28 ABSTRACTS OF CHEMICAL PAPERS.Organic Chemistry.Condensation of Acetylene by the Silent Discharge. ByBERTHELOT (Compt. ?*end., 111, 471--472.)-If the product. of the con-densation of acetylene under the influence of the silent discharge isleft exposed to the air, it absorbs about one quarter of its weight ofoxygen, and can easily be detached from the glass in the form of ayellow, resinous pellisle. It continues to alter spont,aneons!y in thevessel in which it is placed, with formation of a carbonaceous sub-limate which is probably the result of a secondary change. Whensubjected to dry distillation, i t undergoes sudden and explosive de-compositrion, which seems to be exothermic, wihh production of aconsiderable quantity of water, together with some acetic acid, andacetouic liquids which have an odour of caramel, and are similar to,if not ident,ical with, %he products from sugar or tartaric acid. Neitherbenzene nor furfuraldehFde is obtained, and distillation with soda-lirncyields acetone and other simple products.It is clear therefore thattlie condensation of acetylene under the influence of the silent dis-charge is very different from its condensation under the infinerice ofheat, C. H. I3.Combination of Mercuric Cyanide with Lithium Salts. ByR. VARET (Coinyt. rend., 111, 526-527>.-A concentrated solution oflithium iodide is added drop by drop to a saturated solution ofrriercuric cyanide heatred a t 50-60". A further quantit,y of mercuriccyanide is then dissolved in the liquid and more lithium iodide isadded.The liquid is concentrated to a, syrup, filtered, and allowed tocool, when it deposits the compound HgCy2,2LiCy,Hg12 + 7H20 i nlarge nacreous lamellae, which are hygroscopic, very soluble in water,and lose 3 mols. H,O a t IOO", but cannot be completely dehydratedwithout, decomposing. When the salt is carefully heated, it gives offwater and becomes yellow, a sublimate of mercuric iodide forming atthe same time. At a higher temperature, the salt melts and decom-poses into mercuric iodide, mercury, cyanogen, aiid mercurms iodide.Dilute acids decompose the salt with liberation of hydrocyanic acidand precipitation of mercuric iodide, whilst mercuric cyanide a-nd alitliium salt of the particular acid remain in mlution.Coppersnlphate, when heated with a sclution of the salt, qrecipitates cuprouscyanide and mercuric iodide, a result, which indicates tha,t all thecyanogen is not combined with the mercury. These reactions showthat the constitution of the compound is expressed by the formuhgiven.I f lithium bromide is added gradually and in small quantity to afiaturated solution of meimwic cyanide heated at go", the liquid, oncooling, deposits crystals of the compound HgCy,,LiBr + 3+ H,O.They are hygroscopic and very soluble in water, lose 14 mols. H,O at loo", but cannot be dehydrated without decomposing. When heatedgently, i t yields no sublimat,e of mercuric bromide, hut a t a hightempersture i t undergoes complex decomposition. When heated witOItUANlC CBE MISTRY.29copper mlpliatc solution, no cjanogen is evolved, and no precipitateis formed ; it follows that all the cyariogen is combined with themercury.A mercury lithinm cyanochloride is obtained by evaporating asolution of mercuric cyai)ide containing an excess of litliium cliloi-ide.It is so hygroscopic that its composition could not be ascertained.C. H. B.Ethylene Dithiocyanate. By. C. PARENTI (Gnxzetfa, 20,178--183).-By tIeating perthiocyanic acid with alcoholic pchash,E'leischer (this Journal, 18i1, 391) obtained a compound isomericwith potassium thio- and ibothio-cyanate, but differing from thest,compounds in several respects (Annalen, 179, 204). The acid formcdh v decomposing this salt with sulphuric acid was considered to be adithiocyanic acid.To prepare the ethylene derivative, perthiocyw [ti(:acid and ethylene bromide in molecular proportion are dissolved inthe least possible quantity of alcohol, mixed with ail alcoholic solut ono€ potassium hydroxide, and boiled for 5 to 6 hours. The filteredliquid, on cooling, deposits a semi-crystalline mass, part of which isinsoluble in boiling water, and remains in hard ill-defined crystalswhich melt a t 