0RGANIC CHEMISTRY. Organic Chemistry. Investigation of the first Products obtained in the Manufac-ture of Benzene. By K. HELBING (Ann. Chem. clxxii 281-297). ERLENMEYER detected propione while searching for the hydrocarbon C4H4,among the volatile liquids which pass over at low temperatures during the distillation of light coal-tar oils in the preparation of benzene. The author endeavoured to obtain a large quantity of pro-pione from the same source but failing in this he divided the liquid by fractional distillation into a number of parts and examined each closely. The liquid contained still 51 per cent. of benzene and 16.28 per cent. of carbon bisulphide. The part boiling between 18" and 40" was treated with bromine and again distilled and by this means a liquid and a solid product were obtained.The liquid consisted of amylene bromide C5HloBr2, mixed with bromine substitution-pro- ducts ; the solid contained crotonjlene tetrabromide C,H,Rr,. VOL. XXVIII. E ABSTRACTS OF CHEMICAL PAPERS. The part boiling between 50" and 70" was also treated wit'h bromine and gave hexylene bromide C6HI2Br2, mixed with a small quantity of bromine substit,ution-products. G. T. A. Action of Nitric Acid on Paraffin. By A. G. POUCHET (Compt. rend. lxxix 320-324). BY the action of fuming nitric acid upon paraffin the author has obtained very complex products including soluble fatty and other acids and a substance which according to liis statement contains a new acid to which he gives the nameparqfiwic acid.He has not observed the cerotic acid which was observed by Gill and Meusel under similar circumstances. Paraffinic acid is described as a slightly yellowish solid rather lighter than water and combustible. It is soluble in alcohol giving a solution which is acid to test paper and from which it crystallises in pearly scales. It melts between 45" and 47'. The acid is monobasic and its formula deduced from the analysis of the barium lead and silver salts as well as of the acid itself is C24H4802. If this .formala is correct that of paraffin must be C21H,o.. W. A. T. Note on Tertiary Nitrobutane. By J. TSCHERNIAK (Deut. Chem. Ges. Ber. vii 962). THIS body prepared by treating the corresponding iodide with silver nitrite during which operation much isobutylene oxides of nitrogen water and nitrite of ethyl were also pr'oduced gave by reduction with iron and acetic acid much isobutylene ammonia aid a small quantity of butylamine.When treated by the usual methods it yielded neither bromine derivatives nor a nitro-acid. 31. J. S. Constitution of ordinary Bromo-Propylene. By E. REBOUL (Compt. rend. lxxix 317_32,0). THEauthor finds that ordinary bromo-propylene is a mixturc of two isomerides ; one which he distinguishes as a-bromo-propyleiic boils at 48" ;the other ,B-bromo-propgrlenc boils at 59"*5-G0" under a pressure of 740 mm. The latter has the formula CH,-CH=CHBr. These two bodies cannot be separated by fractional distillation but the second may be completely isolated by taking advantage of tlhe fact) that it unites with hydrobromic acid much less rapidly than the first.The new bromo-propylene ccim bines slowly at 100" with hydrobromic acid furnishing a mixture of two propylene bromides which distil bctween 132" and 143". It also combines with bromine yielding a liqiiicl bromide CH3,-CHBr-CHBr2 of specific gravity 2,356 at 18" and boiling at 200"-201" (corr.). The isomeric a-brorno-propylei:e gives with bromine a bromide CH,-CBr,-GHBr which boils at 190". W. A. T. ORGANIC CHERIISTRT. Note on the Etherification of Glycol. By A LORIN (Compt. rend. lxxix 387-389). OXALICacid reacts with glycol nearly in the same manner as with glycerin but some of the formina produced distil over unchanged uhcn the mixture is heated.The author also finds that potassium foimate may bc substituted and with some advantage for the acetate in the preparation of glycol. W. A. T. Action of Ally1 Bromide on Silver Nitrite. By R. SCHIFF (Deut. Chem. Ges. Ber. vii 1141-1145). BRACKEBUSCH states that by the action of allyl bromide on silver nitrite allyl nitrite and nitropropene are formed. On repeating this reaction the author could only obtain besides gaseous products and water an oily liquid still containing much undecomposed allyl bromide and only so small a quantity of nitrogenous products that by using 377 grams of the bromide no definite compound could be isolated. c. s. Diallyl Compounds. By L. HENRY (J. pr. Chem. [Z] ix 476 480). DiaZZyZcZicl~Zor7~y~~~~~, CsH,,(OH),CI,.-The author has formerly shown that ally1 compounds unite with hypochlorous acid to form deri-vatives of glycerin.Some recent experiments have shown that diallyl unites with hypochlorous acid to form diallyl- dichlorhydrin. The mercury used in the preparation of the hypochlorous acid must be removed with hydrogen sulphide taking care not to pass excess of the gas as it acts on diallyl. The chlorhydrin is extracted with et,her and the solution left. to evaporate over sulphuric acid. It forms a thick fluid with a pleasant odour resembling that of' glyceric chlor- hydrin and has a bitter acrid taste. At 7" its specific gravity is 1.4; it is sparingly soluble in water but dissolves with ease in alcohol and ether. It cannot be distilled for on heating it hydrochloric acid is evolved and a carbonaceous residue remains.This body may be regarded as two molecules of glyceric chlorhydrin connected together. The author hopes to be able to form diallyl erythrite C,H,,(OH) from this substance. The two hydroxyl groups and the two atoms of chlorine must as far as analogy shows be con- nected with four separate carbon-atoms ; he therefore supposes that the two allyl groups are united by a double affinity. The author offers a fern remarks on another alcoholic compound of dlyl-ncryZ pi?zccco?zc,CsH,,02. It is obtained by the action of nascent E2 ABSTRACTS OF CHEXICAL PAPERS. hydrogen on acrolein two molecules of ncrolein uniting with one mole-cule of hydrogen. Acrolein is an aldehyde and a,s such must contain the group CHO.Its formula may be expressed by C2H3.CH0. Acryl- pinakone may be regarded as a secondary tetratomic unsaturated glycol and its formula would accordingly be- C2HS-CH.OH I C,H,-CH.OH. If the constitution CH2=CH.CH0 be accorded to acrolein acryl- pinakone would have the formulab-CH2=CH.CH(OH)-CH( OH)-CH=CH,. Henninger's croton glycol derived from erythrite by the action of formic acid has the formula C4H6(OH),. If the formula ascribed to acryl-pinakone is correct it may be possible to transpose it into an octatomic hydrocarbon C6H6 different from propargyl . The products of addition of the halogens [C6H8(OH),X4] must be identical with the derivatives of a normal hexatomic alcohol CeH8( OH)6 probably mannite.It may be possible thus to prepare mannite synthetically. This the author proposes to attempt W. R. Researches on Mannite. By LEOVIGNON (Ann. Chim. Phys. [5],ii 433-473). THISpaper opens with an account of the discovery sources properties and composition of mannite. The work is then divided into three chapters the first,portions of each being devoted to a history of the questions brought under consideration. I. The Action of Mannite on Polarised Light.-Alone mannite exerts no perceptible action on polarised light but on saturating the solution with boric acid and examining its action on a polarised ray in a Soleil's apparatus with a column of liquid 200 millimeters long a comtant deviation of + 1.20" occurred. On noutralising the acid with pure sodium carbonate the deviation increased to + 5.04'.On dissolving borax in an aqueous solution of mannite the liquid becomes strongly dextrogyrate ; other borates show the rotatory power of mannite though in different degrees. A given weight of boric acid in the state of alkaline salt increases the rotatory power much more than the same weight of acid in the free state. A mannito-boric acid solution (satu- rated) gave with yellow light a deviation of a = + 1-38'; the same neutralised with sodium carbonate a = + 5.83"; neutralised with potassium carbonate a = + 6-63"; or with ammonium carbonate a = + 6-73". Borates insoluble in water but dissolved in hydrochloric acid gave the same deviations as boric acid ; diffi~ult~ly soluble borates such as that of lime with excess of boric acid gave intermediate devia- tions.The amounts of the deviations thus caused for all these bodies are immediate and permanent. Arsenates dissolved in solutions of mannite likewise develop rotatory ORGASIC CHEXISTRS. power and other bodies will probably be found to act in a similar manner. Arsenic acid in a solution of mannite causes a deviation which in- creases with time ; thus to a solution of mannite in which the propor- tion by weight of water to mannite was as 6.3589 exactly 10 per cent. by weight of arsenic acid was added. For the yellow ray with a thickness of 200 millimeters the deviation was after one hour a = + 0.3924"; after 24 hours a = + 1*1090°. The solution was then gradually neutralised by the addition of sodium carbonate in portions of 0.5 gram at a time.After the first addition a = + 0.1674" ; after the second a = -11*2059";after the third a = -11.7642". In 40 grams of the mannite solution made as before two grams of neu trxl sodium arsenate were dissolved. This examined for a thickness of 200 millimeters gave ccy = + 0.3574 and after some time only such trifling variation that with tri-sodic arsenate the mannite appears to effect a deviation which is immediate and permanent. Monopotassic arsenate increases with time and according to the quantity of the salt present the extent of the deviation in the mannite solution. Thus in four solutions of the original strength (weight of mannite to water 6.3589) increasing weights of monopotassic arsenato were added and examined after five days.The results were- 1. 61 == 0.036 ........ a = -4.22" 2. B2 = 0.049 ........ a = -8.46" 3. @3 = 0.060 ........ a = -11.59" 4./3& = 0.072 ........ a -16.30" P represents the weight of the salt in one part of the solution. A fifth solution in which /3 = 0.083 became in three days quite solid but without diminishing in transparency. This substance may readily be produced by saturating boiling water with mannite and monopotassic arsenate ; on cooling it solidifies and is as transparent as glass rather friable and it is strongly laevogyrate. It dissolves slowly in water yielding an acid solution. Hence it is inferred that mannite dissolved with arsenic acid or monopotassic arsenate suffers a commence- ment of etherification.Determination of the Molecular Rotatory Power of XurLnite.-Thtt method employed which was the same as that devised by Biot in the case of tartaric acid was based on a comparison of the deviations pro- duced by a series of mannito-boric solutions in which the proportion of water to mannite remained constant while the proportion of boric acid was continually increased. The result gave €or t,he rotatory power of mannite in aqueous solution with tJhe particular proportion of water used in the experiments- (a) = + 018255". 11. Ma,~mitan.-This compound was prepared from mannite by treat- ing it with half its weight of concentrated sulphuric acid at 125" (below this temperature the action is very slow ; above it the mass blackens and only a small quantiiy of impure mailnitan is obtained), the mixture being stirred from time to time.The mass browned 54 ABSTRACTS OF CHEUICAL PAPERS. slightly and became liquid. dfher two lioara it wa4 noutralised with barium carbonate without allo.ving the temp4rature to fall. The mass was then exhausted with absolute alcohol filtered evaporated and dried at 120". By this process mannitan is obtained as a very viscous slightly brown mass very soluble in water and in absolute alcohol having a sweet taste and an odour somewhat like that of caramel. 20 grams of mannite yielded 12 to 15 grains of mannitan. The formation of maiinitan in this process is due tl>the direct dehy- dration of the mannite by the sulphuric acid and not to the formation of sulphomannitic acid and its subsequent resolution into sulphuric acid and mannitan for when barium sulphomnnnitate prepared by neutrali- sing with barium carbonate the product of the action of sulphuric acid on mannitan is heated to 125" it quickly becomes acid and if after two or three hours it be saturated at the same temperature with barium carbonate the products obtained are barium sulphate and mannitan but if the sulphomannitate be previously mixed with excess of barium carbonate so that the mixture may always remain neutral the sul-phuric acid being neutralised as fast as it is set free nothing is obtained but barium snlphate and niannite without a trace of mannitan.It is clear then that the formation of mannitan in the former case is due to the dehydration of mannite by the sulphuric acid set free by the decom- position of the sulphomannitate. The molecular rotatory power of mannitan was found to be- (a>y= +36.5". Nit~oma?mitmzwas obtained by dissolving 1part of mannitan in cz mixture of 10 parts of sulphuric acid and Q parts nitric acid of sp. gr. 1.50. The materials having been left in contact for a quarter of an hour and kept cod the mixture is thrown into a large quantity of water. A white precipitate then falls which is washed with water and digested with ether which dissolves the nitro-mannitan. This ethereal solution is evaporated and concentrated in a vacuum. Nitromannitan wlieii gradually heated evolves nitrous vapouw swells up and burns rapidly leaving a carbonaceous residue.It ex-plodes when struck with a hammer. It is soluble in alcoliol and ether. Its rotatory power determined in an ethereo-alcoholic solu-tion is-(a) = + 53.26". No anal-j-sis of this compound could be effected on account of its physical condition and its proneness to detonation but from analogy the formula C6H7(N02)505 is suggested. Heated with caustic soda solution nitromanni tan yields a blackish gummy mass not explosive by percussion and not containing either mannite or mannitan. With ammonium sulphide it yields mannitan. 111. Actiox of Water OTL JIarzi~itein Xealecl Tubcs nt tlifererit Tenapso-tures.-l. By heating mannite with half its weight of water in a scaled tube for four hours to 280° a yellow translucent liquid is obtained cyntnining blonn flocks in saspension ; no gas is cvolvccl on opening tlie tube.ORGANIC CHEMISTRY. If tlie tube be heated to 295" maniiitan is obtained. 