ClsHlo*-a result confirmed by the quantity of picric acid contained in the picrate and by the analysis of ~lib~on? ojluorene-a well- crys tallised cb:tracteristic derivative obtained by adding the calculated quantity of bromine dissolved in carbon disulphide to a solution of fluorene in the same menstruum. By distillation a residue is left which is freed from a red bye-prodnct by washing with ether ; the insoluble substance is then crystailised twice from carbon disulphide by spontaneous evaporation The crystals belong to the clinorhombic or nionoclinic system and melt at 166-16i" ; they distil unchanged at a high temperature and are not attacked by boiling alcoholic potash.They are nearly insoluble in ether and in alcohol but dissolve readily in carbon disulphide and in chloroform. This bromo-derivative is formed by the reaction. C,,H, + 2Br2 = 2HBr + C1,HeBr2. When heated with red-hot lime it forms clkhenyl melting at 60" and produces lemon-yellow rhomboidal plates with Fritzsche's re-* The author throughout liis paper employs the combining numbers C = 6 and 0 = 8 and adheres to the system of formulz used by Berthelot of whom he is a disciple. He accordingly rLpresents fluorene by the formula C2sHloand fluoreiiic dcohol by C~,~HB(H~O~). ABSTRACTS OF CHEMICAL PAPERS. agent (dinitranthraquinone) hence the author regards fluorene as it ,ene1y12-met1yhew,ipd C12H8,CH2 i.e. as "diphenyl in which H is replaced by an equal volume of meth ylene." If an excess of bromine be employed in the production of dibromo-fluorene or if that body be heated with bromine hydrobromic acid is evolved and tribrornofiuorene formed thus :-CI3H8Br,+ Br = HBr + CI3H7Br3.It is somewhat difficult to obtain this body free from the dibromo derivative ; when pure it melts at 161-162". A tetrabro.rl2o~/~ore?ze and a dibroniide of rnonobromofluorene CI3H9Br(Br,) have also been obtained the latter by avoiding all heating when fluorene and bromine are brought together this being accomplished by passing air charged with bromine rapour slowly into a solution of fluorene in carbon disulphide. This body forms silky yellow needles soluble in benzene but decomposed on frequent crystallisation forming hydrobromic acid and dibromofluorene ; this result is instantly brought about by contact with alcoholic potash.The production of this addition-product is according to the author quite in accordance with the constitution assigned to fluorene ; bromodiphenyl-methylene should be capable of taking up Br ; thus C13BrH7[(CHZ)( -)] +BrZ = C,2BrH,[(CHZ)(BrZ)]. When nitric acid acts on fluorene mono-nitrcfiuorene and &nitro-Jluorene are produced ; the former is a red powder not easily obtained in the crystalline state ; the latter a reddish-yellow mass of needles diffi- cultly soluble in ordinary solvents but crystallisible with difficulty from a mixture of nitrobenzene and light oils when treated with reducing agents it forms an alkalojidal substance (Diumine of JEuowne?).Sulphuric acid forms with fluorene a snlpho-acid the salts of which are either non-crystalline or crystallisable only with difficulty. Chromic acid dissolved in acetic acid or a mixture of pot'aesium dichromate and sulphuric acid attacks fluorene only with difficulty ; after long action there are formed besides formic oxalic and phthalic acids two new bodies-$u orene- quinone and di$ he71yI eiLe carhonyI. These are nearly insoluble in water and are separated by means of a warm mixture of alcohol and benzene. On cooling grains of the former separate whilst the latter remains in solution ; by recrystalli- sation of these grains from benzene fluorenoquinone is obtaiiied pure ; it is formed by the reaction CnHio + 30 = CuHSOz + HZO.Fluorenequinone melts at 181-182" sulphurous acid solution at 100" gives a crystalline product probably fluorene-hydroquinone ; when it is heated to 180" with iodine and phosphorus fluorene is regenerated. CO melts at 81-52". When treated Diphenylene-carbonyl C12H8. with melting potash it forms diphenyZfoywiic acid C,,H8.CH202,the cal- cium salt of which gives rise to diphenyl by dry distillation. Sppar- ORGANIC CHEMISTRY. ently. therefore this oxidation-product of fluorene is identical with the "diphenylenacetone " of Fittig and Ostermayer prepared from diphenyl-oxalic acid (an oxidation-product of phenanthrene) . Hence the relationships between fluorene diphenyl and phenanthrene are expressed by the formuh- By acting on diphenylene-carbonyl (prepared from phenanthrene which is easier) with nascent hydrogen fEuorenic aZcohoZ is formed ;after crystallisation from benzene this alcohol forms hexagonal plates melt- ing at 153" ; it is soluble in alcohol and ether more so in benzene ; oxidising agents convert it into diphenylene-carbonyl i.e.it behaves like a secondary alcohol. The following equations represent the for-mation of the alcohol and its subsequent reconversion into diphenylene carbony1:-By the action of acetic anhydride at loo" fluorenic alcohol forms Juoyeriic acetate a crptallisable body melting at 75" and capable of saponification by baryta-water at 120° with formation of barium acetate and reproduction of the alcohol. When heated to a tempera-ture a little below it's melting point either alone or preferably with ace tic anhydride fluorenic alcohol loses water and forms $uore?zio etkey-~CIJL(H,C))= CiJ&(CuHioO) + HaO.The ether thus formed is a nearly colourless resinous body melting at about 290" very soluble in benzene but only sparingly soluble in alcohol and ether These properties of fluorenic alcohol result accord- ing to the author from the double functions it possesses arising from its being noc only a hydrogenised carbonyl (i.e. an incomplete ketone) but also a derivative of a lion-saturated hydrocarbon ; wherefore it exerts t'he functions of a pseudo-alcohol of incomplete character and is capable of parting with water whilst it can also polymerise the two actions taking place simultaneously.Together with fluorenic alcohol there is formed on hydrogenising diphenj-lene carbonyl with sodium amalgam a small quantity of a body somewhat more soluble in benzene and crystallising in fine needles. Not improbably this body is the relatively complete body of the series formed by the fixation of 2Hz on diphenylene carbonyl and bearing to fluorenic alcohol the same relation as pseudo-propylic alcohol to allylic alcohol. When fluorene is heated to about 275" with ten times its weight of a solution of hydriodic acid saturated at 0" carbon is set free together with various hydrocarbons of less complex character than fluorene ; benzene and toluene are thus produced together with a hydrocarbon boiling near 220° and entirely soluble in fuming nitric acid.If a larger quantity of hydriodic acid be used (40 parts) hexane and hep- tane and a tridecane Cl,Hz, are formed together with a minute quantity of a hydrocarbon volatile at about 360". The tridecane thus produced is not attacked either by nitric acid cold bromine or fuming ABSTRACTS OF CHEMICAL PAPERS. sulphuric acid ; it can also be formed by hsating to 200" fluorene and red phosphorus with hydriodic acid of sp. gr. 1.5. In the hope of synthesizing fluorene from a mixture of benzene and toluene at a red heat in virtue of the reaction- C,H + CsH,.CH = C,H1(C,H,.CH?[-]) + 2H2 Benzene. Toluene. Fluorene. the author passed the vapour of a mixture of these hydrocarbons through a red-hot tube but with no decisive result ; a minute quan- tity of a body boiling near 301" and possessing fluorescent properties mas formed but the greater portion became converted into diphenyl and anthracene.With the same object in view the isomeric hydrocarbons C13H12,diphenyl-methane and phenyl-toluene (frorn liquid bromo- toluene and phenyl bromide by the action of sodium) were heated in sealed tubes wrapped in wire gauze to a dull red heat the air in the tubes having been withdrawn by a pump before sealing the tubes ; no fluorene however was produced in either case. The phenyl-toluene used was found to boil at 255-260" after purification by fractional distillation. Like its isomeride diphenyl-methane it yielded benzene and toluene in the sealed tube ; a viscid hydrocarbon boiling at about 300" was also formed with phenyl-toluene whilst diphenyl-methane gave rise to much anthracene.The author considers that flnorene is formed in coal-tar by an altera- tion of phenanthrene which he supposes first to assimilate hydrogen forming phenanthrene hydride C14H12 which then splits up into acetylene hydrogen and fluorene thus :-2CirHiz = C2H2 + H2 + 2C13H10-No experimental evidence in support of this view is hovrrever adduced. Action qf Heat on Hydrocarbons derived from a Double Ndeczcle of Toluene by elimination of HycZrogen.