137-140". The soluble portion, on recrystallisationfrom boiling water, is obtained in slightly yellowish prisms which meltat 349-150°, and are readily soluble in hot water and alcohol, b u t ,insoluble in ether and benzene. It dissolves in cold conc*entratedsnlphuric acid, and is reprecipitated unaltered on the addition ofwater.After fusion, it resolidifies at 13O", but t h i s temperature isI-educed to 118" after successive fusions. The aqueous solutionirs nut coloured by ferric chloride even after acidification with hydro-chloric acid ; on heating the alkaline solutions, the respective thio-cjanates are formed. The constitution of this salt is prohablyK*C,H,*N. The compound melting a t 137--140" has the composi-tion CaN,S3(C2H4), ; it is slightly soluble in cold concentratedsulphuric acid, and, on warming, a gr*een liquid with a bluefluorescence is prGduced from which sulphur separates after a time.S. B. A. A,FS\\cs/Diacetylcarbinyl Acetate. By A. COMBES (Compt. rend., 111,4~1--423).-Chlo1~aceryIat etone (Abstr., 1890, 1394), when boiledwith potassium acetate in presence of alcohol, yields a pale-jellow liquid which boils at 74.5" under a pressuie of 21 mm.,itlso a large quantity of ethyl acetate.The new product hasthe composition C,H,O,; it bas an acid odour, but yields nitnietnllic derivatives, and reduces Fehiing's solution and aminoniecald v e r nitrate in the cold. It yields a very unstable hydiazoiieCll,H14N202, which resinitit s rapidly when exposed to air and light,and crystallises from ether in large coloui less rhomboidal tableswhich rapidly become red n h t n exposed to light. If this hydrazoneis treated with excess of phenylhydrazine in alcoholic solutiou, i tyields an oaazone CI5H,a4, very soluble in ether, from which it i30 ABSTRACTS OF OHIEMICAL PAPERS.precipitated by light petroleum in crystals melting a t 143-1144'. Itis the osazone of acetol, and can also be obtained by the direct actionof phenylhydrazine on a hot solution of the compound C,H,O, inacetic acid.The cornpound C,H,03 is in fact the acetate of acetol, formed inaccordance with the equations CHAc,Cl + AcOK = CHAc,*OAc +KC1 ; CHAC,.OAC + EtOH = CH,AC.OAC + AcOEt.I n order to avoid the secondary action of the alcohol, monoclilor-acetylacetone was boiled for four or five hours with potassiumacetate in presence of glacial acetic acid, and the product was pouredinto water and mixed wit,h concentrated cupric acetate solution.Agreen precipitate separates, and is purified by solution in chloroformand precipitation with ether ; it forms deep-green crystals of the com-position (C,H,O,),Cu, and is the cupric salt of diacetylcarbinol,CHAc,*OAc, which contains a basic hydrogen atom in the groupZCH-OAC.The copper salt is dissolved in dilute sulphnric acid,and the solution is extracted with ether. Aiter the ether has beenexpelled, the diacetylcarbinyl acetate is obtained as a colourlessliquid boiling at 111" under a pressure of 21 mm. It reducesFehling's solution and ammoniacal silver nitrate iii the cold, has astrongly acid reaction, and decomposes carbonates with formation ofcrystallisable metallic derivatives. When treated with phenyl-hydrazine, it yields a viscous liquid which boils without decompositionin a vacuum a t 235--'240", and which, when treated with hot sulph-uric acid or with oxidising agents, yields a beautiful, blue colour-ing malher, insoluble in watw, but.soluble in chloroform or sulphuricacid, and having all the characteristics of a pyrazole-blue.Attemph to obtain diacetylcarbinol by saponification of the acetatehave not yet been successful. C. H. B.Indian Geranium Oil: Oxidation of Geraniol. By F. W.SEMMLF;R (Bey., 23, 2965-2968 ; see also Abstr., 1890, 951),---Fmthe oxidation of geraniol, potassium dichromate (10 grams) is dis-solved in sulphuric acid (12.5 grams) and water (100 grams), and thcgei-aniol added (15 grams all a t once), the mixture being a t first wellcooled, and af Lerwards allowed GO become warm, and vigorouslyshaken for half an hour. The whole is then made slightly alkalineand distilled in a current of steam.The distillate contains an oil,which has a pleasant odour resenibliiig oranges and lemons, and