2. The aqueous solution obtained by heating to 280° evaporated on a water-bath and dried at lZOo,.yields a thick syrup containing crys- tals of mannite ; and on exhausting this syrup mit8h absolute alcohol evaporating the solution and drying the residue at 120" a yellowish viscid mass remains which is hvogyrate. If this viscid mass be exposed to air either moist or dry or dry hydrogen or oxygen it deposits crystals which are also hvogyrate and therefore do not con- sist of mannitan. The crystals are insoluble in absolute alcohol and appear to have pre-existed in the mass and to have been carried into solution in absolute alcohol by reason of the great excess of the viscous mass which was also soluble.In about a month the viscous mass ceases to deposit crystals ; and if from time to time they are removed the mass then taken up with absolute alcohol tbe solution evaporated the residue boiled for an instant with water the liquid filtered through animal charcoal arid evaporated to dryness the residue washed with ether again taken up with absolute alcohol the alcoholic solution filtered and evaporated and the residue finally dried at 120" till it no longer loses weight a yellowish substance of the consistence of turpen-tine is obtained having the composition of mannitic ether t,he mean of several analyses giving C =41-70 ; H = 7.6; while the formula of mannitic ether CIZH2G011, requires C 41.6 -H 7.5.Mannitiic ether is hvogyrate its molecular rotatory power being (a) = -5.59". It does not reduce Barreswill's liquid nor ferment in contact with yeast. By boiling with dilute snlphuric acid or baryts-water it does not yield either mannite or mannitan. That this substance is really mannitic ether is shown by the facts that when dissolved in concentrated sulphuric acid it yields a sulpho- conjugated acid identical with the one yielded by mannitan ;that when treated with a mixture of nitric and sulphuric acids it yields a nitro- derivative analogous to nitro-mannitan ; and that when heated with a little water to 295" in sealed tubes it is converted into mannitan.3. The Crystalline Xubstan,ce deposited by the Ct-ucle iklccnnitic Ether Xmz,nitone.-This substance is obtained pure by washing with cold absolute alcohol dissolving in water filtering through animal charcoal and then evaporating. It is chemically isomeric with mannitan. The two isomelides do not give two distinct series of derivatives. Mannitonc treated with a mixture of nitric and sulphuric acids yields the same nitro-derivative as mannitan and mannitic ether. Mannitone is lmogyratc (u) = -25". It has a sweet taste and does not reduce a cupro-potassic solution. Heated with water to 295" in sealed tubes for three hours it is completely converted into mannitan. C. H. P. Contributions to our Knowledge of the Starch-group.By W. NAGET~I (Ann. Chem. clxxiii 218-227). STARCH is a mixture of several modifications ; when it is treated with not too coilcentrated acids that portion which is coloured blue by iodine and preponderates in the softer parts of starch is dissolved and 5 6 ABSTRACTS OF CHEMICAL PAPERS. a portion is left to which iodine imparts a yellow coloar. This modi- fication is only slowly changed by acids or boiling water; it still possesses the structure of the granules and its hardest part seems to be identical with or nearly related to cellulose. The “ blue” and “yellow ” modification-meaning thereby the modifications which are respectively termed blue and yellow by iodine-change gradually into each other forming others which are coloured by iodine violet red or orange.Potato-starch contains little of the latter but much of the “blue,” and still more of the “yellow,” and in wheat-starch less yellow occurs and hardly any blue but much of the violet and reddish- violet. When starch is boiled with water the quantity of the “blue ” modification increases. On boiling “ yellow ” starch with water for a long time the greater part dissolves and the solution gives with iodine a violet colour. On evaporation or on allowing the liquid to freeze amylodextrim separakes out in discs having a diameter of 0.035 mm. and consisting of small needles which may be obtained singly by carefully precipitating the solution with alcohol. Under the polariscope the discs show crosses like starch but in a different position being turned about 45”.Amylo-dextrin when freshly precipitated by alcohol is soluble in cold water but it soon loses this property and then dissolves in water only at 6Oo-65O. On cooling no amylodextrin separates out at once but only slowly on standing quickly however when the liquid is frozen. The composition of the substance dried at loo” and after deducting 0.1 per cent. of ash containing phosphoric acid potassium sodium and calcium is C36H6,O:o + H20. Its solution turns the plane of polarisa-tion to the right; the rotatory power being about the mean of that of starch and dextrin. Alcohol does not precipitate it as readily as starch while tannin basic lead acetate and barpta-water do not precipitate it.The solid substance is coloured yellowish by iodine but the solu- tion turns first violet and then red because amylodextrin also exists in two modifications which can be separated by partially precipitating its solution with sodium acetate. The dextrin obtained from amylodextrin also exists in two modifications one being coloured red and the other yellow or brown by iodine. It is also readily converted into sugar even by potash-solution and therefore it reduces Fehling’s solution. c. s. On a mode of Decomposition of Chloral-hydrate. By M. TANRET (Compt. rend. Ixxix 662). IF a mixture of solutions of chloral-hydrate and potassium perman- ganate be made alkaline say with caustic’potash gas is evolved the liquid becomes discoloared and sesqnioxidc of manganese is precipi- tated.If several grams of chloral-hydrate be acted upon and the temperature not raised above 40° the reaction will last for some hours ; then on filtering the liquid the filtrate will be found to contain chloride carbonate and formate of potassium. The gas evolved is carbon monoxide. The reaction occurs equally with very dilute solu- tions and even if borax be substituted for potash. This decomposition ORQA.NIC CHXMISTRY. leads to a theory to account,for the action of chloral-hydrate upon the animal system. It is snggested that when this substance is taken into the circulation it is submitted to oxidizing agencies ; the alkalinity of the serum determines its decomposition ; the carbon monoxide dis- places the oxjgen from the arterial blood and produces an effect similar to that resulting from poisoning by carbon monoxide.The lowering of the temperature of the body and the prolonged action of the chloral-hydrate owing to slow decomposition tend to make this theory more tenable than the assnmption of its conversion into chloro- form. C. H. P. New Method of Preparing Ethylnitrolic Acid. By V. MEYERand J. LOCHER (Deut. Chem. Ges. Ber. vii 1137-1141). Tms acid is formed by allowing a mixture of an alcoholic solution of dibromonitroethane and an aqueous solution of hydroxylarnine to stand for 12 hours-NO2 NO2 CHa-C / + HZN-OH =CH3-C / + 2HBr. \\ N-OH Hydroxylamine gives no crystalline product with monobromonitro- ethane and does not act all on nitroethane.c. s. Ethylic Ethyl-sulphonate. BJ A. KURBATOW (Ann. Chem. Pharm. clxxiii 7-8). THIS substance originally obtained by Carins can be readily ob- tained by heating silver sulphite with ethyl iodide in the presence of ether. T.B. On Sulphocyanocarbonic Acid and its Derivatives. By L. HENRY (J. pr. Chem. [2] ix 464-468). Eulpkocy am-carboiaic etk el^ CO { was obtained by the action of chlorocarbonic ether on potassium or ammonium sulphocyanate dis- solved in alcohol. Potassium or ammonium chloride separates and is separated by filtration off. Most of the alcohol is then distilled off and on addition of water a heavy oil sinks to the bottom and after a short time crystallises. The ether when re-crystallised from alcohol or ether forms long prismatic transparent crystals tasteless and nearly without smell in the cold.It is insoluble in water but dissolves easily in alcohol ether and carbon sulphide. It melts at 41". When dis- tilled it begins to boil at go" with decomposition into carbonic anhj-dridc ethyl sulphide and cyanogen sulphide. The ethyl sulphide ABSTRACTS OF CHEMICAL PAPERS. distils over first. The sulphocyanocarbonic ether comes over heiwecn l60"-21O0. SzcZ~l~ocya~ocarbonntes,-The alcoholic solution of the ether gives a precipitate with alcoholic potash. The potassium salt is very slightly soluble in alcohol even when hot but dissolves easily in water. Other salts are with exception of those of the alkaline metals insoluble in water.The copper salt is blue and the lead and silver salts white ; the latter turns black with formation of silver sulphide. Szc7phocyanoca;rboric Acid.-If hydrochloric acid be added to the potash salt an oil separates out which rapidly crystallises. Af t'er cool- ing the liquid is interlaced with white qeedles. The acid is easily soluble in alcohol ether and moderately soluble in warm water. It may be sublimed with water-vapour. It melts at about 43",has a sharp taste and a slight odonr resembling that of its ether. In a foot-note the author adds that he has failed to form malonic acid bv the action of chlorocarbonic ether on acetic ether neither did the compound { result from its action 011 potassium sulphite. W. R. Structure of the Derivatives of Benzene.By E. WROGLEVSKI (Deut. Chem. Ges. Ber. 1060-1061). WHENin a para-compound a third atom of hydrogen is replaced a 1,3 4,or what is the same a I 2 4 compound is formed. But met&- and ortho-compounds yield also products of this structure. Thus Reilstein and Kuhlberg have found that common monochlorobciizoic acid yie1ds.a dichlorobenzoic acid which is identical with that formed by oxidising chlorinated parachlorotoluene and that orthonitrotoluene and paranitrotoluene yield the same dinitrotoluene. PurLhcr Fittig has shown that pseudocumene may be obtained from isoxylene and from paraxylene. The derivatives of benzene behave in the same way. On brorninating the three dibromobenzenes one and the same tribroinobciizcne is formed which melts at ao, and has also been obtained fi-om dibromo-phenol and dibromaniline.c. s. Electrolysis of Potassium Phenylacetate. By T. SL AJV I IC (Deut. Chem. Ges. Ber. vii 1051-1057). WHENpotassium phenylacetate is decomposed by the galvanic current it is resolved like other salts into the base and acid ; but by the action of the oxygen and ozone the latter is oxidised to benzaldehyde and berlzoic acid which however have only an ephemeral existence being quickly burnt to water and carboii dioxide. A solution of the free acid is but slowly decomposed the same products being formed which are also produced in an alkaline solution together with two neutral solids one melting at 90"-93" arid the other at 115". By the action of potassium pernianganate on an alkaline solution benzoic acid is formed while I)y pissing ozoiie into it the odour of ORGANIC CHEMISTRY.5 9 benzaldehyne is given off and benzyl phenylacetate CsH,.CH2.C0,.CH2. CsH5,is obtained as a light-yellow liquid having a faint aromatic smell the sp. gr. 1.101 and boiling at 317"-319". c. s. Cyrnenes. By F. FITT I c A (Ann. Chem. clxxii 303). THIOCTMENE was prepared by heating together four parts of thymol and one of phosphorus pentasulphide in fine powder in a flask with inverted condenser ; much sulphuretted hydrogen was evolved and thiocymene (b. p. 230") was simultaneonsly formed ; the hydrocarbon isolated from this by fractional distillation treatment with soda-ley and repeated distillation over sodium boiled at 175" (mercury-column wholly in the vapour) and dissolved in strong sulphuric acid without evolving sulphnrous acid ;this serves as a good test of purity.Ptychotis cxmene was prepared by fractional distillation of the expressed oil of Ptychotis Aj02u$n the portion boiling at 170"-210" being heated with sodinm and treated with diluted sulphuric and potassium dichromate or with dilute permnnganate of * potassium until it would bear the test of sulphuric acid. The purified product boiled at 175"-1 StiO (mercury-column wholly in the vapour) . Camphor cymene was prepared by acting on camphor with phosphoric anhydride in quantity sufficient to forin (theoretically) cymene and metaphosplioric acid ;the yield is thus GO-SO per cent. whereas Pott'rJ method with pentasulphide of phosphorus gives only 25 to 30 per cent.; after purification as before this specimen boiled at 175" (mercury-column wholly in the vapour). Beilstein and Kupffer found the same number. These three hydrocarbons were oxidised by dropping into gently boiling red nitric acid (sp. gr. 1.5) ;in each case 71itrotoZuic acid meltling at 189" was produced hence all these are methyl-propyl-benzenes. By acting on them with bromine in presence of iodine a bromocymenc wag produced boiling at 228"-229" in each case and by oxidising this with dilute nitric acid b~oi~zonit.rotoZrcicacid melting at 204"-205" was formed. Strong colourless nitric acid converts these cymenes into drocymmm of two kinds one fluid and incapable of distillation unaltered (save in vncuo) ; the other crystalline and melting after due purification at 125"; by oxidation the fluid varieties yielded a nitroto-luic acid different from the above-mentioned body melting at 189O ;the barium salt of this acid was readily soluble in water and crystallised therefrom in starlike needles ;the acid itself was soluble in 450 parts of water and was readily soluble in alcohol of 90 per cent.and sub-limed without melting ; the solid nitrocymene yielded on oxidation a third modification of nitrotoluic acid subliming without previous melting and practically insoluble in hot and in cold water and only slightly soluble in alcohol of 90 per cent.; it is not yet decided however whether this product is homogeneous or a mixture of jsomerides.The cymene-sulphonates of barium prepared from these three sub-stances contained (C,,H,,.S0,),Ba,3H20 in each case ; the author's fbniier result with only 2H20 was ixicorvwt tlie estimation linviiig GO ABSTRACTS OF CHEMICAL PAPERS. been made in the ordinary way in watch-glasses in the air-bath whereas the pregent determinations were made by sucking air dried by sulphuric acid over the substances in a Liebig's