-The isomerides C14Hll,dibenzyl ditolyl and benzyl-toluene are represented thus- Dibenzyl ...,. . ,.. . .. C6H1.CHz[CH2.C6H,] Ditolyl ... . . ...... . .. CHz.C6&LC6H4.C~H~] Benzyl-toluene........CH2.C6H,[CH2.C6H6] all these being capable of being regarded as being formed from toluene by elimination of hydrogen thus :-2C7Ht3 = Ci4Hi4 + H2. In order to trace out the relat,ivnships between these substances and the three isomerides CIIH1O,anthracene phenanthrene and tolane the former hydrocarbons were heated to 500-60(3" in sealed empty tubes as above described. In this way dibenzyl gave rim to tolzwbe and stilbene C14H12 thus :-2C11H14 = Cl4H1z + 2CTHe. Dibenzyl. Stilbene. Toluene. ORGANIC CHERIISTRY. By the same means stilbene gave rise to tolmne and phe~aant?mme-3Ci4Hiz = ~C~~HICI + 2c7H8 no tolane being found although the production of that body would seem ci p riori probable since the relationships of dibenzyI stilbene and tolane are represented by the formule- Dibenzyl...... C6H4.CH,[CH,.C6H6] Stilbene ... . .. C6H4.C[CH,.C6H,] Tolane ...... C6H4C[C.C,H,] ; phenanthrene being C.CH,[ C,H,.CH,] since the author finds that on heating tolane with hydriodic acid and red phosphorus to 180” stil-bene is formed. The phenanthrene therefore is produced on heating stilbeiie by a sort of “intramolecular movement ” analogous to that whereby ethyl-benzene becomes transformed into dimethyl-benzene at a high temperature (Berthelot). Tolane itself when heated in sealed tube to 509” is almost wholly carbonised a little benzene and traces of what seems to be diphenyl being formed but no phenanthrene or other hydrocarbon. Ditoly1 prepared from solid bromotoluene and sodium gave rise when heated to 500-600° in a sealed tube to no decomposition at all during a short exposure; but after the lapse of a longer time it was wholly destroyed hydrogen being evolved and carbonisation taking place but neither anthracene nor phenanthrene being formed.Simul-taneously with the crysta’llisable di tolyI prepared from solid bromo- toluene the author found that a liquid isomericle called by him p-ditolyl is formed in small quantity. This is different from the ditolyl previously known prepared from liquid bromotoluene inasmuch as when heated in a sealed tube it is wholly destroyed like the solid ditolyl whilst ditolyl from liquid bromotoluene (a-ditolyl of the author) forms under the same conditions toheiie anthracene and phei?n?ithe~ze, the second hydrocarbon constituting the grcatcr portion of the product.The niixture of anthracene and yhenanthrene thus produced was found to give with Pritzsche’s reagent brown rhomboidal plates exactly resembling those assigned to the “phorene” of that chemist whilst the pure hydrocarbons separated by repeated crj-stalli- sation from this supposed phorene gave entirely different products anthracene forming rose-violet plates and phenanthrene clear yellow ones hence the author concludes that “phorene ” is not as Fritzsche supposed a single hydrocarbon isomeric with anthracene but is simply a mixture of phenanthrene and anthracene the more SO as a mixture of perfectly pure anthracene with pure phenanthrene formed brown rhomboidal plates with Fritzsche’s reagent.Benzyl-toluene as prepared by acting on benzyl chloride with zinc in presence of toluene is a mixture of two isomerides both represented by the formula CH,.C&[CH,.C,H,] (just RS the three ditolyls above mentioned are all represented by CH2.C6H4[ CH4.CH4]) the author did not attempt to separate these two but heated the mixture boiling at 277” in a sealed tube. The products were toluene and aizthracene formed from one modification of the benzyl-toluene while from the other mod$cation which rernai~zedunaltered under the conditions of the expe- ABSTRACTS OF CIIEMICAL PAPERS. riment a minute amount of phenanthrene was apparently also formed as the plates thrown down by Fritzsche's reagent were not of a pure rose-violet colour but consisted of a mixture of rose-violet plates with brown ones.To complete the history of the pyrogenic derivatives of the hydro- carbons CIJHIJ the au tlior synthesized a new isomeride pheryl xyZene by Zincke's method viz. acting on tolyl chloride (prepared by the action of chlorine on xylene vapour and boiling at 192-196") with ziuc in presence of benzene. After several fractionations a pro-duct was obtained boiling between 270" and 280" and giving numbers agreeing with the formula CIPHI1. To this body the author assigns the formula (CHz.C6H,.CHz)(C6H,) regarding it as being formed by the reaction- CH,.C,H,.CH + C~HE= H + (CH,.CsH,.CHZ)(C6Hs) Xylene. Benzene. (Phenyl-xylene). whilst benzyl toluene is formed by the reaction- 2(C,H,.CH4) = Hz + (C~H~.CH,)(C~H,.CHP).Toluene. Benzyl- toluene. On heating this phenyl-xylene to 500-600" in a sealed tube there were obtained benzene xylene and anthracene apparently containing a little phenunthrene as brown plates were obtained with Fritzsche's reagent. It hence appears that in pyrogenic actions anthrncene may be formed not only by the dehydrogenation of a double molecule of toluene (or of a hydrocarbon such as benzyl-toluene of the same degree of carbon condensation) but also by the similar reaction between benzene and xylene. A fraction of hydrocarbons boiling at 245-250" was isolated from coal-tar and deprived of solid hydrocarbons by methodical precipi ta- tion with picric acid. The liquid thus obtained consisted of a mixture of saturated hydrocarbbns of high boiling point (paraffins ?) and other hydrocarbons of clinracter analogous to the C14H14 hydrocarbons.On heating this mixture to 500-600" in sealed tubes there were obtaiiied aceiiaphthene and a little benzene and naphthalene whence it is manifest that the coal-tar hydrocarbons of mom saturated character split up under the influence of heat into less condensed carbon groups just as do the hydrocarbons above examined. Phenunthrene. Regarding this hydrocarbon as diphenyl in which H is replaced by acetylene the author tried to synthesize it by passiug through a red-hot tube a mixture of diphenyl vapour and ethylene. The products of the reaction were benzene styrolene and nuphthalene arising from the condensation of the acetylene formed by the action of the heat on the ethylene the first also arising from the decomposi- tion of diphenyl.In addition unthracene and p7tenuntlmme were formed the latter constituting the main portion of the whole product. Hence the reaction was-c12H6(H'2) + CZHZ= HZ+ CJ%(CHZ)Z* Diphenyl. Acetylene. Plienanthrene. ORGANIC CHEMISTRY. In the hope of preparing. the phenanthrene hydride described by GrEbe. the author heated together to 210-240" phenanthrene and hydriodic acid but without any result. At 260" a liquid was formed consisting of unaltered phenanthrene and a paraffin CI4HJo,not attacked by nitric acid cold bromine or sulphuric acid. Hence the author concludes that &=be's product was not a single hydrocarbon C14HIZ, but only a mixture of this tetradecane and unchanged phenan- threne ; although he thinks phenanthrene hydride is formed in small quantity when sodium amalgam acts on an alcoholic solution of phe-nanthrene.The mixture of phenanthrene and the product of its hydrogenation by hydriodic acid was heated in a sealed tube to 500" ; diphenyl hemene and a little phenanthrene were formed by the inverse reaction of that by which phenanthrene is synthesized viz. :-The acetylene thus produced however becomes forthwith polymerised into benzene. Phenanthrene and anthracene are formed simultaneously not only in the above-described cases but also by the pyrogenous reaction of benzene and styrolene and of ethylene and benzene. The anthracene formed by acting on benzyl chloride with water forms with Fritzsche's reagent the brown compound characteristic of a mixture of anthracene and phenanthrene as does also the anthracene produced by reducing alizarin with zinc powder.The only reaction in which phenanthrene is formed without the production of anthracene is when stilbene is heated. When benzyl sulphide is distilled a body expressed by the formula C,J3,,S is formed to which the author applies the term sulphostdliene. This substance forms light white plates melting at 168-169" and readily subliming at a higher temperature. With Frit,zsche's reagent it forms light yellow rhomboidal plates and with picric acid it pro-duces very unstable fine red needles. By oxidation it forms benzylic alcohol.C. R. A. W. Synthesis of Propyl-isopropyl-benzene.Bg E. PATE and RN~ P. SPICA (Qmzetta chimica itaZia,na vi 99-100) .-The authorp find that a powerful reaction takes place when either benzyl chloride or cumeiiyl chloride is treated with zinc-ethyl it being necessary to cool t,he zinc-ethyl with snow and add the chloride drop by drop. With benzyl chloride a hydrocarbon was obtained closely resembling in its properties the cumene from cuminic acid but which if Jacobsen's results are correct must be isomeric with it. Cumenyl cliloride gives a hydrocarbon C3H7.C6H1.CH2.C2H5 It is 231^0~yZ-i.so~~roiP2/1-be'l"%zene. lighter than water and boils at 205°-208*. The authors have not vet carefully examined these reactions but have observed tha,t con- &ensat?ion-p;oductsof high boiling point are formed at the same time.C. E. G. Action of Carbon Tetrachloride on Phenol in Alkaline and FERD.TIE~IANN Solution. By K. REIMER (Deut. Chem. Ges. Bey. ix 1285-l'LW) .