is amixture of the oxidation product with ethereal oils formed by t,heaction of the sulphuric acid on geraniol. To separate the latter, theoil is mixed with s saturated solution of sodium hydrogen sulphite,and allowed to remain for 24 hours. The crystalline magma is the11collected, pressed between filter-paper, washed with ether, mixed withsodinm carbonate, and distilled i n a current of steam. A clear, C0lOUJ'-less oil, haviug the composition C,,HI6O and the above-mentionedcharacteristic odour, is thus obtained, aiid appears from its genera]reactioiis to be an aldehyde. It is at present being more closelyexamined.Alkttl-ine potassium permanganate acts on geraniol in a differentORQANIO CHEMISTRY.31manner, yielding a polyvalent alcohol, which has the closest rcsembl-ance to the sugars. H. G. C.Dihydric Alcohols derived from Isobutaldehyde. By E.STOBODA and W. FOWEK (Monatsk., 11, 383--398).-1t has been pre-viously shown (compare Abstr., 1884, 37, 832) that when alcoholicpotash acts on a mixture of isobutaldehyde and acetaldehyde, methyl-isopropyleth ylene glycol, OH-CHMe*CHP@.OH, boiling at 206-20i0,is formed. When valeraldehyde and benzaldehyde are substitutedfor acetaldehyde, isobut~lisop~o~ylefhylene glycol,CHMe2*CH,*C H (OH) *CHPrfl*O€T,which melts a t 79-80" and hoils a t 23 1-232", and pheniyZisopmpjII-ethylene gZ!/coZ, OH*CHPh-CHP@*OH, melting at 8 1 - 4 2 " and boilingat 286-287", are formed respectively.In the formation of isohutyl-isopropylethylene glycol, potassium isobutyrate is the only other pro-duct; i t must therefore be supposed that a molecule of isohut-aldehyde unites with a molecule of valeraldehyde through their alde-hydic carbon atoms, which, a t the moment of condensation, take upeach an atom of hydrogen, fiirnished by the oxidation of anothermolecule of isobutaldehyde by a molecule of potassium hydroxide.The three glycols yield diacetyl derjvat'ives, when heated for18 hours, in sealed tubes, a t 200", with an excess of acetic anhydride.The compounds thus obtained from methylisopropyl glycol, isopropyl-isobutpletliylene glycol and phenplisopropylethylene glycol, haverespectively the formulae CloHI9O4, C13H2204, and C1sH2004, and theboiling points 220", 240-242", and 295-297".Cn treatment with sulphuric acid, the three glycols behave as pina-cones, and lose the elements ul a molecule of water ; isopropylisobutylglycol is converted by cold concentzated sulphuric acid into ana-pinncoline, C,H,,O, which boils at 150" and has the odour of camphor,and by hot dilute acid into a ,%pinacpline, (C9H180)2, which boils at274" and is without odour.The other glycols give similar products.G. T. M.Sugars derived from Rhamnose. By E. FISCHER anti 0. PILOTY(Ber., 2 3, 3 102-21 10) .--Hh amnose (isodulcite) is metk ylpentose,has the formula CH,*[CH*OH],-c'HO, and, like the other heptoses,yields sugars richer in carbon.I t is proposed to term these deriva-tives rhaninohexose, rhwm noheptose, and rhamnooctose.RhamnitoZ, CH3*[CH.0H],.CH2*OH, is prepared by the reduction ofrharrinose with sodium amalgam, aiid crystallises from alcohol oracetone in t,riclinic prisms, which melt a t 121", and are insoluble i nether. It is sweet t o the taste, is only partially decomposed on dis-tillation, and does not reduce alkaline copper solution. It is readilyoxidised by nitric acid, and is reduced by hpdriodic acid. The yield is60 per cent. of the rhamnose.Rhnwinohexonic acid, CE,*[ CH.OH],COOH, is already known by thename isod~~lcitolcarbox~lic acid, or rhamnosecnrboxylic acid (comp.Ahstr., 1888, 806)..Ehawmohexose, CH,.[ CH*OH-),*CHO, is prepared by the reductionof rhamnohexolactone with sodium amalgam at a low temperature 32 ABSTRACTS OF CBRMIUAL PAPERS.the yield is 60-65 per cent.of the lactose. The compound crysta7-lises from methyl alcohol in thick plates which melt a t 180-181"with decomposition, and exhibit all the characteristic properties ofsugar. I t does not ferment with yeast. The phenylhydmzone isreadily soluble in water, The OSnzune is obtained in stellate groupsof yellow needles which melt a t 200" with evoliition of gas, arid arereadily soluble in aJlcohol, but nearly insoluble in water.BhamnolrexitoZ, CH,*[CH-OH],.CH,.OH, is prepared in a similarmanner to rhamnitol, and crystallises from alcoltol in small, colourlessprisms which melt a t 173", with previous softening at 170°, and haveno action on alkaline copper solution.Rhnmnoheytonic acid, CH,.