tube in a paraffin bath at 140"-150". Normal propyl-meth yl-benzene was prepared by acting with sodium on recrystallised bromotoluene melting at 29O together with pure normal propyl bromide dissolved in ether free from water and alcohol. It boiled at 175"-17Ci0 ; gave paratoluic acid melting at 177" and terephthalic acid on oxidation by nitric and chromic acids respectively ; with nitric acid it also yielded a fluid and a solid nitrocyrnene iden- tical with the modifications obtained from the above hydrocarbons the solid melting at 125" and the liquid body giving by oxidation a nitrotoluic acid identical with that obtained from the liquid nitrocy- menes above described.The author hence concludes firstly that Ptychotis thyrnol and camphor cyrnene are identical and secondly that the hydyocarboi$ thzcs obtained is normal propyhethy 1-benzene and not isopropyl-methyl-benzene ;the different results obtained by other experimenters being explicable by this imperfect purity of the materials worked with; thus Kekul6's normal propyl-methyl-benzene was impure on account of the method of preparation of pure bromotoluene (m.p.29') not having been discovered at the time of his experiments ; and the results of Landolph and others were erroneous on account of t'he presence of hydrocarbons richer in hydrogen in the cymenes used. The thymo-cymene mercaptan obtained from thymol together with nymene by the action of phosphorus pentasulphide was converted into mercury-compound and decomposed by sulphuretted hydrogen ; it then boiled at 230"-231' and did not solidify at -20". The mercury salt melts at a temperature near 78" is very sparingly soluble in alcohol and crystallises therefrom sZowly in greenish rhombohedrons. As the camphor thiocymene gives a mercury compound crystallising from alcohol quickly in stellar groups of needles and melting at log", the author regards the two as isomeric.In like manner the silver-salt of the thymo-compound is amorphous whilst that of the camphor body becomes a mass of silky plates on standing ; moreover by oxida- tion a toluene sulphonic acid is formed different in each case; the acid from thymol is anhydrous and sparingly soluble in water; that from camphor contains Walter and readily soluble in water ; the for-mer gives an anhydrous magnesium salt the latter one containing water of crystallisation. The isomerism of these two derivatives of normal propyl methyl benzene may be represented by the formuh- ORGANIC CHEMISTRY. tj1 Camphor thio-cymene Thymo-thiocyinei ie (cymophenol or thio-(thymo-cymene cymene of Flesch). mercaptan).CH3 CH3 I I C C / \\ /\ HC 'C-SH HC CH I1 I HC CH Note by Abstractor.-The abstractor's experiments on 16 different varieties of cymene obtained from various terpenes and substances allied thereto have led him to the conclusion that there is but one cymene obtainable from all these sources and that this cymene is identical with camphor cymene. The abstractor however has uni- formly found a slightly higher boiling point (when duly corrected) than that obtained by Fittica 176.5" being the mean result obtained with specimens purified by numerous treatments with sulphuric acid and distillation over sodium. C. R.A. W. Tetraterebenthene a Solid Polymeride of Essence of Turpen-tine. By J. RIBAN(Compt. rend. Ixxix 389-3933. THE new compound is produced by the action of antimonious chloride SbC13 on terebenthene.It is an amorphous brittle solid of slightly yellow colour almost insoluble in alcohol soluble in ether carbonic sulphide benzene petroleum and essence of turpentine which on evapo-ration leaves it as a colourless varnish. Tetraterebenthene rotates the plane of polorisation to the right [a],= + 20" whilst the hydrocarbon from which it is produced has a left-handed rotation. Its deiisitg is 977 at 0'. It melts below 100" but passes into a viscous condition which renders it impossible to de- termine the point precisely. Heated to 350" it is not volatilised but above that temperature it undergoes a transformation into hydro- carbons of the same composition but of less condensation.The pro- ducts of this metamorphosis are volatile and are soluble in alcohol. Tctraterebenthene furnishes amorphous compounds with hydrochloric and hydrobromic acids ; from their composition its formula is inferred to be C4,,He1. The author points out that the depolymerisation of tetraterebenthene under the influence of a high temperature suggests the explanation of the fact that certain natural resins copal and amber for example become soluble in the usual solvents only after exposure to 350" or 400". W. A. T. BBSTRACTS OF CI-IENICAL PAPERS. The Physical Properties of Isoterebenthene. By J. R I BA N (Compt. rend. lxxix 314-317). BOILING point 175". Two specimens prepared from lzevogyrate (-39.3j terebenthene from French turpentine gave a left-handed rotation of 9.17" and 9.72" respectively.Density at 0" = a8.586; at any higher temperatuye up to 10~'it is given by the formula- D = -8586 -*0007692t -*0000002375P. Index of refraction for line U at temperatare 25" = 1.4709. Specific refractire energy fn-1 = -5611. L__ a For corresponding characters of terebene and terebenthene see this Journal p. 580 last volume W. A. T. Constitution of Phenyl-bromethyl. By E. BAND n OW s K I (Dent. Chem. Ges. Ber. vii 1016). WHEXphenyl-bromethyl is treated with zinc-dust and toluene a hydrocarbon is produced which boils at 278"-280" and contains C15H16.When this is oxidised by chromic acid mixture parabenzoyl- benzoic acid is obtained together with another substance which was not obtained in sufficient quantity for examination.The above-mentioned liydrocarbon has probably the constitution C,H,-C,H,-C,H,-CCH, and its formation confirms Radzizewski's formula for phknyl-bromethyl. T.B. Action of Heat on Phenylxylene. By P. BARBTER (Compt rend. lxxix 660-462). BESIDES the hydrocarbons C14H14,derived from the double molecule of toluene there exists a whole series of isomeric hydrocarbons resulting from the association of 1 molecule of benzene with 1 molecule of xylene thus :-CsHio + CsH -H = C,,H,,. Each of the isomeric xylenes should furnish its own hydrocarbon C14H,,. In order to get a general idea of the possible reaction the action of heat on the hydrocarbon yielded by coal-tar xylene and hen-zene was investigated.The new hydrocarbon was prepared by the action of powdered ziiic On a mixture of benzene and tolyl-chloride in the proportions of 1to 3. On warming the mixture a lively reaction occurred accompanied by a copious evolution of hydrochloric acid. The product! after repeated fractional distillation gave a liquid boiling at 270"-280" which when kept boiling on sodium till it ceased to attack the latter then again fractionated yielded a liquid boiling at 283"-286" (corrected) of density 1.01 at 0" Laving a slight alliaceous odour and exhibiting 8 blue fluorescence. By analysis it yielded the following numbers :- ORGANIC CHEMIST&I7. C14H14 C ........... 91-8 92.1 92.3 H ......... 7.9 8-0 7.7 Heated in a tube to a dull red heat for tliree minutes phenylxylene solidifies without deposition of carbon to a yellowish-white mass of an thracene mixed with phenanthrene the secondary products being a mixt)ureof xylene and benzene volatile at 14@", and giving terephtalic acid by oxidation.A slight pressure occurs in the tube the gases being hydrogen and a trace of hydrocarbon vapour. The following equation exhibits the reaction :-Triphenylbenzene. By C. ENGLER and H. E. BERTHOLD (Deut. Chem. Ges. Ber. vii 1123-1125). THIS hydrocarbon which is formed but in small quantity only. by the action of phosphorus pentoxide and other dehydrating agents on ncetophenorie is conveniently prepared by saturating this ketone with dry hydrochloric acid. On standing yeliow needles separate out niore of which are obtained by treating the liquid portion repeatedly in the same way.By recrystallising the crude product from ether pure triphenylbenzene is obtained in well defined crystals of the rhom bic system. It melts at 169"-170" boils above the boiling point of sulphur is but sparingly soluble in dilute alcohol readily in absolute alcohol ether and carbon sulphide and very freely in benzene. ~o52obronzotr~hei~yZbeizzene, C2*H1,Br,is formed by leaving a solution of the hydrocarbon and bromine in carbon sulphide to stand. It crystal-lises from alcohol in small colourless needles melting at 104O. Concen-trated nitric acid converts the hydrocarbon into a mixture of nitro-con?pounds. The formation of triphenylbenzenc is perfectly analogous to that of mesitylene from acetone :-3(CH,.CO.CsHtlf,) = C6H,(C6?&)3 + 3H-20.c. s. Mesitylene. By A. LADENBURG (Deut. Chem. Ges. Ber. vii 1133-1137). WHEN amidonitromesitylene (nitromesidine) ,which is fornicd by the action of ammonium sulphide on dinitromesitylene is treated with acetyl chloride &ro-ncetyluzesidine is obtained crystal lisin g from alcohol in silky needles which melt at 188". By act'ing on it with a mixture of nitric and sulphuric acids the dinitro-compound, C6(CH3),(NH.C2H,0)(N0,)z,is formed crystallising from hot alcohol in glisteniiig white needles melting at 275". On heatling this com- pound with fuming hydrochloric mid to 160° it is converted into the same dinitromesidine that Fittig obtained by the reduction of trinitro-mesit-j-lene.It is violently acted upon by A solution of nitrogen ABSTRACTS OF CHEMICAL PAPERS. trioxide in absolute alcohol the same dinitromesitylene being formed that is obtained directly from the hydrocarbon. Mononitromesitylene was obtained as a bye-product in tlhe formation of the dinitro-compound and by means of the diazo-reaction from nitro-mesidine. The two pro- ducts are identical; they crystallise exceedingly well melt at 42" and boil at 255". By the action of tin and hydrochlorlc acid amido-mesitylene was obtained as a liquid boiling at 226"-227" and not solidifying at -15'. Acetyl chloride converts it into the acetyl-compound crystal- lising from alcohol in glistening thin prisms melting at 213"-214" and subliming in needles.The same body is obtained by heating the base with glacial acetic acid. Fuming nitric acid converts it into the same nitro-compound that was obtained from nitromesidine and acetyl chloride. These facts show that the three hydrogen-atoms of mesity-lene have the same value and therefore confirm Baeyer's hypothesis of the formation of mesitylene from acetone. c. 5. Orthocresol and other Ortho-Compounds. By A. KEKUL~ (Deut. Chem. Ges. Ber. vii 1006-1007). THE cresol which the author and Fleischer obtained by treating cary;t- crol with phosphoric anhydride has now been proved to be identical with orthocresol but previous descriptions of this substance are erro- neous as it melts at 31"-31*5" and boils at 185"-186". Ortho-cresotic acid melts at 163"-164".As statements regarding the ortho-iodo-toluene obtained from tolui- dine do not agree this subject was investigated with the following results. This iodotoluene boils at 205"-205.5" (211" with stem in vapour) and when oxidised it yieids an orthoiodobenzoic acid which melts at 156"-157" and yields salicylic acid on fusion with potash. Orthoiodotoluene can be made to yield orthotoluic acid melting at 102*5". T. B. Nitrophenol and Dioxybenzene. By H. SA L K ow s K I (Deut. Chem. Ges. Ber. vii 1008-1013). THE methyl-ether of nitrophenol melting at 114" was reduced by tin and hydrochloric acid the paranisidine thus obtained being then converted into paradiazanisol by nitrous acid. When the sulphate of this compound is heated with water hydroquinone is produced thus confirming Petersen's view that hydroquinone is a para compound.The paranisidine mentioned above forms colourless rhombic tables which have a peculiar smell resernhling that of honey Paranisidine acquires a dark colour on exposure to light boils at 245"-246" solidifies at 51°-52" and is but slightly volatile with water-vapour. The suZphate and rzitrate of para-diazanisol form colourless crystals which become brown on keeping and these salts are acted on very slowly by water unless a temperature of 140" is employed the hydro- quinone which is formed under these circumstarices being nlwa~s ORGANIC CHEMISTRY. 65 accompanied by a brown viscid substance which is probably a methyl- ether of hydroquinone.In order to prove the relation between paranisidine and anisic acid experiments were made the result of which is as follows. Para-nisidine unites with carbon disulphide and when an alcoholic solution of the product is treated with iodine nnkoZ-suZplzurea [c6H4(OCH,) NHzCS] is precipitated. This substance forms silky leaflets which are slightly soluble in alcohol and melt at 18.5". The addition of water to the alcoholic mother-liquor which has yielded anisol-sulphurea causes the separation of a dark coloured oil containing iodine. When this was distilled with water-vapour a small proportion of a light-coloured slightly volatile oil was obtained which boiled at about 270" and appeared to contain C6H,(OCH3)NcS. When the original dark oil is heated with copper-powder the odour of the iso- nitril becomes apparent but soon gives place to that of bitter almond oil.Although the nitril was obtained only in an impure state by rectification its treatment with alcoholic potash led to the production of a brownish product which in one case was found to yield crystals of anisic acid. Attempts were made to convert the bromanisol which is obtained by the action of alkalis on bromanisic acid into a methyl-benzoic acid but the results were not satisfactory. The bromanisic acid obtained by brominating anisic acid under water melts at 213"-214" and yields only a small proportion of bromanisol. T.B. Derivatives of Secondary Phenyl-ethyl Alcohol (Acetophe- nonic Alcohol) and other Ketonic Alcohols.By C. E NGL E R. and H. BETHGE (Deut. Chem. Ges. Ber. Vii 1125-1129). WHENhydrobromic acid gas is passed into cold secondary phenyl- ethyl alcohol CsH5.CH(OH) CH3,obtained from acetophcnone a bro- mide is formed which is identical with that produced by the direct action of bromine on ethyl-benzene. Radziszewsky found that when liquid bromine is added to the hydrocarbon at 140"-150" a large quantity of styrolene dibromide is always formed. This can be almost entirely avoided by following Berthelot's method and passing bromine vapour into the boiling hydrocarbon. The secondary chloride is ob-tained by passing hydrochloric acid into the