-Carbon tetrachloride is but very slowly acted ABSTRACTS OF CHEMICAL PAPERS. on when heated with an aqueous solution of phenol in excess of alkdi but in alcoholic solution the reaction proceeds more rapidly. The products are sali cylic and paraoxybenzoic acids the formation of which is represented by the following equation :-COONa C6H,0Na + CC1 + 5NaHO = C,H,( t 4NaC1+ 3H20. 'ONa The authors employed in their experiments 28 parts of sodium hydrate or 36 parts of potassium hydrate dissolved in a small quantity of boiling water and mixed with so much alcohol that carbon tetra- chloride produced no turbidity in the solution together with 10 parts of crystallisect plienol and I7 park of carbon tetrachloride the mixture being heated to 100" in sealed tubes for two or three days.The relative amounts of salicylic and paraoxybenzoic acids pro-duced were apparently not influenced by the nature of the alkali employed. This reaction of carbon tetachloride on phenol in alkaline solution corresponds exactly to that of chloroform since it produces directly the same acids that are obtained by the oxidation of the aldehydes formed in the chloroform reaction. J. R. Preparation of Hydroquinone. By P. WESELSKI and J. SCHULER (Deut. Cliem. Ges. Bel-. ix 1159-1161).-When diazo-phenol nitrate which is obtained by the action of nitrous acid on a solution of phenol in ether is dissolved in dilute sulphuric aid and the solution mixed with alcohol and ether the sulphate crystallises out which by means of barium chloride is readily converted into the hydrochloride.The diazophenol is identical with that which Schniitt obtained from the nitrophenol melting at 110". When the sulphate is boiled with water a resinous body is formed but on using dilute aulphuric acid (1 5-90 per cenr.) hydroquinone is produced a pure product yielding 46.2 per cent. instead of 50. c. s. Rotatory Powers of the Isomeric Camphols. By J. DE &I o N 'r G o L F IER (CYompt. 1-encl. lxxxiii :341) .-The cainphols of dif-ferent origin natural or artificial differ from one another only by their rotatory power.This is explained by the fact that borneol con- sists of a mixture of an active and an inactive variety the maximum rotation for the active one being + 3'7" for the ray D. It is easy to produce the variety having a high rotatory power but the production of the other is by no means so certain and as yet all efforts have failed to obtain a borneol wholly inactive. By the action of alcoholic potash on camphor a borneol of very low rotatory power is obtained such as 1" 41' 3" and 5" 15'. By using alcohol more and inore dilute the rotatory power of the borneol is progressively increased but other circumstances also affect the results the study of which is not xet completed. By tshe act of combination the rot,atory power of borneol is augmented.Some pure boriicol liaving a rotation of 14" 35' ORGANIC CHEMISTRY. was treated with stearic acid for ten hours at 200'. The portion not combined was removed and found to have a rotatory power of 15" whilst that obtained by decomposing the stearic borneol had a rotatory power of 22" 18'. This is evidently not a separation of the active from the inactive variety. The augmentation of rotatory power is effected by the temperature at which the etherification takes place ; the higher that temperature the greater the rotatory power of the borneol subsequently elimi- nated. Is this really a creation of rotatory power ? The author thinks not because the camphors produced by the action of iiitric acid on borneols of any rotatory power always exhibit the same rotation namely about 44" 40'.These results cannot be explained on the hypothesis of an active and an inactive variety without supposing a partial destruction of the inactive variety by the action of stearic acid and its total destruction by conversion into camphor. But this is not borne out by experiment because there are no products of destruction by the action of stearic acid and the transformation of a nearly inactive borneol such as of I" 30' rotation ought to give only about one-twentieth of active camphor whereas the quantity really obtained was far larger. The hypothesis of an ordinary inactive variety should therefore be aban- doned. It is a new type ; an active body in which the rotatory power is so to speak hidden and is ready to be reproduced by the first action to which it is subjected such as etherification especially at high temperatures.Thus the borneols whether natural or artificial tvoulcl be mixtures of this particular inactive and of the active varie- ties. C. H. P. Crystalline Form,Specific Gravity and Molecular Volume of Oxysulphobenzide. By J. ANNAHEIM (Deut. Che.rn. Ges. Ber. ix 1148-11 50).-To obtain well defined crystals of oxysulphoben-zide (CsH1.OH),SO, it is dissolved in boiling glacial acetic acid and the nearly saturated solution placed in a water-bath which is heated to 100". A second larger inverted beaker is then put over it the whole covered with a cloth and left to itself for 24 hours.The crystals are often 2 cm. long and 5-6 mm. thick and belong to the orthorhombic system being combinations of 00 PG c;o €'g OP P. Axial ratio a b c = 0,53419 1.2829 1. The specific gravity at 15"is 1.3663 corre- sponding with the molecular volume 182.9 which number agrees very closely with that calculated from the atomic volumes of the elements; that of amorphous carbon = 7.5; of rhombic sulphur = 15.6 ; of hydrogen 6.5 ; and of oxygen 5 ;. the two latter being calcu- lated from the molecuiar volume of water. The specific gravities of the following derivatives were also deter-mined :- Spec. grav. Temp. Mol. rol. Tetrachoroxysulphobenzide . . . . . . 1.7774 Tetrabromoxysulphobenzide . . . . . . 2.3775 Tetraiodoxysulphobenzide .. . . . . . . 2.7966 16" 17 19 218.2 238.0 269.5 c. s. 80 ABSTRACTS OF OHEMICAL PAPERS. Two Benzenedisulphonic Acids and their Relations. By W. KOERNER (Gazzetta chimica itnliana vi 133 and G. MONSELISE -142).-Most chemists now consider the relation between the dihy- droxyl and dicarboxyl derivatives of benzene to be that represented by the formuh- C6( OH) (On)% C6( OH)H(OH)& C6( OH)H,(OH)H,. Pyrocatechin. Resorcin. Hydroquinone. C,(CO,H)(CO,H)H,. C6(CO,H)H( COzH)H,. C,(COzH)H,(CO,H)Hz. Phthalic acid. Isophthalic acid. Terephthalic acid. One of the greatest dificulties in the acceptance of this hypothesis is the fact that the benzenedisulphonic acid discovered by Hofmann and Buckton yields both resorcin and terephthalic acid.It seemed not impossible however that the disulphonic acid hitherto considered as homogeneous was really a mixture of two isomeric acids C6(S03H)H(sO3H)H3 and C6(SOsH)Hz(SO:jH)H,. This supposition has been fully confirmed by experimental evidence. The benzenedisulphonic acid was prepared by dissolving two parts of pure benzene in three parts of a mixture of ordinary (1vol.) and fuming (2 vols.) sulphuric acid and heating the product with three- fourths its volume of the fuming acid to 200-245" for 3-5 hours. The black mass was then dissolcred in water and neutralised with calcium carbonate the calcium salt was converted into the potassium salt and the solution evaporated. By this means crystals of two kinds were obtained which had to be separated mechanically.One of these potassium ol-benxenedisu~honccte,C6(S03K)H(S03K)H3+HzO,corre-sponding with isophthalic acid forms large colourless sharply- defined prisms very soluble in water but insoluble in alcohol ;whilst the other potassium P-be~2zenediszLlphoizate,c6(S03K)Hz(S0,K)H,+ H,O corresponding with terephthalic acid was obtained in ill-defined thin iridescent plates less soluble in water than the a-compound. The acids were liberated from the purified potassium salts by adding a con- siderable excess of sulphuric acid precipitating the potassium sulphate by alcohol and finally removing the excess of sulphuric acid with barium hydrate. Both acids are deliquescent crystalline substances closely resembling each other. Derivatives of a-Benzeuedisulphofiic Acid.