[CH-OH],.COOH, is formed by theaction of hydrogen cyanide on rhamnohexose ; on evaporatiC~n, i treadily passes into the l:ictone, which cr~stallises from a,lcohol i nstellate groups of colourless needles melting a t 160", with previour;softening a t 158" ; t'he yield is 63 per cent.of the sugar.Rlmmnohepforiic hydyazide, C8H,,O7*N2H2Ph, is formed by the actionof phenylliydrazine acetate on the acid 01' lactone ; it crystallisesfrom water in slender, white needles which melt above 215" withevolution of y i s , and are very sparingly soluble in alcohol.Iiharnnohepfosc', CH,.[CH.0H]6*CH0, is prepared by the reductionof the lactone, and could not be obtained i n crystals; it is readilysoluble in water or alcohol, but insoluble in ether.The pheny7hydr-rrzone crystallises from water in colourless, sleiider needles ; on treat-ment with hydrochloric acid, the su'?ar is regenerated. The ornzonr!is deposited in slender, yellow needles, which are very sparinglysoluble in water o r alcohol, and melt a t about 200" with decomposition.Bhamnoctonic acid, CH,*[ CH*OH],.COOH, is prepared fromrhamnoheptose; on evaporation, the luctoire is formed, and is beatpurified hy means of the phen) lhydrazone ; it crystallises from waterin colonrless, concentric needles which melt at 171-172" withoutdecomposition, aiid are readily soluble in water or alcohol, but spar-ingly so in acetone.The pheizylhydmzide, CH,* [ CH*OH],.CO*N,H,Ph, cry stallises fromwater in slender, white needles melting a t 220".Rhtr~~zsioctose informed in small quantity by the reduction of the lactone ; i t readilyreacts with alkaline copper solution, and yields an osaxoae, which isinsoluble in water, and melts at 216".The following table gives the speGific rotatory powers of the rham-nose compounds, as far as they are known :-Rhamonolactone ............Rhamnose ................. + 8" to 9"Rhamnitol. ................. + 10.7Rhamnohexonolactone ....... + 83.8Rhamiiohexose .............. - 6 1-1Rhamnohexitol (approximate). + 11.6Rhamnoheptonolactone ...... + 55.6Rlmmnoheptose (approximate) + 8.4H hamnoc t onolac t one ........Specific rotation.-- 5 1 -20J. B. TORGANIC CHEMISTRY.33Arabinose from Wheat Bran and Rye Bran. By E. STEIGERand E. SCHULZE (Ber., 23, 3 1 10-3113). --It has been previouslypointed out by Tollens and his pupils that in all probability the for-mation of furfuraldehyde from wheat bran and from rye bran by theaction of sulphuric acid depends 011 the previous decomposition ofpetitaglucoses (aratinose and xylose) ; neither of these compoundshas, however, hitherto been isolated from the product of the reaction.Wheat bmn, freed from starch and alburiiinoiis mat,ter, is boiled forseveral hours with 3 per cent. dilute siilphuric acid; the acid isneutralised with barium carbonate, the solution filtered, concentrated,and extracted with alcohol ; on evaporation, arabinose crystallises out ;i t waq identified by its specific rotatory power, arid its ozazone.The arabinose is probably formed by the hydrolysis of a compoundwhich the aiithors term metarahan.This is a constituent of the cellmembrane, and cannot be prepared qnite pure. I t gives a cherry-red colour on warming with hydrochloric acid and phloroglucinol,and is insoluble iri water, arid in cold dilute alkalis or acids. Onwarming, it readily dissolves, and becomes converted into sugar.Other samples of wheat bran gave similar results, as did also1.J-e bran. No galactose or mannose could be detected in any of thesolutions. J. B. T.Starch. By C. SCHEIBLER and H. MITTELMEIER (Be?.., 23,3060--3O75) .