alcollol as a liquid boiling with some decomposition at about 194". By acting with sodium on one of these compounds a mixture of products is formed containing dipheny Z-dinzethy Zet72 aize C,H ( CH3) ( C6H5),.It clay s tallise8 from ether in needles melting at 123.5". When the secondary phenyZ-buty Z alcohol C6H,.CH( OH). C3H, is treated with hydrochloric acid the chloride is obtained as a liquid which is decomposed by heatiug. ; and Linnemann's benzhydrol (C6H5),CH.OH yields a chloride which sometimes solidifies at 140",and sometimes remains liquid. On heating it hydrochloric acid is given off and tctraphenyl-ethene is formed. c. s. VOL. XXVIII. F ABSTRACTS OF CHEMTCAL PAPERS. Derivatives of Phloretin. By H. SCHIFF (Ann. Chem. 356-360). PURE phloretin is readily obtained by heating a solution of 20 grams of phloriain in 140 grams of water nearly to the boiling point adding an almost boiling mixture of 10 grams of sulphuric acid and 40 grams of water and keeping the liquid ,at this temperature.After a few minutes a white magma of phloretin separates out which has only to be mashed with water on the filter-pump. To resolve it into phloro- glucin and phloretic acid 20 grams are boiled with 1.50 grams of potash solution of sp. gr. 1.20 for three hours. The solution is then exactly neutralised; then a very slight excess of acid sodium carbonate is added and the phloroglucin extracted by shaking four times with ether. After acidifying with sulphuric acid the phloretic acid is isolated in tihe same way. The ph€oroglncin thus obtained is quite pure but the phloretic acid always contains a little phloroglucin.When phloroglucin is heated with phosphorus oxychloride for some hours it is converted into yldoroglucide C12HloOs, which after distilling off t'he excess of oxychloride and washing the residue with water alcohol and ether is obtained in fine greasy scales. On heating yhlo- retic acid with the oxychloride to 60" no compound resembling a tannin is formed but triphloretide C27H2607! which is insoluble in water and hot alcohol and crystallises from glacial acetic acid in small thin white plates. Quinic acid gives with phosphorus oxychloride an amorphous anhy- dride and meconic acid yields carbon dioxide and a derivative of comenic acid. By the same reagent paraoxybenzoic acid is converted into an isorneride of tetrasalicylide but citric acid yields a compound having the properties of a tannic acid.This body is not directly derived from citric acid but is perhaps a product of condensation of acetone. c. s. Synthesis of Anthraquinone Derivatives from Benzene De- rivatives. By A. BAEYER and H. CAR@(Deut. Chem. Ges. Ber. vii 968-976). THEaction of phthalic acid (1mol.) on the phenols is to form either (with 2 mols.) a phthalein or (with 1 mol.) an antlwaquinone deriva-tive. The reactions occur at an elevated temperature with or without the aid of dehydrating substances. If a moderate use be made of these agents phthaleins are produced whilst if they are more largely resorted to anthraquinones result. The phenols are to be divided however according to their behaviour into two classes thus resorcin and pyro- gallol yield phthaleins even without the aid of sulphuric acid but it has not hitherto been possible to prepare anthraquinone from them.Phenol hydroquinone and pyrocatechin on the other hand do not act upon phthalic acid unless sulphuric acid is present but these yield according to circumstances either phtlialeins or anthraquinones. Phenol and Phthalic Acid.-When phenol is gentiy warmed with phthalic anhydride and sulphuric acid the mixture assumes a brownish ORGANIC CHEMISTRY. 67 yellow colour from the formation of phe~Lol-~7LthnZeirt. On adding more sulphuric acid phenolphthalein-sulphonic acid is produced and if the heating be continued and the temperature raised the colour changes finally fo brownish-yellow.The addition of water at this stage causes the precipitation of yellow or brownish flocculi of ozyantl~ra~?~inone. The formation of the phthalein does not appear to be essential to the production of oxyanthraquinone since if phenol bc added to a suffi-ciently hot mixture of phthalic acid with sulphuric acid the anthra- quinone is obtained without the coloration due to the phthalein being observed ; and as phenolsulphonic acid phenol-disulphonic acid and oxysulphobenzide give a similar result there is reason to suppose that the phenol-phthaiein is converted by heating into phthalic acid and a sulpho-acid of pheiiol which substances at a higher temperakuro gradually react to form oxyanthraquinone CBH4O3 + 2CGHGO C21jH1404+ OH,; C2IjH1404 + 4S04HZ = C8H4O3 + 'LCGHGSZO + SOH ; CBH403 + CGHGS207 + OH = CI~H~O~ + 2SOaHZ.Salicylic acid anisol and even anisic acid behave like phenol ; with salicylic acid particularly when small quantities are employed the reaction takes place with greater regularity than with phenol. The oxyanthraquinone from phenol is a mixture of two isomerides- oxya.i~thmpui~~one, identical with that obtained by Grmbe and Lieber- mann and a new body erytlLroxZlniztl~rapuin,one.They may be separated by taking advantage of the fact that when the former is boiled with water and barium carbonate it forms a soluble barium derivative whereas the latter is without action on the carbonate. Erythroxyanthraquinone crystallises from alcohol in groups of pome-granate-yellow needles which are more soluble in hot than in cold alcohol.It melts at 173"-180" but sublimes already at 150" con-densing in long reddish-yellow needles of the colour of alizarin ; when sublimed it crystallises in very fine needles. Oxyanthraquinone crystallises from alcohol in single sulphur-y ellow needles or plates which aye scarcely more soluble in hot than in cold alcohol. It melts at 268"-271" and sublimes more difficultly in yellow plates. Erythroxyanthraquinone is almost insoluble in dilute ammonia and only slightly soluble in concentrated ammonia oxyanthraquinone being easily soluble in ammonia. The former yields with baryta or lime-water a dark red almost insoluble lake which is decomposed by car-bonic acid ; the latter is easily soluble in barytn and lime-water for&- in= a reddish-yellow solution.The absorption-spectrum of a solution of erythroxy anthraquinone in concentrated sulphuric acid exhibits a narrow band in the green which does not appear in that of the isomeric body. Both yield ordinary alizarin when fused with pot'assium hydrate ; the erythroxyanthraquinone is however less readily acted upon. Pyrocafechirt and Plzthnlic Acid. -When pyrocatechin is gently heated with phthalic anhydride and sulphuric acid the corresponding phthalein is apparently produced ; but if the temperature be raised to 140° the colour changes from rose-red to brown and after a time water precipitates ;t brownish-black mass. The residue from the alcoholic F'd ABSTRACTS OF CHEMICAL PAPERS.extract of this mass yields alizarin on sublimation. Guajncol behaves similarly. Protocatechuic acid also yields traces of alizarin but is in great part decomposed in other ways. Hydropinone awd Phthalic Acid.-The formation of quinizarin takes place not only with these materials (this Journal [2] xi l234) but according to the authors with all substances which when heated with sulphuric acid yield either hydroquinone or its sulpho-derivatives. Thus it is formed from quinic acid which is converted into a-hydro- quinone-disulphonic acid on heating with sulphuric acid ; and from potassium thiochronate which on heating with sulphuric acid fur-nishes 6-hydroquinonedisulphonicacid (Gmbe) . With regard to the constitution of the four anthraquinone derivatives oxyanthraquinone erythroxyanthraquinone alizarin and quinizarin which can thus be formed from phthalic acid and phenols since all of them correspond with the same anthracene it necessarily follows that the “ entry of the phthalic acid into the benzene group” takes place in the same manner in every case and t.he difference in constitution can therefore be due only to a difference in the relative posit,ion of the hydroxyl groups.It may be regarded as certain that in the dioxy- derivatives the hydroxyls are in the same relative position as in the phenols from which they are derived so that the two hydroxyls in alizarin are in the same relative position as in pyrocatechin and those in quinizarin in the same relative position as in hydroquinone.More-over the. two hydroxyls must be in the same benzene group. Two questions remain however to be settled concerning the constitution of anthraquinone namely the nature of the group C,O which unites the two benzene groups and the position of the two carbon atoms of this group in the one benzene group their position in the other being suffi-ciently determined by the formation of phthalic acid from alizarin and the synthesis of alizarin from phthalic acid. The former question need not here enter into consideration ; with regard to the latter Behr and van Dorp (this JourmaZ [2] xii 470) have shown that the pair of carbon atoms which unite the two groups cannot be joined in the para-position and the formation of two isomeric oxyanthraquinones confirms this conclusion.Whether however the position of the CzO group is 1 2 or 1 3 must remain at present undecided although the easy and perfect resolution of anthraquinone into benzoic acid on heating with potassium hydrate solution is in favour of the assumption of the 1 2 position. In the former case the forrnulze to be assigned to alizarin and quinizarin are ORGANIC CHEMISTRY. In the latter OH H c-c -c-c C,H,. C2040nc// 'c=c )COH. TT H a H. E. A. Synthesis of Purpurin. By F. DE LALANDE (Compt. rend. lxxix 669). ATJZARIN, perfectly free from purpurin was submitted to the action of oxidising agents whereby purpurin was obtained. 1 part of dry pulverised alizarin was mixed with 8 or 10 of sul-phuric acid and 1 part of arsenic acid or manganese peroxide added the whole heated to 15O0-16Oo till one drop of the mixture thrown into dilute caustic soda gave the red coloration of purpurin.The whole was then poured into a large bulk of water the precipitate exhaust,ed with cold water dissolved in a saturated solution of alum and then treated with an acid. The solution thus obtained deposits a>bundant ffocculi of purpurin. The yield is pretty large the chief cause of loss being the production (especially with arsenic acid) of a colouring matter soluble in water to a yellowish-brown and in alkalis to a red solution. The opinion which the author held that purpurin was not as generally supposed trioxyanthraquinone and that the atom of oxygen by which it differs from alizarin not belonging t.0 a hydroxyl group might be added by direct oxidation is thus substantiated.C. H. P. Derivatives of Benzyl-toluene and Tolyl-phenyl Ketone. By H. PLASCUDA (Deut. Chem. Ges. Ber. vii 982-and ZINCKE 986). ZINCKE'S benzyl-toluene is believed to cont,ain two modifications a-and 6- the former yielding a-tolyl-phenyl-ketone melting at 54"'together with benzoyl-benzoic acid melting at 194"; while the latter yields B-ben- zoyl-benzoic acid which melts at 85"-87" when hydrated or at 12'7'-128" when anhydrous. Treatment of a-tolyl-phenyl ketone with fuming nitric acid led to the production of a substancc containing C,4Hll(N0,)0 and identical with the similarly constituted substance which Milne obtained from benzyl-toluene.The further nitration of this or the direct nitration of a-tolyl-phenyl ketone with nitro-sul- phuric acid led to the formation of a trinitrotolyl-phenyl ketone which separates from alcohol or acetic acid in small yellowish pris-matic crystals melting at 165" and which do not undergo sublimation without change. When dinitro-bcnzyl-toluene is oxidised a corre-sponding ketone is obtained the nitration of wliicli gives rise to a diizitro-tolyl-pher~lketone C1PHIO(N02)20, melting at 126"-127" and ABSTRACTS OF CHEilIICAL PAPERS. forming thick yellowish needles which cannot be sublimed without decomposition. A tririitrotolyl-pheriyl ketone identical with that described above is obtained by the further nitration of the dinitro- ketone last described.These results indicate that mononitrotolyl-phenyl ketone contains its nitro-group in the CGHj,whereas the trinitrotolyl-phenyl ketone contains two nitro-groups in the CsH5,and one in the CsH4,while it is at the same time probable that dinitro-tolyl-phenyl ketone contains one nitro group united with each benzene nucleus. This view is con- firmed by the fact that the slow oxidation of dinitro-tolyl-phenyl ketone gives rise to para-nitrobenzoic acid and dinitrobenzoyl- benzoic acid. This latter acid separates from water in silky leaflets or from alcohol in yellowish needles melting at 211"-212". The oxidation of the mononitro-ketone was less satisfactory bcnzoic acid being produced together with a mono-nitrobenzoic acid melting at 140° and yielding a barium salt containing four molecules of water ; and this result pro- bably indicates that the nitro-ketone in question contains its NOz in the meta-position.When the potassium salt of the crystalline sulpho-acid which Milne obtained by treating benzyl-toluene with sulphuric acid is fused with potash a mixture of phenols is obtained together with paroxybenzoic acid and a small proportion of a higher acid perhaps containing C14H8( OH),Os. Probably Milne's crystalline sulpho-acid is derived from a-benzyl-toluene the amorphous sulpho-acid being most likely a mixture. All endeavours to obtain derivatives which are certainly produced from P-benzyl-toluene have failed although during the nitration of benzyl-toluene a second dinitro-derivative C14H,,(N0,)2,is produced in a small proportion.It melts at 100° and forms radial tufts of needles. This substance is probably derived from a-benzyl-toluene as its oxida-tion yields resinous products similar to those obtained by the oxida- tion of the ,@-ketone. T.3. Amido-Derivatives of Benzene. By H. SA J K o w sK I (Ann. Chem. clxxiii 39-71}. THEresearch on chryanisic acid has shown that the ethers of nitrated phenols behave towards ammonia like true saline ethers being readily converted into amido-compounds. This is the case even if they contain the carboxyl-group or are oxy-acids for when in such a compound the hydrogen of the hydroxyl as well as that of the carboxyl is replaced by an alcohol-radical that which is combined wit8h the pheiiol- oxygen is much more readily eliminated than the other.Further