-The bnritut?t-sfilt C,(S@,,H(S03)H3 -t'2Hz0 crystallises from a dilute solution in Iarge \/ Ba colourless prisms which are sometimes quite transparent whilst from 8 concentrated solution it separates in nodules consisting of colourless needles. The lead salt C,(SOdH(SO3)H3 +2H20 appears to be 'Pb/ isomorphous with the barium salt. The copper saZt c6(S03)H(S03)H3 \/ cu +6H30,forms blue needles ;the sodiwn salf c6(SC),Na)H( S03Na)H + crystallises in colourless needles and the cadinium salt iu small colourless prisms. ORGANIC CHEMISTRY. a-Dicyanobenzene C,(CN)H(CN)H, is obtained together with ammoniuni carbonate bj distilling a mixture of the potassium a-disul- phonate with potassium cpnlde. It is readily purified by washing with water and crystallisation from alcohol in which it is very soluble.It forms needles which melt at 156". It is readily decomposed by boiling with potassium hydrate solution yielding potassium isophtha- late with evolution of ammonia. The isophthalic acid melts above 320" and yields the characteristic soluble barium salt. a-Be?Lzenediszc~?l~oi2ic clhride C,( SO,Cl)H( SO,Cl)H, formed by the action of phosphorus perchloride on the potassium salt of the a-acid crystallises from ether in large colourless prisms which melt at 6:3" ; it is converted into the corresponding nmide C6(S02NH2)H( S02NH2)H3 by the action of ammonia-solution. The amide crystdlises in needles resembling snblimed benzoic acid and melts at 229". Tkioresomhz is formed by the reducivg action of tin and hydrochlo- ric acid on the chloride and after beizlg purified by distillation in a current of steam forms a crystalline mass of aromatic odour resem- bling that of the leaves of some species of geranium.It melts at 27.1" and distils unaltered at 24.5". It readily yields metallic derivatives. DeTivatives of P-ne?2z~nedisu~ho?aicAcid,-The barium mlt C,(S03)H,(S03)H + H,O forms crystalline crusts? consisting of \/ Ba microscopic needles much less soluble in water than the corresponding a-compound. The lend sdt c,(so,>&(so,)H,+ H,O forms small 'Pb' graniilar crystals which under the microscope are resolved into nodules of minute needles. This also is somewhat less soluble than the a-compound.p-Dicyrcnobeizzeizs is readily prepared in a manner similar to the a-compound the yield being considerably greater. It crystallises in large lustrous needles which melt at 222" but begin to sublime at 153". It is very slightly soluble in alcohol even when boiling and is deposited again almost entirely when the solution is cold. By the action of a boiling solution of potassium hydrate the cyanobenzene is converted quantitatively into terephthalic acid. P-Benzened?~~su~ho?~~c SO,Cl)H,. The action chZoride C,( S02C1)H2( of phosphorus perchloride on the ,B-disnlphonate is much less violcnt than with the a-compound the product being obtained at once in the crystalline state. It is less soluble in ether than the a-dicyanobcnzene crystallising in long transparent needles which melt at 131".l'hc rcmide C,(S02NH2)€I,(SO?NH,)H, crystallises from water in very thin scales and fkom alcohol in small plates which melt at 288". T721:07~ycZroqi~ino?~e is formed from ('3-benzenedisulphonic chloride hy the action of tin and hydrochloric acid subliming in lustrous hex-agonal plates. It is purified by distillation in a current of steam and crystallisation from boiling alcohol in which it is but slightly solublc~. The colourless crystals become oxidised on exposure to the air with formation of a yellow powder. Thiohydroqninone melts at 9S" and possesses an aromatic odour distantly resembling that of the tropmtZut,i. YOL. XXXT. G ABSTRACTS OF CHEMICAL PSPERS. It yields metallic derivatives the lead compound being an orange-red precipitate which is unaltered by a concentrated solution of potassium hydrate even when heated wit11 it at 200" for several hours.C. E. G. Sulphoparachlorobenzoic Acid. By T H. C OL L E N and C. BO T-TINGE R (Deut. Cheru. Ges. Ber. ix 1247-1251).-The preparation and properties of this acid and some of its salts were described in a former paper (see this Journal 1876 ii 412). Some other compounds have now been examined. The acid sodizm sn7t crystallises in tufts of needles which contain 2 mol. of water and are easily soluble in water. The inccyiiesizm sn7t forms needles containing 6 mol. of water which is given off at 150". The anhydrous salt absorbs moisture with avidity. The zinc salt is very soluble and crystallises from concentrated solutions in long shining needles containing 4 mol.of water. The neutral silver salt forms brilliant pointed needles containing 1 mol. of water which it gives off at 120" the salt decomposing at a somewhat higher tempe- rature. It dissolves in water. The potassium salt is not converted into dioxybenzoate by fusion with potash. When fused with potassium formate it yields benzoic isophthalic aiid terephthalic acids. The free acid when treated with sodium-amalgam is deprived of chlorine and at the same time reduced. No definite products of the reaction have been obtained. Phosphorus pentachloride acting on the acid forms a chloride which crystallises from ether in long needles melting at 150" and agrees in composition with the formula C6H~Cl.C0.S02.0H.Cl.This body when dissolved in alcohol is converted into the efh~~Z-co.nyioi~nd C6H3CICOS020HOC2H5 which forms long needles melting about 150". The chloride when treated with alcoholic ammonia yields the ammonium salt of the amide C6H3C1.CO.SO2.ONH4.NH2,whicli crystallises in hair-like needles melting at about 230". J. R. Sulphoparabromobenzoic Acid. By C. BOT T I NO E R (Deuf. Chenz. Ges. Bey. ix 125l).-In a previous paper the author stated that this acid yields a chloride melting at 155" with decomposition. Further examination of the reaction has shown that various mono-chlorides are formed according to the temperature. The chloride formed in the cold (that previously described as above) melts at -* i/6" and is convert'ed at a higher temperature into another chloride melting at 108".The former of these is designated a-chloride the latter P-chloride. The a-chloride has an acid reaction. The ethyZ-coTnpomd melts at 165". The amide melts at 252-254' and crystallises in long needles its ammonium salt melts at 203". The @-chloride forms an ethyl-compound melting at go" and crys-tallising in laminm which sublime nndeconiposed. The amicle melts at 829-230" aiid fornls an ammonium salt crystsllising in needles and melting at 125-126". J. R. ORGANIC CHEMISTRY. Action of Chloroform on Aromatic Oxy-acids in Alkaline Solution. By K. RE~MER TIEIIANN and FERD. (Deut. C?zenz. Ges. AcrD.-'Cvhen pure salicylic acid Be?-.,ix 1268-lE78).-S~~rc~~rc (14 parts) and solid sodium hydrate (25 parts) dissolved in water (50 parts) are boiled with chloroform (15 parts) for some hours and the product of the reaction is clissolved in water arid strongly acidified with hydrochloric acid a yellow precipitate is thrown down which dissolves readily in ether and is taken up therefrom almost entirely by an aqueous solution of acid sodium sulplzite.The latter solution when boiled with dilute sulphuric acid deposits a crystalline precip- itate scparabIe by crystallisation from water into the two following bodies :-/COOH 1. Paraldeh?ldosalic?lZic acid C,H,'OH .-This substance crystal- \CON lises first in long delicate yelIowish needles melting when pure at 248-249" and dissolving freely in et8her and hot alcohol but very sparingly in water and chloroform.The aqiieous solution produces a deep cherry-red coloration with ferric chloride. It decomposes car- bonates with efferrescence and combines with acid sodium sulphite thus behaving both as an acid and an aldehyde whence it appears that it is formed by the introduction of the aldehyde-group into sali- cylic acid. Its calcium salt when submitted to dry distillation with calcium hydrate yields paraoxybenzoic acid. The author concludes therefore that the aldehyde-group occupies the para-position in re-lation to the hydroxyl. 2. Ortlcots~cleh~jrlosalic~jll~c acid,-This body is contained in the mother- liquor 9f the preceding and is taken up therefrom by ether which leaves it on evaporation in the form of a white crystalline mass.When pure it crystallises in delicate needles which melt at 166" and sublime without decomposition at a somewhat higher temperature. Its aqueous solution is coIoured yellow by soda and red by ferric chloride. It decomposes carbonates with effervescence and combines with acid sodium sulphite like the preceding compound with which it is iso-meric. Its calcium salt when distilled with calcium hydrate yields pure salicylic aldehyde whence it is concluded that the aldehyde- group occupies the ortho-position in relation to the hydroxyl. The formation of the foregoing compounds is represented by the equation-COONa C&< + 3NaHO + CHCI = ONa ,COONa C,H,-ONa + 3NaCl + 2H,O. 'COH PARAOXYBENZOJC acid when treated with sodium hydrate Acm-This and chloroform in the same manner as salicylic acid (see above) yields the two following products :- ABSTRACTS OF CHEMICAL PAPERS.XOOH 1. Ort~aoaldehydo-oxydraeyZic acid C,H LOH .-A substance 'COH crystallising in thin yellow prisms which melt at 243-244" and sublime in long white needles at a somewhat higher temperature. It dissolves sparingly in chloroform and water easily in alcohol and ether. The aqueous solution is coloured an intense yellow by soda and brick-red by ferric chloride. It decomposes carbonates with effervescence and combines with acid sodium sulphite and must therefore be regarded as an aldehydo-oxybenzoic acid. Its calcium salt when submitted to dry distillation yields salicylic aldehyde and a small quantity of phenol showing that the aldehyde residue and the hydroxyl-group occupy the same positions as in salicylic aldehyde.Hence the above name. COH 2. Pamoaybenzaldehyde C6H4/ .-This substance which is se-'OH parated from the preceding with difficulty melts at 115-116'. Its aqueous solution has an acid reaction and gives with ferric chloride a faint bluish-violet coloration. Its formation from paraoxybenzoic acid is represented by the equation- ,COONa + CHCI + 4NaHO = C6H4<ONa COH C&d + Na2C03i-3NaC1 + 2H,O. 'ON% J. R. Rufigallic Acid. By W. K LOB uK o w s R I (Dezd. Chenz. Ges. Be,-. ix 1256-1262).