--The autliors give 3 historical review of the investip-tion of starch and of tlic compounds derived from it by hydrolysis,followed by a sketch of the recetit work arid present theories on thes u bjeot.The experimental Imrt of the present communication is l i m i t ~ l toan investigation of dextrin.Commercial dextrin can be purified by precipitation with alcohol,care being taken that tlie quantity of alcohol piwent never exceeds85 per cent.of the total solutiott ; after precipitating three times, theproduct ceases to give an insoluble osazotie, and after repeating theoperation several times the dextrin timy be considered to be free fromsugar. Good results arc also obtained by dialysis and subsequelktprecipitation with alcohol, but a product free from sugar could not beproduced by fermentation.Pure dextrin becomes yellow or brown on heating with potash, andit readily reduces alkaline copper sdlution, thns showing that, as it isitself not a definite compound, its constituents must beltlng wholl~,o r in great part, to the class of sugars which contain an aldehydic orketonic group.This view is supported by th9 fact that, on digesting solid dextrinwith excess of phenylhydrwzine a t ordinary temperatures, it dis-solves, and on heating with alcohol a white precipitate is obtained ;t h i s is washed free from phenylhydrazine, and purified bydissolving in water and precipilatiiig with alcohol.This corn-pound contains 1.02 per cent. of nitrogen, corresponding with theformula C96H62080*S2HPh, and closely resemhles dextrin i n itschemical properties and i n solubility ; it is decomposed by hydro-chloric acid in a manner similar to the pheiiylhydrazones of sugarsVUL.LS. C34 ABSTRACTS OF GHk;M1CAlA PAPERS.wit,h high molecular weiyhts. By heating on t,he wat,er-bath f o rtwo hours with phenylhydrazine acetate, and treating the productwith alcohol, a, pale-yellow osazo?ze i s formed, which is less soliible inwater than the phen-ylhydrazone, and may be precipitated bv alcohol.The percentace of nitrogen varies somewhat. thus showing t h a t i n a l lprobability the body is a mixture of osazoiie with unaltered phenyl-hydrazone.An aqueous Kolution contdining 8 per cent. of dextrin is repeate3lytreated with smnll quanrities of sodium amalgam, dilute acetic acidbeing added from time to time ; after several days, alcohol i s addedto the slightly acid solution, and the insoluble product pnrified byrepeatpdly dissolvirig in water and precipitating with alcohol.Theauthors propose t o call this colonrless compound de.i-tvitol; i t does notredilce alkaline copper solution, is inst-)luble in phcnylhgdrazine evciion warming, and the solution (300s not brcomc yellow on boiling withp Itash. Ry the action of concentrated acids or of diastase on dex-ti-itol, a liquid is formed which readily reduses alkaline copper sulu-tion.An 8 per cent. aqueous solution of dextrin is liented with R fewdrops of bromine and allowed t o stand uiltil the colour disappeai-s, asecond quaiit,ity of hromine is then added, and, as soon as this hasrettcted, the dextrin is precipitated with alcohol in order to frve i tfrom hydrobmmic acid ; the product is disholved in v a t e r n,nd timteilwith hromine as before, the process being repented until t h e c7exti.inceases t o reduce alkaline copper solution.After repeated purifica-tion, a white powder is obtained which is soluble i n phenylliydi-mine ;an aqueous solution reddens litmus paper, and decomposes calciiimcarboi,ate on warming. No precipitate is obtained with lime-waterand lead wetate ; hy the action of diastase, or by heating with amineral acid, a product is obtained which readily reduces alkalinecopper solution.The above results all point to the presence of a n aldehydic group indextrin, and this view is supported by the fact that the products ofhydrolysis are also aldehydes.By the hydroljsis of starch, the authors have only obtainedglucose, but? from commercial “ starch sugar ” they have isolated anunfermeritable compound which rcwxnhlcs dextrin, and, from theanalysis of its osazone, has the formula C1LH22011, being thus isomeiicwith maltose.J. B. T.Stereochemical Isomerides of Nitrogen Compounds. By A.HANTZSCH and A. WERNER (Uer., 23, 2764-2769 ; see also Abstr.,1890, 34t\, 9iO).