proofs of this are found in the following reactions. While dinitranisic acid is readily obtained by nitrating the mono- nitro-compound the corresponding dinitrometliylsalicylic acid is 110t produced in that way. When mononitromethylsalicylic acid pre-pared by boiling methylsalicylic acid with five times its weight of nitric acid of specific gravity 1.4 for a fcw minut'es is heated longcr with the acid oiily a little dinitrosalicylic acid ad picric acid are ORGANIC CHEMISTRY. formed while on boiling the mononitro-acid with three parts of fuming nitric acia for half an hour itl is hardly changed only a very small quantity of a more highly nitrated product being formed.To obtain hhe dinitro-compound oil of winter-green is dissolved in a mixture of five parts of fuming nitric and five parts of fuming sulphuric acids. The methyZ-di:nitrosaZicyZate C6Hz(N02)2(OH)C02.CHs, which by this method was first prepared by Cahours crystallises from alcohol in slightly colouyed plates melting at 127"-128". On heating its silver- salt with ethyl iodide the methyl-ethyl ether C6H2(N0,)z(OC,H5)C0,. CH, is formed which crystallises from a dilute alcoholic solution in thick and very brilliant monoclinic prisms with terminal faces con- sisting of two different augite-pairs and melting at 80". a b c = 0.3517 1 0.2535. Angle a c = 71" 13'. When this compound is heated with aqueous ammonia on a water-bath it first melts and then solidifies again being chiefly converted into methyl dinitranthranilate while the ammoiiiacal solution contains dinitranthranilic acid which on the addition of hydrochloric acid is obtained as a deep yellow precipitate crystallising from alcohol in scales resembling chrysanisic acid and melting at 256".The forma- tion of this compound is explained by the following equation :-C,H,( NO,),( OC2HS)C02CHz +2(NH,-OH) =C,H,( NOz),(NHz)COPH, + CH40 + CZH60 + HZO. Ammonium diuitramtlwad ate C,H (NOz),(NH,) .CO,NJ& + HZO forms yellow or brownish long needles. The methyl-ether which as already mentioned forms the chief product crystallises from hot alcohol in narrow yellow plates or feathery needles melting at 165". It is hardly attacked by boiling sodium carbonate but on boiling it with soda-lye ammonia is evolved and the dark-red solution changes into orange.When now hydrochloric acid is added a precipitate of di4rosaZicylie acid is obtained crystallising from hot water in colour- less slender needles melting at 165" ; its aqueous solution gives with ferric,chloride a red colour. When hydrochloric acid is passed into an alcoholic solution of dini- tranthranilic acid the ethyl-ether C6HZ(NOz),(NHz) CO,C,H is formed which is sparingly soluble in boiling alcohol and crystallises in small yellow plates melting at 135". Dimethy Z cli~itroscd icy1ate C6HZ (NO,) (0CH,) C0zCH3,which was obtained by t,he action of methyl iodide on the above silver-salt is isomorphons with the corresponding ethyl-compound and melts at Ammonia decomposes it like the ethyl-ether.6CLO. J C6H2(N02)z( ZtliyZ ~Ziizitrosnlic~late OH) CO2.CzH5,-which was pre-pared by the action of hydroclzloric acid on an alcoholic solution of thc acid forms small colourless plates melting at 98"-99". The ammo- nium-salt C6Hz(N0z)z(ONHI,).C02.C2H5,crystallises in long golden needles. By decomposing it with a silver-solution the corresponding silver-salt cannot be obtained in a pui*e state. To prcpare it silver oxide :nid tlie ct hgl-ether both ver~finely divictc~l,are lieated with t~ ABSTRACTS OF CHEMICAL PAPERS. large quantity of water first very gently and then gradually nearly to the boiling point. On cooling the salt crystallises in slender orange needles or yellow spherules but only if the solution be not too dilute or else the liquid.solidifies into a gelatinous mass. When this salt is treated with methyl iodide the compound C,Hz(NOz)2( OCH,) C02CzH5 is formed crystallising from alcohol in large thin six-sided plates melting at 47". The corresponding diethyl ether C6Hz(NOs)z(0CzH~) C02C2H5,separates like the preceding compound from a concentrat'ed solution as an oil and from a more dilute one in flat prismatic crystals. The results show that the group OCH3or OCzH5,which is linked to the benzene-nucleus is much more easily attacked than if combined with GO and further if the latter be acted on no amido-compound is formed but an ammonium-salt. When mononitranisic acid is treated with ammonia a complete reaction takes place only at 140"-160".The n~tropnrn7~aidobenzoic acid thus formed is identical with Griess' nitramidodracrylic acid. On heating it with tin and hydrochloric acid it is converted into @-dianzido-beaaoic acid yielding by dry distillation orthocZia~~idobep~zene, melting at 99". By treating nitroparamidobenzoic acid with a hot alcoholic solution of nitrous acid a mixture of compounds was formed containing monocldorobenzoic acid the chlorine being derived from the calcium chloride which was used for drying the nitrous fumes. But when nitroparamidobenzoic acid is introduced into a cold solution of nitrous acid in absolute alcohol it is gradually changed into small light-yellow plates of nitrodiaxobenzoic acid C,H,(NO,),N,CO,.On boiling this compound with alcohol common or metanitrobenzoic acid is formed. If the meta-compounds belong really to the I. 3 series it follows from the above facts that the diamidobenzene melting at 99" is an ortho- or 1.2 compound. Further it is easily seen that in this case the three diamidobenzoic acids of Griess possess the following constitution :-C02H COzH COzH Besides these three three others can exist :-NH C0,H Of these the first and second are known the former being obtained from the common dinitrobenzoic acid the other from the dinitrobenzoic acid produced by oxidising dinitrotoluene. Both yield the diamido- benzene melting at 63" which must also be obtained from the last yet unknown acid. ORGANIC CHEMISTRY.Aqueous ammonia acts but slowly on anisic acid even at 250"-285" some phenol being formed and a small quantity of an acid which appears to be paraoxybenzoic. Methylosybenzoic acid yields under the same conditions some oxybenzoic acid and methylsalicylic acid is principally converted into salicylic acid. Decomposition of some Diazo-compounds by Water. By E. WROBLEVSKI (Deut. Chem. Ges. Rer. vii 1061-1062). THEauthor has formerly shown that by decomposing the diazo-com- pounds of several substituted toluenes no cresols are formed but sub-stituted hydrocarbons. The same is the case with some other deri- vatives of benzene. Thus the dibromaniline which is obtained by brominating acetanilide yields a dibrornobenzene identical with that which Meyer and Stuber obtained while the dibromaniline from the solid dibromobenzene yields dibromophenol and chlorinated para-tohidine is converted into metachlorotoluene.The relative position of the side-chains appears to be the cause of this difference in the reaction. c. s. Synthesis of Aromatic Acids. By V. v. BICHTER (Deut. Chem. Ges. Ber. 1145-1147). WHENnitrodibromobenzene is heated with potassium cyanide and alcohol to 120'-140" and the product boiled with alcoholic potash a new dibromobemzoic acid is obtained crystnllising from hot water in pearly flat needles melting at 151". (C,H,Br,.CO,),Ba + 6Hz0 is readily soluble in water and forms warty crystals consisting of microscopic needles ; (C6H3Br. C02),Ca, -+ 3H,O forms indistinct crystals.c. s. Oxidation of Orthotoluic Acid to Phthalic Acid. By W. WE~TH (Deut. Chem. Ges. Ber. vii 1051-1060). WHILEin an acid solution orthotoluic acid is completely burnt to carbon dioxide and wafer it is oxidised to phthalic acid by adding potassium permanganate to an alkaline solution. c. s. Dibenzylacetic Acid and a New Synthesis of Homotoluic Acid. By LY D IA SE s E M A N N (Inaugural- Dissertation. Zurich 1874). WHEN the yellow solid product which is obt,ained by heating acetic ether with sodium gradually to 160° is mixed with benzyl chloyide and then heated to 200" in a flask which is connect'ed with a reversed condenser the ethyl ethers of bew:yZncetic (hydrocinnamic) acid and c7;beuzylacetic acid are formed according to the following formulae :- 74 ABSTRACTS OF CHEMICAL PAPERS.CH,Na CH,.CH,.C,H, I + ClCHpCtjH = I + NaCl C0.0C,H CO.OC2H CHNa CH( (332. CsH,), I + 2( ClCH,.C6H,) = I + 2NaCl. C0.0C2H5 co.0C,H Ethyl benzylacetate is a limpid liquid boiling at 245"-250" and having a fruity smell. The acid contained in it is identical with that described under the names homotoluic hydrocinnamic and phenyl- propionic acid. Ethyl dibenzylacetate forms a golden-yellow fragrant oil which boils above 300". On saponifying it and decomposing the salt with hydro- chloric acid the free acid was obtained which crystallises from petro- leum-naphtha in quadratic prisms melting at 85"; it is insoluble in water but dissolves readily in alcohol and ether. T'he barium salt [(CsH5.CH2)2CH.C02]zBa is a dense white precipitate which is in- soluble in cold water sparingly in boiling water and crystallises from it in fine white needles.The calcium salt is a similar precipitate con- taining one molecule of water and the 'silver-salt forms a flocculent and perfectly insoluble precipitate. An aqueous solution of the am-monium-salt containing 10 per cent. gave the following characteristic precipitates :-In the cold. On heating. Ferric chloride. ...... Pale-yellow Ochre- yello w. Cobalt nitrate. ...,.. . Reddish-violet Dark-violet. Manganese chloride .. White Bro wnish-yellow. Nickel sulphate ...... White Apple-green ; on cool-ing fine needles sepa- rated out. Copper nitrate. .... . .. Light- blue Dark-green. By the action of phosphorus pentachloride on the acid no chloride but apparently a substitution-product was obtained.When barium dibenzylacetate is heated with soda-lime some benzene is formed and dibenzyZnzelhane CH2( CH2.CsH5), an oily liquid boiling above 300". On adding it in small quantities to warm fuming nitric acid LZiiLitro-dibenzyZmethane CH2( CHzC6KN02)2 is formed separating from a solution in petroleum-naphtha as a pasty mass which by washing with carbon sulphide is converted into an amorphous powder melting at 186". The formation of the above two acids is quite analogous to Frank-land and Duppa's synthesis of butyric and diethylacetic acid &c. But while these chemists observed at the same time the formation of earbacetonc-carbonic ethers bcnzyl chloride does not forni similar com- pounds.This shows that the latter compound which belongs at the same time to the aromatic and to the fatty group does not behave exactly as the haloid ethers of the ethyl-series. c. s. ORGANIC CHEMISTRY. a-and P-Benzoyl-benzoic Acid. By H. PLA s c u D A (Deut. Chem. Ges. Ber. vii 986-988). THEmost characteristic properties of the 8-benzoyl-benzoic acid origin- ally described by the author and Zincke are detailed this being followed by a similar account of some derivat'ives of a-benzoyl-benzoic acid. p-Benzoyl-benzoic acid C,1H,o03+ H20melts at 85O-87' when air- dried or at 127"-128" when dried at loo" and it cannot be sublimed without change. The zinc sdt (C,4H90,)zZn+ 2Hz0 melts under hot water or if dry it melts at 140".The methyZ-ether forms rhombic prisms melting at 52" while the ethykether melts at 58" and forms rhombohedrons which gradually grow into long prisms. P-benzoyl benzoic acid yields amorphous product,s on nitration. Derivatives of a-berzzoyl-bewzoic acid. The potassium salt forms tufts of fine needles which are less soluble than the corresponding /%salt. The nrnrnoriiuin salt forms long thick needles which are not very soluble in water. The solution easily loses ammonia and becomes acid. The copper snlf was obtained as a green crystalline precipitate soluble in hot water. The methyZ-ether forms large shining leaflets which melt at 107" and are less soluble than the a-ether. The etlyZ-otlhev forms tabular monoclinic cr stals melting at 52".Water sepa- rates it in shining scales from its $coliolic solution. The nitration of a-benzoyl-benzoic acid led to the formation of a dini- trobenzoyl-benzoic acid which is isomeric with that obtained by the oxida- tion of dinitro- benzyl-toluene. It separates from water in shining leaf- lets which melt at 240" and are easily soluble in alcohol or acetic acid but less soluble in water. The unzrnowium salt forms shining easily soluble scales while the copper snZt separates fi-om hot water in shin- ing bluish needles. The xir~csalt is amorphous and the barium saZt [C14Hi03(N02)2]2Ba + H,O forms nodular tuft's of needles which are very slightly soluble in water. The cccZciuna saZt cr-j-stallises in shining white leaflets containing two molecules of water this being driven off at 120".T.B. Catechuic and Catechutannic Acids. By J. L~WE (Zeitschr. Anal. Chem. 1874 113-124). THE author assigns the formula C,,H,iO7 to pure catechuic acid ; this acid he has also obtained by less prolonged drying in combination with one molecule of water forming the substance C,,H,,O,. If either of these acids be slowly heated until it rneIts (160°-165") it undergoes partial decomposition producing a substance which dis- solves in water with a yellow colour arid shows the characteristic react,ionof catechutannic acid. By comparing this acid and its lcad salt with the acid and its lead salt obtained directly from catechu the author shows that this lattey is really catcdiutnnnic acid and he assigns to it the formula C,,H,,O,,.M. M. P. 31. ABSTRACTS OF CHEMICAL PAPERS. Isomeric Sulphocinnamie Acids. By W. RUDNET (Ann. Chem. clxxii 8-20). ONE part of cinnamic acid purified by crystallisatiom from ligroi'n was gradually added to 3.5 parts of fuming sulphuric acid (containing 20 per cent. of SO,) the products being then diluted and treated with sufficient barium carbonate to remove the free sulphuric acid. The mixed sulpho-acids thus obtained were separated by a fractional crystallisation of their acid barium salts the para-salt forming long needles and the meta-salt forming nodules. Para-su~~oci?zi~anic acid C6H4(S0,H) CH.COOH + 5H20 forms colourless monoclinic prisms which effloresce over sulphuric acid with loss of 4H20 a temperature of 100" being required for the removal of the-last molecule.The- crystals undergo aqueous fusion at looo and are readily soluble in alcohol but less soluble in ether. Para-sulpho-cinnamic acid readily converts alcohol into the acid ether which forms long needles but in presence of water a neutral