-The author has continued his experiments on the reactions of this acid. (For an abst'ract of a previous paper see this Journal 1876 i 259).Rufigallic acid dissolves in cooled fumin,q nitric acid and in weaker acid on warming evolving large quantities of gas-chiefly carbon dioxide. The solution yields oxalic acid when evaporated. Fuming sulphuric acid dissolves rufigallic acid with dark purple- red colour and deposits it unaltered on dilution. The solution evolves sulphur dioxide when heated. Sulphuric anhydride mixed with the acid converts it into a thick violet-coloured pulp from which the acid is recovered unchanged on addition of water. Bromirie and phosphorus pentachloride both act on rufigallic acid but no definite products of the reaction have been obtained. Rufiigallic acid submitted to dry distillation with lime or baryta is mostly carbonised a slight sublimate only apparently of naphthalene being formed and an inflammable gas evolved.Rufigallic acid heated with h-j-driodic acid and phosphorus yields a yellow crystalline body the composition of which agrees -71th the formula, C14€Ilo07.This substance is not soluble without decompo- sition. Distilled with zinc-dust itJ yields anthracene. When heated ORQANIC CHEMISTRY. with acetic anhydride it is converted into a crystalline compound agreeing in composition with the formula- CZ6H22013 = C,,H,( C2H,O)sO,. The action of hydriodic acid on rufigallic acid ClaH,O, is there-fore to replace an atom of oxygen by two atoms of hydrogen. Now if rufigallic be regarded as a body formed from two substi- tuted benzene-nuclei united by two GO-groups the acid and the re- duction-product may be represented thus H C (H0)aHC /i\ 0 CsH(OH), \A/ H and the acetyl-compound thus H c (CH,OO),HCs /I\ O C~E(OC,H,O),.\A/ H These formule however are based on the assumption that the acid is capable of taking up six acetyl-groups the presence of which has not yet been demonstrated experimentally in the acetyl-compounds of either. the acid or the reduction-product. J. R. Action of Phosphorus Pentachloride on Nitronaphthalenes. By ALBERT (Dezct. Chenz. Ges. Ber.. ix 1187-1189).- ATTERBERG Nitrochloronaphthalene melting at Go,when heated with an equi- valent quantity of phosphorus pentachloride yields a dichloronaph-thalene which crystallises in long brittle needles melting at 66" and is identical iii properties with the /3-dichloronaphthalene of Faust and Saame.Nitro-ydichloronaphthalene similarly treated yields a trichloro-naphthalene crystallising in long colourless needles which melt at 129". This product is not identical with any of the known trichloro- naphthalenes all of which melt at lower temperatures. a-Dinitrochloronaphthalenemelting at 106" is only partially acted on by phosphorus pentachloride the product being a trichloronapli-thalene apparently identical with that just mentioned. a-Dinitronaphthalene heated to 217" with phosphorus pentachloride yields a chloronaphthalene which crystallises in fine laminae melting at 107" and is identical in properties with the y-dichloronaphthalene pre- viously described by the author.@-Dinitronaphthalene heated to 170" with phosphorus pentachloride ABSTRACTS OF CHEMICAL PAPERS. yields a trichloronaphthalene melting at 129" and identical with that obtained from nitro-y-dichloronaphthalene and a-dinitrochloronaph-thalene (see above). a-Nitronaphthol wheu heated with phosphorus pentachloride yields a small quantity of P-dichloronaphthalene melting at 6i". Hence P-di- chloronaphtlialene a-nitronaphthol and nitrochloronaphthalerie are corresponding and similarly constituted bodies. Naphthoquinone must also belong to the same series Liebermann having obtained it from a-nitronaphthol. J. R. An Isomeride of Dibromanthracene. By 0swA L D M IL L E R (Liebig's Aiimaleiz clxxxii 366).-Dibromanthraquinone when heated to 150" with hydriodic acid and red phosphorus yields by reduction a substance isomeric with dibromanthracene.The new body is ex-tracted from the products of the reaction by benzene. It cr,ystallises from alcohol in brilliant golden-yellow rectangular tables which melt at 190-192". It dissolves sparingly in alcohol and benzene. Strong sulphuric acid dissolves it easily forming a reddish-brown solutioii from which water throws down unaltered dibromanthracene. By oxidation it is converted into dibromanthraqninone. The investi- gation is being continued. J. R. Anthranol. By C. LIEBXRMANN and TOPF(Deut. Chern. Gcs. Ber. ix 1201-1203) .-Anthraquinone when treated with hydriodic acid and phosphorus in excess yields anthracene dihydride C,,H,, which may thus be obtained with ease in large quantities.It crystal-lises from alcohol in large lamin= melting at 108". But when the reducing action is allowed to proceed for a short time only the product is a body intermediate in composition between anthraquinone and anthracene dihy dride. This substance called anthrarzol by the authors crystallises from alcohol in yellow necdles. Its formation is represented by the equation- Anthranol forms with acetic anhydride yellow needles of a monacetyl- compound CI4H,( C,H,O)O melting at 126-131" ; whence the authors conclude that if the constitutioii of anthraquinone be represented by the first of the following formulze that of the new substance must be expressed by the second Anthraquinone.Anthranol. Anthranol is reduced to anthracene by zinc-dust at a red-heat and is oxidised to anthraquinone by nitric or chromic acid. Fuming nitric acid in the cold converts it into a nitro-compound crystallising in needles. It does not dissolve completely in alkalis on prolonged boiling of the solutions it is partially converted into anthraquinone. ORGASIC CHEMISTRY. 57 It melts at temperatures varying between 163" and 170° and at higher temperatures turns green and carbonises without volatiljsing. J. R. Xanthopurpurin. By H. PLATH (Dezit. Clienz. Ges. Ber. ix 1204-1206) .-Xanthopurpurin is best obtained by the reduction of purpurin with stannous chloride in alkaline solution. It sublimes mheLi pure in yellowish-red needles which melt at 262".It crystallises from glacial acetic acid in brilliant short needles. Xanthopurpurin forms crystalline sodium bnriu172 and caZcium siilts the last named crgstallising in dark reddish-brown needles which agrm in composition with the formula C1,H6(02Ca)0,. Di1?Leth~Z~uir;tho~uipzL,.in7 C,,H (CR,O),O,. -This substance is ob-tained by heating to 120" a mixture of xanthopuypurin methyl iodide and potash in molecular proportions. The product crystallises from glacial acetic acid in small pale-yellow needles melting at 178-180". n,btli~Zxa,iil~c~u,p111"i72, C,,H,(C,HjO),O, obtained in the same manner as the preceding compound forms yellow needles easily soluble in alcohol and glacial acetic acid but insoluble in water. It melts at 170".TJibi.oitioxa~itlio~~i~~2~rirz~ is formed by tlie direct action C14HGB~*204 of bromine on xanthopurpurin. It crystallises from glacial acetic acid in orange needles melting at 227-230O. Its ai??riroir.;unz-co~?~ozLll(~, Cl&IF1Bra(@.NHl)202, formed by boiling it with a solution of ammo-nium acetate crystallises in red matted ncedles having a fine metallic lustre. D.ilLitroxa.ntht~u,puri?z is formed by the action of C14H6(K02)20$ nitric acid of sp. gr. 1.48 on xanthopurpurin in the cold. It dissolves in water ether alcohol and glacial acetic acid and crystallises froin the last in bright-red needles melting at 249". The bariUm-ConZplJzL~~~ ClIH4(NOz),(O,Ba)O, formed ~iiadding baryta-water in excess to an aqueous solution of dinitroxant hop urpurin crystallises in dark-red needles.The anz~t~o~i'i~~i~~-~o~~~oz~~~d, C14H4(N02)2( OH) (0.NH4)O, is obtained in bright-yellow silky needles by dissolving the nitro-corn- pound in a boiling solution of ammonium acetate. When xanthopurpurin is dissolved in strong sulphuric acid and nitrous acid is passed into the soliltion a substance is formed which crystallises from glacial acetic acid in steel-blue needles appearing reddish by transmitted liglrt. This substaiice dissolves easily in water ether and other solvents melts at 249" and has the composition of dinitroxantliopurpurin ; but whether it is identical or only iscmeric with the compound described above is not yet made out. J. R. Constitution of Compounds of the Coniferyl and Vanillin Series.By PERD.TIEMBNK (Deut. Chem. and B. MEXDELSOHN Ges. Ber. ix 1278-1284).