-Ttie authors in this paper sum u p their views withregard l o the isomeric relatioiiships of the oximes as follows :-(1.)The oximes X:C:N*(I)H behave as titutumeric compounds, and yieldtwo different a1 kjl der.ivat,i ves having the struct ura1 form.; 1~X:C:N*OR and X:C-N*R, wbich may be distinguished as “ o x ~ - g e nethers ” and “ nitrogen ehhers.” (2.) Cert’ain asymmetrical oximesexist i r twc otereoc~hemically isomeric: forms, which, accoding t o thethcbry propwed by the authors, are represented by the formula3‘0ORGAN10 CHEMISTRY.3 5X y Y( 3 . ) Each of these isomerides can yield twoN-OH’ x‘G*y andIT0.Nstructurally isomeric etliyl derivatives, and therefore an asymmetricaloxime of the formula $>C:N*OH should yield four alkyl dwiva-tives, namely :-I n 110 one case have all four alkyl derivatives been prepared, onlythree being known in most cases, two of these being “oxygenethers ” and one a “ nitrogen ether.” I n the case of furfuraldoxime,however, the two isoineric 9‘ nitrogen ethers ” have been prepared,thus giving an indirect proof of this part of the theory.Auwers and Meyer have suggested that the isomerism of theoximes is due, not to the nitrogen atom, but t o the asymmetricalconstitution of the hydroxjlamine itself, as represented in theformulae $>C:N*O/H and T>C:X*O (Abstr., 1890, 1264).Theauthors point, out that this hypothesis does not explain the existenceof two isomeric nitrogen ethers, and also that the formulm proposedby Auwers and Meyer do not represent distinct isomerides, but onlyphases of an intermolecular atomic motion, which pass one into theother by the simple rotation of the hydrogen atom of the hydroxylgroup around the axis N-0. Further, ~ f , owing to the combinedatti*action of the nitrogen atom as well as that of’ tlie oxygen atom,the h5drogen atom tskes up a position intermediate between the two,it rnust) be also supposed that thy oxygen atom is attracted out of theplijne by the hydrogen atoms of the wmido-group; this, however,siniply means, in other words, that the h j droxglttmine moleculeassumes the tetrahedral configuration /I\ , which is simply aspecial case of the authors’ general hypothesis.Sccording toBehrend’s hypothesis (Abstr., 1X90,575), the isomeric benzaldnximesshould show very slight differences in their piiysical properties, but,as a matter of fact, the two coriipoiirids are completely distinct.Moreover, the latter hypothesis gives no explanation of the readyformation of benzonitrile from isobenzaldoxime.In concliision, the authors state that their hypothesis, like thoseof Van’t HOE arid Wislicenas, is riot dependent on any specialassumption as to the direction of valencies, &c., but is simply deducedfrom general s j mmetrical relations.Attempts to prepare Stereochemical Isomerides of NitrogenCompounds.By A. BANTZSCH (Bey., 23, 2769--2773).-’l’heinvestigation described in this paper was undertaken to detjermine, ifpossible, the conditions nnder which stereochemical isomerides of‘HNHOEHH. G. C.a 36 ABSTRACTS Ofr OHEMICAL PAPERS.iiitrogeii compounds are formed. ( 1 . ) The study of t'he question ofthe existence ct' an asynirnetricnl nitrogen atom i n derivatives ofammonia and of hydrazine has not yet led to any positive results (seealso Kraft, following abstract). (2.) All attempts to ohtain stereo-chemical isomerides of compounds, other than the oximes, with Rdouble linkage between the nitrogen and carbon atom, have beenwit,Iront success.It was found that urethanes do not condense withcarbonyl coimpoclnds according to the equation=CO + H,NC@OR = =C=N*COOR + HzO,and that isomeric derivatives cannot, be obtained fmni benzylidinc-;tniline (this vol., p. 50). Further, i t was found that nitriles(lo not form additive compounds in the mauncr represented by theequation :-N-Y - - N YX.? + z X.6.Z *( 3 . ) The compounds which yield isomeric oximes incliide almost allaromatic aldehydes and asymmetrical ketones, their meta- and para-substitution products, arid also diketones of the benzile type andphenylglyoxylic acid.The fatty aldehydes and ketones, and all com-pounds containing even a single alcohol radicle, CtLHZ,L+l. in comhina-tion with the carbonyl group, yield only a single oxinie. This is alsothe case with all compounds containing a carbonyl group in a closedchain, and in all aromatic a1dehTdes and ketones in which substitutionhas taken place i n the ortho-position relatively to the carbonyl group.When substitution has taken place in both