ether is formed. The neutraZ barium saZt C9H6BaS05+ H20 forms crystalline crusts which are but slightly soiuble in water. The acid barium salt (C9E17S05)2Ba+ 3H20 separates from water in long colourless needles. The neutral calcium salt C~H~SO&L+ aH20 forms small crystals very slightly soluble in water. When its solution is treated with hydrochloric acid and alcohol the acid salt separates in needles. The nezctrab potassiwm salt CgH6K2S05 + 12H20 is not hygroscopic and was obtained in nodules.When treated with hydrochloric acid it yields needles of the acid salt. The acid copper sa& (C,H7S05)PC~ + 6H20 forms greenish prisms easily soluble in hot water. The Yzeutral silver salt was obtained in large anhydrous prisms and the lead salt in long hydrated needles. When para-sulphocinnamic acid is fused with potash paroxybenzoic acid is produced and when it is oxidised by chromic acid mixture para-sulphobenzoic acid is formed. MetnsuZphocin7zamic acid crystallises with 3H,O forming nodules consisting of small prisms which effloresce easily over sulphuric acid and decompose at 80" The .rzeutyal barium saZt C,H,BaSO + 1+H,O is more soluble than the para-salt and requires a temperature of 180' for perfect dehydration.Acid 71ariun2 salt (CgH7S05),Ba+ 3H,O. Nodules which are tolerably soluble in boiling water. NezctraZ caZciurn saZt C9H6CaSo5+ 1$H20. Crystalline and easily soluble in water. SiZver salt C9H6Ag2S05.Amorphous and slightly soluble in water. The potassium salt is very soluble in water or alcohol and separates in the crystalline form from the concentrated alcoholic solution. The fusion of meta-sulphocinnamic acid with potash leads to the formation of metoxybenxoic acid but its oxidation by chromic acid led to unsatis- factory results. Aldehyde and acetic acid were among the products in this case. T.R. ORGANIC CHEMISTRY. ParamidorthotoluenesulphonicAcid. By F. JE N s sEN (Ann. Chem. clxxii 230-239).WHENsulphur trioxide is passed into a mixture of paranitrotoluene and pure sulphuric acid until the mass dissolves completely in water paraizitrorthotol uenesdprphorh acid is formed crystallising from water in yellow well defined rhombic prisms which begin to soften at 130" and melt at 133.5" ; on cooling the anhydrous acid solidifies to fine needles melting at 130". It is readily soluble in water alcohol ether and chloroform.-[ C7H6(NOa)S03],Ba + 3H20,is sparingly soluble in water and crystallises in long needles. [C7H6(NO2)SO3]2Pb+ 3H20 forms yellowish needles and the potassium and ammonium salts crys- tallise in long slender needles which may be heated to 190" without loss of weight. C7H,(N0,)S0,C1 crystallises from ether in rhombic plates melting between 43" and 44.5".C7H,(N02) SO,.NH is sparin@y soluble in alcohol and ether readily in hot water and very freely in concentrated ammonia it forms yellowish long and very brittle needles melting at 186". By passing hydrogen sulphide into an am- moniacal solution of the nitro-acid paranaidorthotoluenesu~/1onicacid C7H6(NH,)S03H + H,O is produced crystallising in hard colourless rhombohedrons and not in yellowish flat prisms as Beilstein and Kuhl- berg have stated. It dissolves but sparingly in hot water and is in- soluble in alcohol and ether. Its salts are very soluble and do not crystallise well. By adding bromine to the boiling soldtion of the acid only the monobrominated acid is formed even if the bromine is in excess. Brornop~ramidorthotoluerzesu~ho.lzic acid C7H5Br(NH,)SO3H is insoluble in alcohol and ether sparingly soluble in hot water but more freely in hydrochloric and hydrobromic acids.C7H3Br(NH2)S03K + H,O forms compact hard prisms. [C7H3BrNH,S0,]2Ba + ~HzO crystallises from water in compact prisms and from alcohol in needles. The lead-salt forms very soluble plates and the silver-salt long white needles which dissolve sparingly in cold and more freely in hot water. The diazo-compound of the amido-acid forms yellow or brown needles and yields when boiled with absolute alcohol under pressure ortho-tolueneszclphonic acid which forms a syrupy mass while Terry (Ann. Chem. Pharm. clxix 27) describes it as a laminated crystalline mass. (C7H7S03)2Ba+ H,O is readily soluble in alcohol and water and form small glistening plates.(C7H,S0,),Pb $. H,O crystallises in warty groups consisting of small needles. The chloride of the acid is an oil yielding with ammonia the amide crystallising from water in needles melting at 148O and from ether-alcohol in compact monoclinic prisms melting at 155" which agrees with the melting points found by Wolkow and by Hiibner and Terry. On heating the diazo-corn- pound with water pilrac~esoZ0i~t7zo~z~~hoi~ic acid C7H6(OH) X03H -I-5H20 is obtained crystallising from water in long white needles melting at 98.5" ; over sulphuric acid they lose all the water and melt then at 187"-188". None of its salts could be obtained in the crystal- line state ; the solution of the barium salts gives with ferric chloride a violet colour which disappears on addins alcohol.When the diazo- compound is decomposed with hydrobromic acid parab.1.ornorthotoZue~ze-sulphonic acid is obtained crystallising in fine needles. ABSTRACTS OF CHEMICAL PAPERS. (C7H6RrSO2),Ba+ H20is sparingly soluble in cold more freelyk boiling water and forms either small plates or crusts which look quite amorphous. (C5H6BrS03),Pb+ 3H,O is readily soluble in alcohol and water and crystallises in needles. The eldoride crystallises from ether in plates or prisms melting at 30"-35". The arnide crystallises fkom water in needles melting at 165-5" and from ether-alcohol in compact prisms melting at 167"-168". This acid is identical witlh the P-parabromotoluenesulphonic acid of Hiibner and Post.By the action of hydrochloric acid on the diazo-compound parncldorortho-loluenssulpl~onicacid was obtained which appears to be crystalline and yields a barium salt. (C,H,ClSO,),Ba + H20 crystallising in small plates. This acid is probably identical with Hiibner and Post's B-para- chiortoluenesulphonic acid. c. s. Paramido-metatoluenesulphonicAcid. By H. TON PECHMANN (Ann. Chem. clxxiii 195-218). THISacid is formed together with ihe ortho-acid and a disulpho-acid, by heating paratoluidine with twice its weight of fuming sulphuric acid to 180" until sulphur dioxide is given off the chief product being then the meta-acid ; but if the heat be continued the quantity of the others increases. Thus on heating 5 grams of the pure meta-acid with 10 grams of fuming sulphuric acid for twenty minutes to 180"-200" 3 grams of the ortho-acid and about 1gram of the disulpho-acid werc formed.On the other hand on treating pure ortho-acid in the samc way only 1gram was changed int'o meta-acid the latter being less stable than the other. The acids are separated by diluting the product with twice its weight of water and distilling with an excess of baryta-water to remove free toluidine. From the residue the barium is removed by sulphuric acid and the free sulpho-acids are separated by crystallisa-tion the ortho-acid being the least soluble in vater and alcohol and the disulpho-acid being very soluble. Pfl,ram,~do-rnetatoZLe~~~~~~~~orLz'c acid 2[C611,(CH3)(NH,)S0,H]+H20 forms sulphur-yellow needles but on decomposing its lead-salt with hFdrogen sulphide the yellow colour disappears.It dissolves in 10 parts of water at the common temperature much more freely in boiling water scarcely in absolute alcohol and not at all in ether. Its solutions and those of its salts assume a reddish colour in the light. The aqueous solution gives with ferric chloride a red colour wliich becomes deeper on heating. When the dry crystals are heated to 130" they lose their water but in presence of more water they decompose at this temperature into paratoluidine and sulphuric acid. (C7H8NSOJ)2Ba+ 3H20is readily soluble in water not in alcohol and forms transparent six-sided plates. (C,H8NSOJ2Pb + 2K20 crystallises in long needles less soluble than the barium-salt.C,H,NSO,Ag is a precipitate consisting of shining crystals and dis-solves but sparingly in boiling water. When the acid is distilled with potash R little paratoluidine is formed while by fusing it with potash ORGANIC CHEMISTRY. until the mass becomes thick paraoxy benzoic acid is formed together with a trace of protocatechuic acid CsH SO,H + {: 3KOH = CsH3 COZK H + SOsK2 + NH3 + 4H. {OH When the finely divided acid is suspended in alcohol or better still in water at 30"-40" and nitrogen trioxide is passed into the liquid { Sp the diazo-compound C,H3(CH,) is obtained as a red crystal- line powdcr. Water at 60" dissolves it and on cooling the compound crystal-lises either in pale red or if a little nitric acid is present in colourless plates.On boiling with alcohol under pressure m eta-toZicei~csr.cll~l~oilic acid is obtained as a crystalline deliquesceiit mass. (C7H7S03),Ba-+ 2H,O is readily soluble in water less in alcohol and forms warty crystals. ( C7H7S03)ZPb+ H,O crystallises from water in nodules. According to Miiller this salt crystallises from alcohol in long needles with 2 mol. of water; this the author could not obtain. The chloride is a yellowish oil. The amide crystallises from dilute solutions in rhombic plates and from a concentrated solu-tion in small glistening plates or needles melting a little below 100". PnracresoZnzetasu~hoiiicacid C,H3(CH3)( OH)SOJH is formed by boiling the diazo-compound with water. It is a reddish-brown syrupy mass giving with ferric chloride a beautiful blue colour.With basic lead acetate it yields a white precipitate. The composition and pro- perties of the salts of this acid agree with those which Engelhardt and Latschinoff have described. When the acid is heated with nitric acid a ciinitmcresoZ is formed identical with that which Martius and Wichel- haus obtained by decomposing paratoluidine with nitric trioxide. By decomposing the diazo-compound with hyarobromic acid? parabrorn,o-metatolzceraesui~Lo~z~c acid is produced which is identical with the acid described by Post and Retschy (Ann. Chem. clxix 7). When paramidometatoluenesulphonic acid is treated with 2 molecules of bromine it is converted into dibromotoluidine which seems to be identical with that obtained by Wroblevsky and is also formed togc- ther with brorno~Cr,rami~o~netntoZue~tesu~lLonic acid 3[C6H2Br(CH,) (NH,) SO,H] + 2H,O which crystallises from a concentrated aqueous solution in yellowish nodules consisting of short needles and from a dilut8e alcoholic solution in slender sulphur-yellow soft needles.On distilling it with potash iizo;12ob1.o.motoZzLidi?Leis obtained as a colourless oil form- ing crystalline salts. C7H7BrNS03Kforms thick colourless prisms. ( C7H7BrNS03),Ba+ 2H20crystallises in small hard g!istening rhombic plates. (C7H7BrNS03),Pbis very sparingly soluble in cold water and crystallises from hot water in colourless soft glistening needles. C,H7BrNS03Agis a crystalline precipitate separating from a hot solu- tion in long dolourless needles.The diazo-compound- ABSTRACTS OF CHEMICAL PAPERS. is a brownish-red crystalline powder which when boiled with alcohol under pressure yields bromometatoluenesdp honic acid a colourless crystalline mass which dissolves readily in water. C,H,BrSO,K crysta,llises in transparent prisms. 2[ (C,H,BrSO,),Ba] + 7H,O is sparingly soluble in cold water and forms compact needles. (C7H6BrSO3),Pb3-3H,O crystallises from hot water in groups of needles. The chloride crystallises from ether in long needles melting at 53". The amide is readily soluble in alcohol and ether sparingly in cold water and crystallises from hot water in shining plates or needles melting at 134'. The free acid is converted by fuming nitric acid intooytho~zit.1.o-dinxo-.Inetato luenesulphonic acid C,H2(CH,) NO {">N c- crystallising on slow evaporation in dark-violet brittle needles.When boiled with absolute alcohol under pressure it yields an orthowibonzetn-toluenesulphowk acid. [C7H6(N0,)S0,],Ba + 2H20 is sparingly soluble in cold water and crystallises from a hot solution in glistening yellow plates. By the action of hydrogen sulphide on the ammonium-salt orthamidonzeta-toZuenesulphonic acid is formed crystallising from hot water in micro- scopic needles and giving with ferric chloride an intense reddish- yellow colour. On distilling it with potash pseudotoZuidirze is formed. PnranzidotoZueemedisu~72onac acid [C6H2(CH,) (NH,) (SO,H),] + H,O remains in the mother-liquors of the ortho- and meta-acid and sepa- rates from a very concentrated solution in soft warty crystals.C7H7N(S0,)2Ba+ 3H,O separates when alcohol is added to a hot con- centrated solution in fine glistening plates. The lead salt is still more soluble than the barium salt and forms warty crystals. The two sulpho-groups in t,his acid have most probably the position 2 3. c. s. Metatoluidine. By LORENZ (Ann. Chem. clxxii 177-190). THE author has followed Beilstein and Kuhlberg's (Ann. Chem. clvi 83) method for the preparation of metatoluidine (called by them orthotoluidine) and confirms their results. Acetoparatoluide is converted into metanitroparacetotoluide and then with alcoholic potash into metanitropuratoluidine which with nitrous acid and subse- quent boiling with absolute alcohol gives metanitrotoluene.This body is then reduced with tin and hydrochloric acid to metatoluidine boiling at 197". The following table contains a comparison of the reactions of the three toluidines with the reagents which according to Rosenstiehl are characteristic for the ortho- and paratoluidine. 1. The base dissolved in SH,04.H20 is treated with a solution of chromic acid in sulphuric acid of the same concentration. The mix-ture is coloured ORGANIC CHEEJ1ISTR.T. Orthotoluidine (pseudotoluidine). Metatoluidine Paratoluidine Blue changing on dilu-Yellow -brown which Yellow. tion to a permanent red- becomes greenish-yellow on violet. addition of a small quantity of water and on further dilution colourless.2. Nitric acid is added to a solution of the base in SH,Oa.H,O. An orange-colour is pro- The mixture becomes at Blue streaks are pro-duced and with very con- once red changing quickly duced which soon tinge centrated solutions a to intense blood-red then the whole liquid ;after one brown becoming yellow to a dirty dark red and on minu tc the colour becomes on dilution. dilution to ormge. violet then red and after some hours brown. 