-Wlzen 1 niol. of vanillic acid is boiled for some hours with 1 rnol. of chloroform and an aqueous solution of 5 mol. of sodium hydrate and the product of the reaction is dissolved in water and acidified with hydrochloric acid a sparingly soluble body is thrown down which proves on examination to be aZdehydovadZic mid whilst vanillin remains in solution. as ABSTRACTS OF CHEMICAL PAPERS. The former product dissolves in ether and is taken up from the solution by acid sodium sulphite. It crystallises from boiling water in yellow silky needles melting at 221-222" dissolves easily in alcohol and ether and decomposes carbonates with effervescence. The reactions by which these products are formed may be repre-sented thus /COONa C6H3-OCH3 + 4NaHO + CHCI = 'ONa C6H3LOCH + 3NaCl + Na,C03 + 2H,O.'ONa (Sodium-vanillin). ,COONa CGH3LOCH + 3NaHO + CHC1 = \ONa COONa C6H2'~$~3+ 3NaC1 + 2Hz0. \COH (Sodium aldehydoranillate) . This behaviour of vanillic acid is perfectly analogous to that of paraoxybenzoic acid under the same circums tances whence the authors conclude that in the molecule of vanillic acid the carboxyl-group occupies the para-position in relation to the hydroxyl ; and accordingly \Tanillic acid is to be regarded as metamethoxyl-paraoxybenzoicacid and vanillin as metamethoxyl-paraoxy benzaldehyde. Aldehydovanillic acid must for the same reason be regarded as a derivative of salicylic aldehyde and in fact it exhibits the characteristic behaviour of such derivatives giving an intense yellow solution with soda and a distinct reddish-violet coloration with ferric chloride.J. R. The Constitution of Veratric Acid and Veratrol. By G. KOERN E R (Gaxxetta chimicu itnlium vi 142-148).-1t VI as found that veratric acid yielded prot30catechuic acid when submitted to the action of fused potassium hydrate a result in accordance with the author's idea that this rare acid was a trisubstitution derivative of benzene resembling anisic acid. He was thus induced to study the action of hydriodic acid on veratric acid and found that when the two were heated together for some time at 150-160" niethyl iodide was formed together with protocatecliuic acid (m.p. 199") and a small quantity of another acid which again heated with hydriodic acid at 170" yielded methyl iodide carbonic anhydride aiid pprocatechin. This result distinctly proved that veratric acid is identical with di- methylprotocatechuic acid but in order to obtain additional evidence tile author prepared dimethylprotocatechuic acid synthetically. Pure protocatechuic acid (from essence of cloves) mas converted into methylic dinietliylpro t ocatechuate by treating it with sodium methylate and ORGANIC CHEMISTRY. methyl iodide. The ether when pure crystallises in colourless needles melting at 58" and possessing an agreeable although feeble aromatic odour. It is easily saponified by treatment with solution of potassium hydrate and the solution on the addition of hydrochloric acid deposits the dimethylprotocatechuic acid in needles which have the same melting point as veratric acid namely 179*5",and is identical with the latter in all its properties.Veratric acid is therefore closely allied to vanillin being identical with methyl-vanillic acid the formulse C6(OCH,) (0CH,) H(C0OH)H3 and c6(OCH,) (0CHS)Hi representing veratric acid and veratrol respectively. The author thinks that the different results obtained by Koelle (Am. Chew €'harm. clix 240) are probably due to his dimethyl- protocatechuic acid being contaminated with a small quantity of monomethylprotocatechuic acid. C. E. G. Usnic Acid. By E. PATE ~wi,(Gazzetta chimica italiann vi 113-l33).-The research described in this paper has already been briefly noticed (this Journal 1876 vi 202 and Deut.Chem. Ges. Ber. ix 345). The memoir commences with an historical summary after which the method of preparation of the acid from Zeoia sordidu is fully described and its principal reactions given. Treated with sulphuric acid and potassium dichromate it yields acetic acid. Acetyl chloride I has no action on usnic acid even when boiled with it whilst at 100" in sealed tubes the acid is converted into carbonaceous products. Decayb-z~slzicacid Cl5HI6O5,is formed not only by the actioii of ethyl alcohol at 150' on usnic acid but also by the action of methyl alcohol and ally1 alcohol. Water also acts in the same manner but very slowly owing probably to the slight solubility of the acid in it.Amongst the products of the action of a solution of potassium hydrate on usnic acid the author has verified the presenrje of carbonic anhydride acetic acid and acetone so that the equation- C18H1607 + 3HzO = Ci,H,,Oj + C02 + C2H402 + C3IZjO really represents the formation of pyrousnic acid Cl2HL2O5, from mnic acid C,,H1,O7. It is not improbable that decarbusnic acid is formed as an intermediate product which becomes transformed into pyrousnic acid thus- Ci5Hi~05-I-H2O = CizHnO + C3H60-The formation of acetone renders it highly probable that usnic acid and perhaps decarbusnic acid contains the group C(CH,),. When pyrousnic acid is heated it decomposes yielding a crystalline sublimate which melts at 175" ; but in order to obtain a satisfactory result the operation should be conducted in a current of hydrogen the residue left is then very small.This new substance which not oiily melts 20" lower than pyrousnic acid but is also much less soluble in water appears to be formed without elimination of wfiter. Its solu-tion in potash absorbs oxygen from the air and becomes green. If usnic acid be treated with potassium hydrate in a manner similar to that for the preparation of pyrousnic acid but instead of boiling the solution it be merely heated to loo" acetone is produced and on 90 ABSTRACTS OF CHEMICAL PAPERS. adding hydrochloric acid to the alkaline solution a yellow flocculent pre- cipitate is obtained. This after being purified by washing with ether and crystallisation from alcohol is obtained in colourless micaceous plates quite different from decarbusnic acid and from pyrousnic acid.It is but slightly soluble in water and its alkaline solution alters readily in contact with the air but does not turn green. It melts at a lower temperature than pyrousnic acid and when heated in a current of hydrogen yields a cr-ystalline sublimate meltiiig at about 160" the alkaline solution of which does not become green on exposure to the air. The memoir concludes with some criticisms on Salkowski's paper on usnic acid. C. E. (3. Ethyl Santonate. By F. SE sT I K I (Gazzettic chimica itnliam vi 148-150) .-This compound is most conveniently prepared by heating silver santonate with excess of ethyl iodide distilling off the excess of iodide and extracting the residue with ether.On the evaporation of the ether the ethyl santonate is left in large prisms. It may also be prepared by saturating an alcoholic solution of santonic acid with hydrochloric acid and heating but is then difficult to purify. The ether which has the composition C,,H,,( C2Hj)04,melts at 88-89'. It is readily decomposed by boiling with a dilute solution of sodium hydrate with formation of sodium santonate ; also by prolonged contact with nitric acid santonic acid being liberated. C. E. G. Oxidation of Aromatic Acetamines by Pot*assium Perman- ganate. By A. W. HOFMANN (Deut. Chem. Ges. Ber. ix 1299-1303).-\Then a concentrated solution of potassium permanganate is added to a hot aqueous solution of the acetoxylide melting at 127-128" a product is formed which appears to be a mixti1i.e of at least two acids.Orie of these which can easily be isolated as it forms an insoluble blue copper salt is ucetwiz idoplithalie acid It is very sparingly soluble in water more freely in alcohol and separates from dilute alcohol in small white crystals melting with decomposition at 270-280". The acet,yl-group is not removed by heating with hydrochloric acid to ?20" whereas at 200" carbon dioxide is given off and probably an amiclobenzoic acid and perhaps also aniline is formed. Acetoparatoluide yields with potassium permangannte an acetamido- benzoic acid which crystallises from alcohol in needles melt'ing with partial decomposition at 250" and easily converted by boiling hydro- chloric acid into the hydrochloride of paramidobenzoic acid.c. s. Action of a-Dinitrochlorobenzene on Amido-compounds. By WILLGERODT (Deut. Chenz. Ges. Ber. ix 1178-1181).-While aniline acts already in tlie cold on a-dinitrochlorobenzene metani- traniline does not even at 150" ; but on heating an alcoholic solution with magnesia to 200' the following reaction takes place :- ORGANIC CHEMISTRY. 2(HzN.C,H,.N0,) + ZC,EIs,(NO,),Cl + MgO = The a-dinitrophenylnletanitraniline thus formed is sparingly soluble in boiling alcohol and less so in water ether dilute hydrochloric acid and dilute potash but freely in boiling acetic acid from which it crys-tallises in short yellow needles. When a-dinitrochlorobenzene is heated with oxamide and alcohol for six hours to 200-230" dinitraniline is formed C2Oz(NH,)2 + C,H,(NO,)ZCl + 2(C?H,.OH) = HzN.C,H,(NOz)z + (CzH,),O + CO2 + CO + NH.iC1.But when magnesia is added the reaction takes place at 150' and requires only two hours Aniline-black. By R. NIETZKI(Deut. Chem. Ges. Bey. ix 1168 -1170) .-When aniline is heated with aniline-black a blue colouring matter is formed which is obtained pure by boiling out the crude black with alcohol and treating the residue with soda to obtain the base which is converted into the acetate by moistening it with acetic acid. The dry acetate is then heated with 8-10 times its weight of aniline to 160-180" for 6-8 days. The product is then treated with an excess of dilute hydrochloric acid which does not dissolve the hydrochloride of the new base.The latter was obtained in the free state by the action of soda and purified by dissolving in ether precipitating this solution with hydrocl~loric acid and repeating this process. The free base which has either the formula CB6HB3NS but probably or C36H31N5 the former dissolves in ether with a magenta-red colour. C36H34N5.c1H crystallises from hot alcohol in needles having a coppery lustre while by precipitating the ethereal solution of the base with hydrochloric acid it is obtained as a crystalline violet powder with little lustre. C3,H3,N5.1H is a very similar compound and CZ6H3,IIU',. C6H3(NOZ)~O is obtained as a crystalline precipitate by adding an aqueous solution of picric acid to an alcoholic solution of the hydrochloride.