ortho-positions, the com-pound does not yield any oxime. This agrees with the results of Kehr-mann, but the author differs from Kebrniann in so far as he regardsthe configuration of the molecule, rather than the space which i toccupies, i s determining the possibility of the existence'of isomerides.H. G.C.Displacement of Halogens by the Amido-group. By E.SEELIG (Be?.., 23, 2971- 2972). - In the usual process for thedisplacement of a halogen by the amido-group by treatment withwith aqueous or alcoholic ammonia, the reaction, as a rule, does notstop with the simplc! displacement, but proceeds further, with forma-tion of secondary and tertiary bases. If, in place of the solution ofammonia in water or in alcohol, phenol diluted with 15 per cent. ofvrater and saturated with gaseous ammonia is employed, the reactionproceeds much more smoothly. Thns benzyl chloride treated withthis reagent, gives 24 per cent.. of the theoretical yield of benzglamine,whereas with aqueous or alcoholic ammonia, only traces of t,he arnineare obtained. Ethylene bromide, heated in a similar manner, gives ayield of 38 per cent.of ethylenediamine hydrate. H. G. C.Isobutylamine. By H. MAL~IOT (Couzpt. Tend., 111, 528-529).-The author has investigated the conditions which give the largesty~elcl of isobutjlamine by the reaction of isobutyl chloride wit1ORGANIC CHEMTS FRY. 3 7ammonia. The chloride was heated witn different proportions ofammonia in sealed tubes a t 100" for various periods of time. Details oft h s experiments are given. The best results are obtained when 1 mol.of isobutyl chloride is heated with 10 or 15 mols. of ammonia; in thefirst, case the quantity OE diisobutylemine formed is twice as great asin the second, but it is easily removed by washing with water. Themixture must be heated for 3 to 34 days.C. H. R.Action of Secondary Amines on Imido-ethers. By A. Pmsclr(Rer., 23, 892 7-2933) .-Tetrethylsziccinamidine hyJrochloriJe.NH:C(NE~)*CH2*C(NH)*NEt,.2HC1, is prepared by the action ofdiethylamine on et,hylsuccinirnidinc hydrochloride ; after remainingfor about eight days, it separates in lustrous, prismatic crystals. Onrecrystallisation, ammonia is eliminated, and tetrethllZsuccitl,imid~~~,~C H: C ( N E tz)CH,*C(NEt,)hydro c h 1 o r i d e , I >N,HCl, is formed, crystallising in large,thin plates. The &at&ckioride is deposited in yello wish-red, Iu~troiis,pointed Drisms which melt at 202".>N,HCl, 7 H:C ( NPra,)CH,*C (NPra,)TetrapropyIsuccirLil?i idiiie hydrochloride,which closely resembles the tetrethyl derivative, is 'prepakd by thcaction of dipropylamine on phen-ylsuccinimide hydrochloride ; theintermediate succinamidine could not be isolated ; the condensationtakes place much more readily than with diethylamine.The nitrate,C,,H,,N,,SHNO,, melts a t 53". The ylntinochloride is very spariuglysoluble in water, from which it crystallises in large, pale yellowplates melting at 174".The constitution of the above compounds cannot be regarded asbeing definitely proved, but the fwmulse assigned to them appear tobe the most probablep-Bromopropaldehyde and p-Bromopropionic Acid. ByL. LEDERP:~; ( J . pi-. Chew. [2J, 42, 384). /j-Bmrnopropnldehyde isobtained by passing dry hydrogen bromide into well-cooled acyalde-hyde to saturation, and evaporating the excess of acraldehyde at; itlow temperature.It is a thick, yellowish oil, and does not crystallise; it soon decomposes at, the ordinary temperature, and, whenheated to 45" in abwnce of air, i t evolves hydrogen brsniide andch a 1's.p-Bromopropionic acid, obtained by oxidising the aldehydo with woll-cooled nitric acid (sp. gr. 1-48> and extracting with ether, crystsllisekin large, colourless tables which melt, a t 62*5", and dissolve in theusual solvents (Beokurts and Otto, Abstr., 1885, 506). The ethyl saltJ. H. 1'.boils atl 89" (40-50 mm.). A. G. r3.Action of Hydrocyanic Acid on Unsaturated Aldehydes. ByG. JOHANNY (Xonatsh., 11,399-412 ; compare Gauiier, Bull. SOC. Chim.,25, 481; Lobry de Bruyn, Abstr., 1885, 242; 1886, 924).