3. To a solution of the base in equal volumes of water and ethcr n few drops of a clear solut'ion of bleaching powder are added. The layer of muter be- The layer of water be- No reaction. comes first yellow and then conies a thick brownish-br>wn. The ether sepa-yellow; the ether asaumes a rated from the water and reddish colour.When sepa- when treated with dilute rated and shaken with a sulphuric acid is perma-few drops of dilute sul. nently coloured a red phuric acid the under sur-violet. face of the ether is coloured violet. The author has prepared and aiialysed the following salts of met a-toluidine. The solbbiiities of each in water alcohol ind ether have been observed :-Acid metatoluidine oxalate C7HgN.C2H20,. An oxalate of the formula (C711gN),.(C2H,0,),. An unstable neutral metatoluidinc oxalate (C7HgN),.C2H204. Metatoluidine sulphate (C7HgN) 2. SH204. Metatoluidine nitrate C7HgN.NH03. Metatoluidine hydrochloride C7H,N.HC1. NH To prepare this body one part of metatolu'idine is heated to 160"-175" with 8 parts of fuming sulphuric acid.After purification the acid crystallises in thick white rhombic tables insoluble in alcohol and nearly so in water. Heated above 275" the acid is carbonised. without melting. The barium and lead metamidotoluene-orthosulphonates have the formulae (C7H8NS03)nBa.9H20, and ( C7H8NS03)2Pb,3~H20. The barium salt crystallises in thin tables or long prisms like urea tthe lead salt in yellowish-grey nodules. If bromine-water be added to a cold saturated solution of metamido-toluene-orthosulphonic acid microscopic needles of tribromometatolui-dine are precipitated which after recrystallisation from alcohol melt at 95" after sublimation at 101". This body is insoluble in concentrated soda-solution and in hydrochloric acid but is dissolved by concentrated sulphuric acid and precipitated malt ered by water.VOL. XSVIII. G ABSTRACTS OF CHEMICAL PAPERS. To decide what position the sulpho-group occupies in metamido- toluenesnlphoiiic acid the powdered substance suspended in alcohol of 60 per cent. was treated with nitrous acid until a sample was entirely dissolved on warming with strong alcohol. The diazo-compound thus obtained was heated with absolute alcohol forming a toluenesulphonic acid. The acid was then converted into the potassium salt and this by phosphorus chloride into a liquid chloride which with concentrated ammonia gave toluenesulphonamide. This body crystdlised from water melted at 1.54!"-155" crystallised from alcohol at 161" and is therefore the amide of tolueneorthosulphonic acid whilst the original acid must have the formula- Metamidotoluenedisulphonic acid is contained in the mother-liquors and washings from the crude metamidotoluene-orthosulphonic acid.After removing the sulphuric acid with barium carbonate and unat-tacked nietatoluidine with excess of baryta and this in turn with carbonic acid a salt is obtained on concentration crystallising in white felted needles which have the formula [C7€17N( S03),],Ba.12-$H20(2). Lead metamidotoluenedisulphonate C,H,N( SO3),Pb,2K,0 crystallises in hard yellowish-white crusts. The author did not succeed in obtaining the acid itself in the pure state. The author in a separate notice (pp. 190-191) states that Rosen- stiel-11's method for the estimation of orthotolnidine in presence of paratoluidine by oxalic acid is improved if a piece of blue litmus be thrown into the solution of the substance in ether.The colour changes as soon as all the paratoluidine is converted into oxalate. A still more accurate method is to add more oxalic acid than is required to combine with the whole of the bases present and after filtering off the insoluble paratoluidine oxalate to estimate the oxalic acid in the filtrate with decinormal soda-solution. W. H. P. A new Nitrotoluidine. By 0. CUNERTH(Ann. Chem. Pharm. clxxii 221-229). THE liquid dinitrotoluene which is formed together with the solid on nitrating orthonitrotoluene was prepared by adding toluene to well- cooled fuming nitric acid as long as any action was perceptible and then heating the solution gently.On adding water a precipitate con- sisting of a mixture of the two dinitrotoluenes and a little paranitro- benzoic acid was formed which after being washed with water and sodium carbonate was dissolved in strong alcohol from which first the solid compound crystallised out and then an oil separated consisting chiefly of the liquid compound. By the action of alcoholic ammonium sulphide it was converted into nitrotoluidine which in order to free it ORGANIC CHEMISTRY 83 from that derived from solid nitrotoluene was converted into the benzopl-compound by heating it gently with benzoyl chloride. By fractional crystallisation from alcohol a separation was easily effected the benzoyl-compound of ort honitroparatoluidine being much less soluhle than that of the new nitrotoluidine.Benxoy Ztoluirline is very readily soluble in alcohol and forms short yeiloaish needles or warty crystals melting at 145"-146". By the action of boiling alcoholic potash or better still by heating it with concentrated hydrocbloric acid to 150" it yields the new nitrotohidine crystallising from hot water in long light yellow needles melting at 94.5". It is sparingly soluble in water readily soluble in alcohol and strong acids forming with them very unstable salts. By the diazo reaction it was converted into orthonitrotoluene .-consequently the nitroxyl occupies the position 2 and the amido-group must be either in 5 or 6 because the two other orthonitrotoluidines in which the amido-group occupies the positions 3 or 4 are known.When the new nitrotoluidine is heated with acetic anhydride for four hours to 150" acety ZnitrotoZzci~iIze is obtained crystallising from hot water in glistening colourless prisms melting at 155.5". By reducing the liquid dinitrotoluene with tin and hydrochloric acid some orthctparstoluenedianiiue was obtained together with a new diamins which on accouiit of its small quantity could not be examined more closely. Benzoyl-orthonitrotoluidine which has already been mentioned is very sparingly soluble in a1coho1 and forms long glistening needles melting at 168". It forms an acetyl-compound crystallising in long silky needles which melt at 160". When the ortho-compound is dis-solved in cold fuming nitric acid a benzoyl dinitrotoluidine is obtained crystallising from alcohol in flat rhombic prisms melting at 203'.c. s. Action of Nitrous Acid on Dimethylaniline. By A. BAEYER and H. CAEO (Deut. Chem. Ges. Ber. vii 809-811 963-968). ITis known of the action of nitrous acid on the amines:- 1. That the primary amines of the fatty series yield the correspond- ing hydroxyl derivatives whilst those of the aromatic series yieId diazo-compounds or derivatives of the same. 2. That the secondary aniiies 01the fatty series yield nitroso-deriva- tives in which the nitroso-group is united with the nitrogen; and Griess has recently shown that in a similar manner a secondary arnine of the benzene series ethylaniline furnishes nitrosoeiliyl-aniline.3. That the terliary amine tripthylamine is not acted upon when its hydrochloride and potassium nitrite am simply brought togethcr but that on warming nitrosodiethylamine is produced. It was therefore to be expected that nitrous acid would either be without action on dimetlhylsniline or would convert it into nitroso-metZ-LyZnrdiqLe. The aut,hors find however that it is converted into nitrosodinzethylanili?ze .thus CGH~N(CJiI-T,),HCl+ NOZH = CsHa(NO)N(CH,)2HCl + OHz. G2 ABSTRACTS OF CHEMICAL PAPERS To prepare nitrosodimethylaniline 100 parts of amyl nitrite is added to a mixture of 50 parts of dimethylaniline with 100 parts of con-centrated hydrochloric acid and 750 parts of a mixture of 1volume of hydrochloric acid with 2.volumes of alcohol which is well cooled with ice.After a short time yellow needles separate ;as soon as these no longer increase in quantity the mass is thrown on a vacuum-filter and washed with ether-alcohol. An almost quantitative yield of pure nitrosodimethylaniline hydrochloride is thus obtained in the form of small sulphur-yellow needles ;these melt at 177" but are apparently decomposed ;they dissolve in water forming an intensely yellow solu- tion. On adding potassium carbonate to the hydrochloride suspended in water the pure base separates in green flakes ;it may be extracted with ether and on evaporating the solution is obtained in large green plates which melt at 92" and are slightly volatile in a current of steam. The sulphahe and nitrate of the base are obtained in fine yellow needles on adding sulphuric or nitric acid to an e€hereal solu- tion of nitrosodimethylaniline.Nitrosodimethylaniline is easily re-duced by tin and hydrochloric acid a base different from dimethyl- aniline being produced. When boiled with an alkali it is resolved into dimethylamine and nitrosophenot C6Ha(NO)N(CH,)z +OH2 =NH(CHa)2 +CsH,(NO)OH. NitrosophenoL-A mixture of 90 parts of water with 10 parts of sodium hydrate solution (sp. gr. 1.25) is heated to boiling in a flask connected with a reversed condenser and 2 parts of nitrosodimethyl-aniline hydrochloride is gradually added care being taken each time to await the dkappearance of the oily drops of the base before a fresh quantity of the salt is added. The boiling is continued until the dark greenish-yellow coloui has entirely disappeared and changed to reddish-yellow.The greater part of the dimethylamine passes over during the boiling and is collected in hydrochloric acid ;in this way it may be prepared in a state of purity in any desired quantity. To obtain the nitrophenol the alkaline solution is well cooled rendered slightly acid with sulphuric acid and extracted with ether ; on dis-tilling off the ether it remains in the form of a brown crystalline mass or if the ethereal solution be slowly evaporated it separates in large brown rhombic plates measureinents of which by Dr. Hintze are given. Nitrosophenol melts when heated and between 120"-130" decom-poses with a slight explosion. It is moderately soluble in water very soluble in a dilute sodium hydrate solution ;dilute acids separate it from t,he latter solution as a pale-brown precipitate whilst concentrated sodium-hydrate solution precipitates its sodium derivative in red-brown needles.On oxidation by nitric acid or by an alkaline solution of potassium ferricyanide it is converted into nitrophenol (m.p. 114"). By reduction with tin and hydrochloric acid it is converted into amido- phenol. If it be dissolved in an excess of phenol and a small qitantity of sulphuric acid be then added the mass assumes a dark cherry-red colonr and on the addition of potassium hydrate and water yields a magnificent blue solution. This reaction probably furnishes the clue ORGANIC CHEMISTRY. to Liebermann’s recent observations (last volume p.692j on the colouring matters formed from the phenols by the action of’ nitrous acid. The first stage is in all probability the following N/C6H,0H /C,H4.OH* + C6H5.0H= N-C6HbOH. \O \OH The coIoured body thus produced is it is to be supposed then con- verted into the colouring matter either by oxidation or by condensa- tion. Weselsky’s diazoresorcin is evidently formed in a similar manner from nitrosoresorcin and resorcin :-2CcHs(NO)(OH) + CsH,(OH)z = C,sH,,N,06 + 20HZ. The formation of amidazobenzenc from diazoamidobenzene can also be easily explained if it be assumed that the diazobenzene undergoes conversion into the isomeric nitrosaniline which then acts upon t,he aniline present ; thus C,H,N.N( OH) =CsHd(NH2)(NO) ; (NO) + CsH,(NHg) =C~H~(NHZ)N.NC~H, CGH~(NH~) + OH,.From the foregoing it is evident that nitrophenol cannot co-exist either with nitric acid or with phenol in presence of a strong acid ; and in order to prepare it directly from phenol it is necessary to bear this in mind. The authors find that it is possible to obtain an almost quantitative yield in the following manner :-5 parts of phenol and 20 of potassium nitrite are dissolved in 1000 parts of water and the solution is cooled as well as possible with ice-water ; 10-12 parts of ordinary acetic acid diluted with 10 volumes of water is then added little by little and with constant shaking. After 12-16 hours t,he brown liquid is filtered from a small quantity of resin and extracted with ether ; in order to avoid the action of any excess of phenol and of the nitrous acid present on the nitrosophenol which would occur on distilling off the ether concentrated sodium hydrate solution is added and the mass of sodium-nitrosophenol which separates is spread upon porous plates.The dry sodium derivative is dissolved t,he nitro-phenol is separated by sulphuric acid and slightly washed then rapidly dissolved in hot water and the solution is filtered and extmcted with ether on distilling off’ the ether pure nitrosophenol remains. H. E. A. Diphenylgugnidine. By W. WEITHand B. SCHROEDER (Deut. Chem. Ges. Ber. vii 937-947). THE authors have compared the a-and 6-diphenylguanidines dis- covered by Hofmann and pronounced by him to be isomeric and find that the P-diphenylguanidine (melaniline) prepared by the action of chloride of cyanogen on aniline possesses the same properties as the * Liebermann has since shown that nitrosophenol is indeed 6rst produced but that it reacts with 2 mols.of phenol 1nzol. of water being sepmated,-the colouring matter having the composition C,,H,,NO,.-H.E.A. ABSTRACTS OF CHEMICAL PAPERS. a-diphenylguanidine from diphenyl-sulphocarbamide ammonia and oxide of lead. Both bodies melt at 147" (Hofrnanii found the melting point of 6-diphenylguanidine to be 131") and both possess the same solubility in water and alcohol. No difference could be observed between the two substances which the authors therefore regard as identical. Of the three possible formulae for diphenylguanidine-I.11. 