(C3,H3,N,. CIH),PtC14 is a violet crystalline precipitate which is sparingly soluble in alcohol and insoluble in water. c. s. Action of Phosphorus Pentachloride on Acetotoluidide. By 0. WALLACH (Deut. Chena. Ges. Be)-. ix 1214).-Amongst the products of t'his reaction is the imido-chloride CH3CC1NCsH4CH3,a crystalline easily decornposible substance yielding with aniline tolui- dine and naphthylamine the following amidines :-Ethe?c,yij~ henyltoly 1arnidiqie. White needles melting at 86-88'-CH,C// NC6H4CH3 \NHC,H ABSTRACTS OF CHEMICAL PAPERS. Et~Le"iL1/lditolylamidine,a crystalline substance melting at 117-118O-CH,C //Nc6H4CH3 'NH C6W,CH3' EtJze~~ylna~Z~thyltol~la;l~iidi.ne, a body not yet obtaincd in definite form-CH,C//NcBH4CH3 \NHC,,H The imido-chloride when heated evolves hydrogen chloride and yields the hydrochloride of a base C18H,,C1N, which melts at 71-72" and decomposes at 130° the hydrochloride of a new base being formed.J. R. Xylidines. By A. W. HOFMANN (Deut. Chem. Ges. Rer. ix 1292- 1299).-The author has isolated from the crude oils of high boiling point obtained in the manufacture of aniline a xylidine which forms sparingly soluble salts with nitric and hydrochloric acids. This he calls provisionally a-xylidine to distinguish it from an isomeride occurring together with it (p-xylidine) which forms a sparingly soluble nitrate but an easily soluble hydrochloride.The two isomerides were separated by repeatedly crystallising from hot water the mixture of acetyl-compounds obtained by boiling them with glacial acetic acid the a-compound being the less soluble was thus obtained pure. a-AcetoxyZidide forms large flat white needles which melt at 127- 128" and dissolve easily in alcohol. When boiled wit,h strong hydro- chloric acid it is converted into xylidine hydrochloride. The base separated from this salt is an oil colourless at first but rapidly turning dark its boiling-poilit is 212" and its sp. gr. 0.9184 at 25". Analysis of the platinum salt agrees with the formula [C6H3( CH3),HC1],PtC14. A xylidine having the same properties as the foregoing is obtained by the action of methyl alcoliol on toluidine hydrochloride ah 300".The following derivatives of a-xylidine have been prepared. U~;eylyZsu?p/tocnI-Zln iilide CS[ NH.C,H,(CH,),], was obtained by digesting xylidine with carbon bisulpliicie till hydrogen sulphide ceased to be evolved. It is insoluble in water and but sparingly soluble in boiling alcohol from which it is deposited in dazzling-white hard crystala melting at 152-153". XyZyI sulpl~ cyccwate is formed by distilling the preceding compound with phosphoric anhydride. It is solid at the ordinary temperature but melts very easily. DixyZyZgua?ziditie CNH[NH.CsH,( CH3)& is readily formed by the action of lead oxide on xylylsulpliocarbamicle in presence of alcoholic ammonia. It crystallises from hot alcohol in delicate white needles which melt at 156-158" apparently undergoing decomposition.It is insoluble in water. NitracetoxyZidide C,H (CH3),( NO,) NH( C,II,O) formed by the action of strong nitric acid on acetoxylidide crystallises from hot water or alcohol in ye!low needles melting at 172-173". ORGANIC CHEMISTRY. Nitromylicline (Nitramidoxylene) CsH2(CH,)2(N02)NH2,is formed by boiling the last compound with strong hydrochloric acid till the liquid acquires a deep-red colonr. It crystallises from hot water in fine orange-red needles melting at 69" and dissolving sparingly in water and more freely in alcohol. It is only very slowly attacked by boiling soda- ley. Xylene-diarnine (Diamidoxylene) C6H2(CH,),(NH,), is formed by the action of tin and hydrochloric acid on nitroxylidine.It forms glittering laminae or delicate white needles which melt at 74-75". It is a faintly alkaline base and forms crystallisable salts. J R. Fluorescence of Quinidine Sulphate. By E. S CHAE R (Deut. Chenz. Ges. Ber. ix 1314).-A solution of Pasteur's quinidine sulphate (Hesse's conquinine) in chloroform after standing in the diffused light for some months assumed a splendid green fluorescence resem- bling that of certain uranium-salts. c. s. A Homologue of Caffeine. By L. PHILI PS (Deu,t. Chem. Ges. Ber. ix 1308-1310) .-When theobromine-silver is heated with ethyl- iodide ethyl-theobi-omine C7H7(C2H,)Na02is formed which separates from alcohol in white prismatic cryst,als which are somewhat freely soluble in boiling water. It is a weak base forming with nitric acid and hydrochloric acid crystallised salts.Its aqueous solution gives with silver nitrate a precipitate C7H6Ag(C2H5)N402.Ethyl-theobro-mine melts above 2$0" and sublimes without decomposition. With chlorine-water and ammonia it gives the same reactions as caffei'ne. c. s. On Atropine. By F. SELMI (Gazzetta chimicn italiana vi 153-156).-Si??zpli$ed Method of Eztracting tha Poisonouts Al?;aloi'ds) .-The alcoholic extract of the viscera acidified and filtered is evaporated at 65" ; the residue taken up with water filtered to separate fatty mat- ters and decolorised by means of basic acetate of lead leaving the solution in contact with the air for 24 hours. It is then filtered the lead precipitated with sulphuretted hydrogen arid the solution after concentration repeatedly extracted with ether.The ethereal solution is then saturated with dry cai.bonic anhydride which generally causes a precipitate of minute drops adhering to the sides of the vessel and containing some of the alkaloids. The ethereal solution is then poured into a clean vessel mixed with about half its volume of water and a current of carbonic anhydride passed for 20 minutes which may cause the precipitation of other alkaloids not precipitated by dry carbonic anhydride. Dsualljy the whole of the alkaloids present in the ether are thrown down by these means but if not the solution is dehydrated by agitation with barium oxide and then a solution of tartaric acid in ether added to the clear liquid taking great care not to employ excess of acid ; this throws down any alkalo'id that may remain.In order to extract any alkaloids that may still remain in the viscera they are mixed with barium hydrate and a little water and agitated with 2mi-i$ed aniylic alcohol ; the alkaloids may subsequcntly be extracted from the alcohol by agitation with very dilute sulphuric acid. ARSTRACTS OF CHEMICAL PAPERS. Af~opine.-As atropine is readily decomposed into tropine and atropic acid and might become altered in the process of extraction the author studied the action of various reagents on the alkaloid. Boiled with a solution of barium hydrate in contact with the air it gave a pleasant odour of hawthorn flowers ;but no odour was observed on distilling the mixture.The residue contained tropine which was extracted with ether. Atropine was decomposed when boiled with dilute sulpliuric acid or with a solution of tartaric acid but no odour was developed ; a substance (A) being obtained from the solution on treatment with ether very different in its reactions from tropine. The action of ammonia on atropine yields two substances of the nature of an alkaloiid ; one (B) precipitable by carbonic anhydride from the ethereal solution ; the other (C) Eot precipitable. Their reactions are as follows :-Tropine. A. B. C. Tannic acid.. .................. Whit,e White White - Iodised hydriodic acid .......... Brown drops -Brown Brown Platinum perchloride .......... Turbidity None Kone None Picric acid ....................-Id. Id. Id. Meyer's reagent.. .............. White Id. Id. Id. Gold chloride.. ................ Yellow Yellow Ycllow Yellow Brominated hydrobromic acid. ... None -Yellowish Id. Mercuric chloride .............. Straw yellow White White T;CThite Sodium phosphotungstate. ....... -Id. Ia. -Iodide of potassium and bismut,h 3range-yellcw Yellow Yellow Iodide of potassium and cadmium White White From experiments made on the putrified viscera of an animal poisoned with atropine and on the alkaloids generated by the putre- factive process in the viscera themselves tthe author finds that one of those formed in the latt,er case and which may be extracted by the use of amylic alcohol (although not by ether) closely resembles atropine in its action on the animal organism.Atropine may be dis- tinctly recognised however by the characteristic odour of hawthorn given off during evaporation with baryta; by the bitter taste of the ethereal extract ; and by the poisonous action of the ethereaZ extract accompanied by dilation of the pupil. C. E. G. Betulin. By U. HAUSXANN (Liebig's AnnoZen, clxxxii 368-380).-The author prepares betulin a's follows :-The outer bark of the birch tree previously boiled with water and dried is boiled for three or four hours with 20 times its weight of 90 per cent. alcohol ; the extract is strained while hot and at once mixed with alcoholic neutral lead acetate so long as a precipitate is produced thereby. The mixture again heated to the boiling point' is filtered and the filtrate is freed from lead by means of ammonium carbonate and allowed to cool whereupon it deposits a mass of crystals of impure betulin.This pro- duct is purified by treatment with ether arid crystallisation from boiling alcohol. ORGANIC CHEMISTRY. 95 Pure betulin forms long thin colourless prisms which when dry present the appearance of asbestos. It is inodorous and tasteless. It melts at 258" (corr.) to a colourless liquid which solidifies in a glassy amorpilous mass; at a somewhat higher temperature it begins to sublime in long extremely delicate needles. When strongly heated it gives off vapoiirs smelling strongly of Russia leather. It is insoluble in water sparingly soluble in cold alcoliol ether chloroform and benzene but freely soluble in the hot liquids.It dissolves also in glacial acetic acid oil of almonds and turpentine. Its composition agrees with the formula C,,H,,O,. Betulin is dissolved and acted on by strong sulphuric acid in the cold and by hydrochloric and hydriodic acids when heated therewith in sealed tubes. It is attacked also by chlorine bromine arid iodine but as yet no definite products of these actions have been obtained. Betulin yields by dry distillation a number of volatile products amongst which is one of thick oily consistence boiling at 243" of sp. gr. 0.951 and having the composition of an anhydride of betulin -C36H560. Betzslin D2'ncetafe.-This body was obtained by heating to 1%"a mixture of betulin and acetic anhydride.It crystallises in long colour- less prisms which melt at 223" (corr.) and solidify in a crystalline mass on cooling. It dissolves easily in benzene sparingly in alcohol and ether. Its composition agrees with the formula C4,,H6,05. RefuZi?.linnzaricAcid.-The author calls by this name a bocly obtained by adding betulin gradually to nitric acid of sp. gr. 1.51. The yeilow liquid thus formed leaves when evaporated a residue which after washing with water is pure betulinamaric acid. Dried over sulphuric acid it has the composition represented by the formula C36HgJ016,but when dried at ll.OO it loses 2 mol. of water yielding the anhydride C36H18011. The acid and anhydride both dissolve easily in alkalis forming bitter salts whence the name. They are nearly insoluble in water to which they impart a yellow colour and faint acid reaction.They disscilve in all proportions of alcohol and ether and are soluble also in concentrated acids. The anhydride melts at l85" undergoing decomposition. The acid forms two classes of salts one containiiig 4H20less than the other their general formuh bcing C36H1001ZR'4, and C36H480,6R'4. These are regarded by the author as salts of two different acids sus-ceptible of transformation one into the other by elimination or assimi-lation of water. The potassium snZf C36H&12K4 obtained by evaporating a solution of the acid and potassium carbonate in water exhausting the dry mass with alcohol and evaporating is a yellowish-brown hygroscopic mass. From it are derived the calcium salt C3,HloOl2Ca2; the barium salt C36H100L2Ba2 all yellowish-white pre- ; the lead salt C16H10012Pb2 cipitates ; and the copper salt C36H48016C~2, which is a green precipi- tate.The cahium salt C36HJ8016Ca2, was obtained by evaporating a solu-tion in water of the acid and calcium carbonate. The Zead saZt C36H48016PbZ, was precipitated by neutral lead acetate from an alcoholic solution of the acid. ABSTRACTS OF CHEMICAL PAPERS. When betuli~amaric acid dissolved in alcohol is saturated with hydrogen chloride and heated to 120" in sealed tubes a compound is formed agreeing in composition with the formula C44H64014, which is that of the neutral ethyl ether of the acid mimes 2 mol. of water (C,,H,,o1,(C,H,),-2H,o).It melts at 119" (con-). BetuZinic Acid.-This acid is formed together with resinous products on adding chromic anhydride to a solution of betulin in glacial acetic acid and gently warming the liquid. It forms when pure a white powder nearly insoluble in water but easily soluble in alcohol It melts at 200" (corr.) and gives on analysis numbers agreeing with the formula C,,H,,O,. Its alcoholic solution gives with neutral lead acetate an amorphous precipitate agreeing in composition with the formula (C,6H5,06),Pb3 whence it would seem that the acid is hi-basic. J. R and R. BENEDICT Glycyrerretin. By P. WESELSKY (Iie.u;t. C'hem. Ges. Ber. ix 1158-1159) .-This compound which is formed together with sugar by boiling glycyrrhizin with dilute acids J-ields when fused with potash only paroxybenzoic mid.c. s. Lignite-tar. By 0. BURG(DeuLt. Chem Ges. Ber. ix 1207-1209).-The heavy high-boiling oils of lignite tar contain a substance capable of combining with picric acid to form a compound which crys- tallises €rom benzene in long needles and gradually decomposes in the air. When the crystals are decomposed with ammonia and the oil thus liberated is dissolved in carbon bisnlphide or chloroform and saturated with bromine or chlorine pale-yellow crystals of a bromine- or chlorine-compound are deposited. These compounds are insoluble in water alcohol ether chloroform carbon bisulphide and benzene and soluble in xylene and the high-boiling oils of coal-tar only on pro-longed boiling. They are deposited from their solutions in small needles agreeing in composition with the formula Cl,H,Brl or Cl8H*CL.The same compounds may be obtained by treating the crude oils directly with bromine or chlorine. They are not acted on by sodium- amalgam or by potash. When heated with zinc-dust they yield a hydrocarbon crystallising in lamin% which melt at 122" and dissolve in alcohol glacial acetic acid ether chloroform and carbon bisulphide forming greenish-yellow fluorcscent solutions. The boiling point of the hydrocarbon lies above 360". Its formula deduced from ana3pis is C,sH,z. A solution of the hydrocarbon in chloroform gives on addition of bromine a yellowish-white precipitate of a broniine-compc,uncl, Cl,H,Br3 which dissolves in boiling benzene and crystallises therefrom in small needles.The hydrocarbon is converted by oxidation with chromic acid into a quinone-like body of reddish-brown colour agree-ing in composition with the formula Cl0H6O2. J. R. Some Constituents of Adonis Vernalis. By F. LINDEROS (Liebig's Ann~17er~,, clxxxii 365).-Accorcling to the authoZ"s iuvestiga- tion the leaves of this plant gathered at the time of flowering contain ORGANIC CHEMISTRY. 9i 18 per cent. of their weight (when dry) of aconitic acid in the form 0f calcium and potassium salts. J. R. On the Acids inRoman Chamomile Oil. R~RUDOEPH FITTIC; (Deect. Clmn. bes. Bey. ix 1195).-The author has obtained from this oil an acid melting at 45" and boiling at 185" and a second acid melt- ing at 65" and boiling at 198.5'.These acids are present in about equal proportions. Both agree in composition with the formula @,H,O,. Besides these the oil contains another wid boiling at 360". The investigation is being continued. J. R. Some Constituents of Gelsemiurn Sempervirens. By F. L. SONNENSCHEIN (Dezcf. Chem Qes. Be?*.,ix 1182-1186).-The root of this plant which in North America is used for medical preparations contains according to Wormsley a peculiar acid which he calls ye7-semic mid. This body is however idelltical with Esculin. Besides this compound the root contains also an alkaloid gelseinine which was obtained as an amorphous colourless or slightly pinkish mass melting below 100" to a colourless liquid. It dissolves but sparingly in water pllore readily in alcohol and freely in ether and chloroform.Its solu-lution has a very bitter taste and a strongly alkaline reaction. Its h-j-drochloride is amorphous neutral readily soluble in water and the solution is precipitated by tannic acid solution of iodine in potassium iodide gold chloride phosphomolybdic acid &c. Platinic cliloridc prodnces an amorphous lemon-yellow precipitate which dissolves 011 warming and crystallises on spontaneous evaporation in transparent quadyatic octohedrons which on the addition of water are changed into the amorphous compound while platinic chloride goes into solu-tion. The composition of gelsemine is C,,H,,NO,; that of the hydro-chloride (C1,H,,KO2),ClH and of the amorphous platinum-salt- 2[C,lH19N02),HC1] + PtC14.The pure alkalo'id dissolves in coneenti-ated nitric acid wit11 a greenish-yellow and in sulphnric acid Tith the same colour which however soon changes into a reddish-brown and dirty-red. When potassium dichromate is added to the sulpharic acid solution the liquid changes first into cherry-red and then into bluish-green whilc by using cerosoceric oxide a bright cherry-red colour is produced. On administering 0.012 gram of the h-j-drochloride to a large pigeon it died with convulsions in 36 minutes and frogs exhibited the same symptoms. c. s. VOL. XXXI.