111. Ct3H5.N.H CGH5.N.H C6H5.N.C6H5 I I I C=N.H C=N.CGR~ C=N.H I I 1 CeH5.N.H H,N.H H.N.H No. I11is the least probable since in none of the decomposition-pro- ducts of this compound do bodies appear containing two phenyl groups attached to one nitrogen-atom. Further evidence against this formula is afforded by the fact that no diphenylamine is produced by heating either a-or P-diphenylguanidine with hydrochloric acid to 250". Hofmann has shown that the reaction of melaniline with carbon disulphide may be expressed by the equation :-C,,H13??,(HN) + CS(S) = C13Hu(CS) + CSHN. Melaniline. Sulplzocarbanilide. a-diphenylguanidine also undergoes the same change. Two bye- products were observed in this reaction a small quantity of phenyl sulphocarbimide and a body not yet further examined containing sulphur and crystallising iu colourless needles (melting point 152"-153") ;no rnonophenylsulphocarbamide could be observed.Thus with carbon disulphide both guanidines belisve alike and both give as prin- cipal products siilphocyanic acid and dipbenylsulphocarbamide. In case formula I1represented the constitution of dipheny lguanidine phenyl-sulphocarbimide and monophenylsulphocarbamide should be formed by the action of carbon disulphide thus :-c6H5.N.H C6H5.N.H I I C=N.C6H5 4-C8.s = CS=N.CsH5 + c=s I I N.Hz N.H,. Formula I therefore most probably represents the structure of diphenyl-guanidine and the action of carbon disulphide must be represented thus :-C,H,.N.H C,H5.N.H I I C=N.H + CS.S = CSNH + cs 1 I C,H,.N.H C6H,.N.H .w. H. Y. ORGANIC CHEMISTRY. Diphenylguanidine. By A. W. HOFMANN (Deut. Chem. Ges. Ber. vii 947-950). THE author confirms the results of Weith and Schroeder and finds with them that a-and 6-diphenylguanidine have the same melting point 147". He remarks that it is however not impossible that under certain conditions an isomeric diphenylguanidine may be pro-duced from chloride of cyanogen and aniline ; since a small quantity of mclaniline still in his possession retained its melting point 131"after recrjstallisation from alcohol as well as after conversion into platinum salt and reconversion into the base. The platinum salt gave satis- factory numbers on analysis.The author corrects the statement made in a former communication (Deut. Chem. Ges. Ber. i 147) that a-diphenylguanidine is produced by heating guanidine hydrochloride with aniline. The body mistaken for a-diphenylguanidine was subsequently found to be diphenyl-urea. The guanidine salt was probably converted by some water present into urea which by its action on aniline gave diphenyl-urea. W. H. P. Cinchonine. By H. WEIDEL (Ann. Chem. Pharm. clxxiii 76). BY treating cinchonine with nitric acid of sp. gr. 1.4 a mixture of acids results the relative proportions of which vary with the strength of the acid and the duration of the action ; these acids are formed by the following reactions :-Cinchonine. Cinchoninic acid.C20HaN20 + 402 = 5HzO + CzoHl4N204. Cinchomeronic Cinchoninic acid. acid. C2oH14NZO4 + NHO2 + 5NHOs = 3HzO + 4NO2 + C1,H,NzO,. Quinolic acid. + C,H,N,Oa. 0xycinchomeronic Cinchomeronic acid. acid. Ci1HeN,Os + 02 = CiiH8N20.9 Cinchonine in half kilograms at a time is heated with ten parts of nitric acid in a capzcious retort; in an hour the mixture begins to boil and an energetic reaction sets in the liquid becoming dark orange- yellow ; the source of heat shoiild be removed till this stage is over ; finally the whole is boiled for 70 to 80 hours until a sample diluted with water and supersaturated with ammonia gives a clear solution the precipitate first thrown down being re-dissolved by the excess of ammonia. The excess of acid is then distilled off and the residue evaporated to a syrup diluted with a little water and then dissemi- nated through 4to 5 litres of water.After 24 hours a clear liquid A and a yellow precipitate B are obtained; the aqueous solution A (together with the washwaters of B) is treated with ether whereby a ABSTRACTS OF CHENICAL PAPERS. solution is obtained which leaves on evaporation an indistinctly crystal- line slightly coloured mass C. The aqueous liquor thus exhausted by ether deposits crystals on standing for several days D ;and the mother- liquors of these when evaporated give another crop oi needles E whilst the last mother-liquors F are uncrystallisable. B and C consist chiefly of quinolic acid ; the mixed substances are dissolved in hot strong hydrochloric acid and filtered from a little resin ; on cooling crystals form consisting of a hydrochloride of quinolic acid stable only in presence of strong hydrochloric acid and completely decomposed by water ; these are dissolved in dilute hydrochloric acid ; the solut-ion after treatment with animal char- coal and filtering deposits fine needles of pure quinolic acid.D is purified by dissolving it in hot dilute nitric acid filtering after boiling with animal charcoal whereby resin is removed and leaving the solution to crystallise; the crystals are dissolved in a large bulk of boiling water and treated with milk of chalk until the liquor is only feebly acid. The precipitate contains much calcium oxycinchomeronate some of which salt also crystallises from the filtrate on cooling ; the calcium salts are dissolved in hot dilute hydrochloric acid from which solution oxycinchomeronic acid crystallises in transparent tables.The filtrate from the crystals of calcium salt is evaporated and treated with hydrochloric acid when cinchomeronic acid separates in crystals ; this is the least soluble of all the cinchonine oxidation-products. By crystallisation this first product is purified ; finally it is transformed into copper-salt by addition of copper acetate to the hot aqueous solu-tion and decomposed by sulphuretted hydrogen. E consists chiefly of cinchoninic acid and is purified by recrystal-lisation from water and treatment with animal charcoal. F contains cinchoninic and cinchomeronic acids separable by satura- tion with ammonia filtration from resin treatment of the filtrate with silver oxide and of the silver salt thus formed with hydrochloric acid whereby a solution is obtained which gives a crystalline mass on eva-poration ;of this part is left undissolved on boiling with not too large a bulk of water ;this is cinchomeronic acid.Cinchoninic acid crystallises usually with 4molecules of water and is very difficultly soluble in alcohol and insoluble in ether; when anhydrous it is far more soluble in water than when hydrated; the calcium salt is C20H,2CaN20,. 1&H,O; the copper salt C20H12CuH20~ (anhydrous) ; the silver salt C2,H,,Ag2H204 ; the potassium salt C~oH~2K2N204.H20 ; ; it forms a platinum salt CzoH,4N20a.2HC1.PtC14 heated with nitric acid it forms quinolic and cinchomeronic acids ; but no carbonic or oxalic acid.Quinolic acid forms light woolly crystals resembling quinine sul-phate; it tastes sour at first then bitter and is but little soluble in alcohol and insoluble in ether and water save when a mineral acid is present. It crystallises anhydrous forms a silver salt CgH,AgN204, and unites with hydrochloric acid to form a hydrochloride CgH5AgN204. HC1 ; it also forms a platinum salt (CgH,L%gN20J3C1)2PtC14.By the action of bromine it furnishes a body melting at 88"-990" and of composition C9HBr,N ; by the action of sodium amalgam this seems to give rise to quinoline. ORGANIC CH.EII1ISTRY. Cimhomeronic acid crystallises anhydrous ; its calcium salt is (CllH,Nz06)zCa,.10H,0 ; the barium salt is ( CllH5N20,)2Ba3.4H20, and the silver salt Cl1H,Ag,N,O6 ; unlike cinchoninic and quinolic acids it does not form a platinum salt.The calcium salt formspyridirte on dis-tillation with excess of caustic soda; heating with nitric acid forms oxycinchomeronic acid. Oxycinchomeronic acid crystallises with water (amount not stated) which is lost at 120"; it is readily soluble in hot water and dilute alcohol but not in ether ; with ferrous sulphate it gives a blood-red colour like ferric sulphocyanate ; the calcium copper silver and potassium salts are respectively (~ll~5~z~8)z~a3, (c11&N203) cu, ClIH&,N2O8 and CIlH4&N208 ; when treated with sodium amalgam it evolves all its nitrogen as ammonia forming CilzcAolzic acid CllH1409.This acid does not precipitate silver nor copper salts or those of the irm group mef,als ; lead acetate gives a white precipitate. It does not reduce Trommer's copper-solution ; the silver copper and calcium salts are respectively CllHllAg309,( C11Hl10g)2Cu3, and ( CllH1109)2Ca3.Its formation is expressed by the equation CiIHeN206 + 3HzO + 3H2 = 2NH3 + CI1HlaOg. When submitted to dry distillation cinchonic acid yields a crystalline acid melting at 95" and of composition CloHlo05, the silver salt being CloH7Ags05; the formation of this is represented by the equation :-Cl,I-I1409 = 23320 + c02 + ClOH1005. Hence this substance is termed pyrocinchonic acid. [It seems to be isomeric with opianic acid.obtainable from narcotine by oxidation.-C. R. A. W.] Acetyl chloride has no action on it; melting caustic potash oxidizes it to oxalic acid and lower fatty acids ; when boiled in alkaline solution with sodium amalgam it forms hydropyrocinciio& acid C10H1607, the silver salt of which is CloH13Ag30,.This acid is apparently formed by the reaction :-CioHioO5 + Hz + 2H2O = CioHi60,. The author attributes to cinchonine the formula- This would readily give by oxidation C9Hl6N.CO2H this formula being half that attributed above to cinchoninic acid. OH Quinolic acid is probably dih ydroxyl-nitro-quinoline CgH4N OH , {NO2 as it yields nitrite of potassium on fusion with caust,ic potash and is converted by tin and hydrochloric acid into a resinous easily decom- posed amido-product.ICO.OH Cinchomeronic acid is probably C8HsN2 CO.OH. tCO.OH ABSTRACTS OF CHEMICAL PAPERS. OH OH Oxycinchomeronic acid C8H,Nz CO.OH. C0.OH CO.OH Cinchonic acid being c8H8{ [CO3H),' 013-whilst pyro-cinchonic acid is C8H8{ (CO.OH), bearing to cinchonic acid the same relationship as itaco& \acid to dihic acid. The author discusses the results of Stahlschmidt Schutxenberger Caventou Willm and Zorn and considers that the isomerism of cin- chonine and cinchonidine may be due to the conversion of the ethylene radical into ethylidene possibly the formule may express the composition of cinchonine ; it explains its power of taking up H2and even H (Zorn). The author dissents from Zorn's view that cinchonine contaius hydroxyl viewing the "cLlorocinchonide " of that chemist as not being truly indicated by the relationships- C,H2,NZ.OH cinchonine. CmH23N2 . C1 chlorocinchonide. C. R.A. W. Noh by Bbstractor.-In reference to the last paragraph Schutzen- bcrger obtained some years ago by the action of acetyl chloride on cinchonine a syrupy non-crystalline base apparently an acetyl-ch-cholaine; and from experiments now in progress by the abstractor it seems probable that the same or an analogous product is obtained by the action of acetic anhydride on cinchonine the hydroxylic character of this alkaloid would therefore seem probable. C. RV. A. W. Essential Oils. By A. KURBATOW (Ann. Chem. Pharm. clxxiii 1-5). OiZ of OZibawum.-A specimen of the gum yielded 7 per cent of oil boiling between 160°-1700.A fraction of this which boiled at 156"-158" was found to contain CloH16, and is called olibene. This hydrocarbon has a specific gravity of 0.863 at 12" is resinified by nitric acid and unites with hydrochloric acid to form a compound melting at 127" and containing CIoH,6.HC1. Another fraction of the crude oil boiled above 175" and contained 83.55 per cent of carbon mith 5.57 per cent. of hydrogen. When the resin of olibanum is distilled traces of acid products are ORGANIC CHEMISTRY. 91 formed together with solid semisolid and fluid substances which a'ppear to be condensation-products of the hydrocarbon CloH16. Calamus 0iZ.-The principal tei-pene of this oil boils at; 158"-159" and unites with hydrocliloric acid a compound melting at 63" being formed.When the blue portion of calamus oil which passes over between 250" and 255" is treated with soda it is decolorised and a terpene is obtained which boilsat 255"-258" has a specific gravity of 0.942 at 0" and does not unite with hydrochloric acid. Calamus oil contains portions of more volatile terpenes (158"-159"). rn~ 1. u. On a Substance called Myrlsticin. By I?. A. FL~~CEIGER (Pharm. J. Trans. [S] iv 136). THE published statements concerning myristicin being very con-tradictory the author was induced to submit the substance to further examination. A large quantity of ordinary nutmegs (Jfiipis-tica fragrans) was distilled as were also some " long nutmegs" (M.fatua). After three days' distillation the crystals which had collected on the water with the oil were analysed. They smelt strongly of nutmegs which smell it was found impossible to remove even after repeated purifications from alcohol ; the odour was however lost after the crystals had been kept for some months. They are readily soluble in warm alcohol which was used as a medium for their purification. In water the crystals are insoluble. The alcoholic solution is devoid of rotary power but reddens litmus slowly. The crystals are doubly refractive melt at 54.5",evolve offen- sive vapours but cannot be sublimed. The crystals from Myristica fatua are found by analysis to be iden-tical with those obtained from Jf.fragrans. They yield a soap with alkalis and when this soap is warmed with absolute alcohol and anhydrous sodium carbonate for some time a neutral solution is obtained from which on the addition of an acid the original "myristicin" separates.The formula of this substance is found to be ClaHzsOz,which is that of myristic acid. The author supposes that in the older investigations impure substances had been worked upon. Several salts of myristic acid have been formed. It is monobasic and is present in nutmegs as glyceryl trimyristicate or myristicim. E. W. P. On Chrysenin. By T. L.PHIPSON (Chem. News XXX 69). IFchrysene be treated with twice its volume of boiling water so as to render it fluid and the water be acidulated with hydrochloric acid cooled and filtered a liquid of a bright yellow colour is produced from which chrysenin separates on addition of ammonia as a brick-red precipitate mixed with quinoleine and other bases.It may be purified by forming and decomposing the sulphate several times and finally exposing the dark orange-coloured liquid to sunlight for a few weeks. Ammonia then throws down the base as a bright yellow flocculent precipitate. Its vapour is irritating to the eyes and forms 92 ABSTRACTS OF CHEMICAL PAPERS. dense fumes with vapour of hydrochloric acid; it has a hot acrid pungent taste is strongly alkaline and forms a nitro-compound with hyponitric acid &c. E. W. P. On the Albumins of White of Egg. By A. B~CHAMP (Compt. rend. lxxix 393-396). THE author infers from his experiments that white of egg cont,ains three soluble albumins the rotatory powers of which as determined by Soleil's saccharimeter are -33" -54" and -71" respectively.Normal white of egg rotates 42"to the left W. A. T.