-Whenmethylethglacraldehyde is heated with am equal volume of anhydroushyclrocyanic acid in sealed tubes for 50 hours at 45", the hydrocyanide38 ABSTRAOTS OF OHEMIOAL PIPERS.CsHloO,HCN, is formed, but the compound is so uristable that itcannot be isolated in a pure state, although its acetyl dei-irativeCHEt.CMe*CH( CN).OAc, obtaiiied by heating it with excess ofacetic anhydride in a iaeflux apparatus, may be distilled without de-composition at l l ~ - l 1 4 ° under a reduced pressure of 35 mni.a- Hydro3 y -p-prop2/lidiliebutyrait~i~e7CHEt:CMe*CH (OH).CONH,,is formed when the above-described acetj-1 compound is treated withfive times its weight of fuming hydrochloric acid and the mixture isallowed to remain a t or.din;try temperatures i n a closed flask forthree days.From an alcoholic solution, it crystallises i n colourless,rhombic plates which melt a t 100--101”, arid on heating with milk oflime, ammgnia is evolved, and the calcium salt of a-hpdroxypropyl-idenebutyric acid, (CTH1103)2Ca, + BHzO, obtained ; this crystallisesfrom water in needles. G. ‘1’. $4.Molecular Weight of Glycocine and its Anhydride, ByT. CURTIUS and H. SCH~JLZ (Iler., 23, 3U41--304Y).--I)etermina-tions of the molecular weights o€ amidoacetic acid and of variousderivatives by R8aoult’s metliod, with water as the solvent, give re-sults in accordance with the simple formula NH,*CH,.COOH.Similar experiments with the auhydride point t o the FurmulaThe results previously obtained from vaponr density determina-tions by Hofmann’s method are thus fully confirmed.J. B. T.Glycocine. By J. MAUTHNER and W. SUIUA (Monatsh., 11,373-382 ; compare Abstr., 1889, 139) .--The authors have preparedglycocine by a more satisfactory method than those previously de-scribed, in the following way :-‘I0 a well-cooled solution of chlor-acetic acid (100 grams) in water (10G c.c.) or alcohol, 20-22 percent. aqueous ammonia (1 litre) was gradually added. After i*emain-ing for a week a t ordinary temperatures, the solution was heated,first alone, and then with lead oxide, to expel ammonia; after filter-ing, the lead was precipitated by the addition of freshly preparedammonium sulptiide, the lead salyhido filtered off, the solution evapo-rated to dryness, aid the crystalline mass thus obtained dissolved ina little water and boiled with copper carbonate.On cooling thefiltered solution, copper glycocine crystal lised out in masses ofneedles which, when recrystallised from a, little water, gave, besidesthe needles, a number of bluish-violet, glistening scales. ‘l‘liese scaleshave a similar composition, (C,H,NO,),Cu + H20, to tho needles, but,give up their water of crystallisation at a much lower temperature.‘I’he modification crystdlising in scales may be obtained by heatingthe needles with a quantity of water insufficient to completely dis-solve them, rapidly filtering, and allowing the solution to crysta1:ise.The yield of copper glycocine obtained by this method was about 28per cent. of theoryORGANIC CHEJIISTRY.39Calciiinz 07"fhOtoZyZylycocine, (C9HloN02)2Ca + 3H,O.-This salt isprepared bv a rnetliod siinilar to that used in the preparation ofcalcium orthophenylglycocine (compare Abstr., 1889, 1068). Whencrystallised from water, it forms flat,, glistening needles which are in-soluble in absolute alcohol. On clry distillation with calcium formate,:(r product was obtained which appears to be orthotolindole (compareRascheri, Abstr., 1887, 956).Culciiim a-nap hthylghjcocine, ( C12HIoN02),Cn + 3H20, is obtainedby dissolvifig a-nap~thylglycocine in dilute ammoilia, and precipi-tating the warm solution with cttlcium chloride. When crystallisedfrom dilute alcohol, the sitlt forms clusters of flat needles. On heat-ing with calcium formate, a mlxtailce W R S obtained .which resemblesSctilieper's a-naphthindole jibid., 963) in crystallising in needles, buthas a lower melting point, 163".Yhenylylyc~oci~z~pal.nrcc?.bo,o!/l~~ ucid, C9H9N01, is ol3tained by boilingfor several hours a mixture of paramidobenzoic acid (25 grams),chloracetio acid (20.6 grams), and sodium carbonate (32.8 grams),dissolved in water (1 litre).On acdifjing the cooled solution, a yellowpuwder (yield 50.2 graius) is precipitated, and this, on recrystallisa-tion from water, forms a crystdline rnass which melts with decom-position at dlY--221". The barium salt, C,H7NOiBa + 4H20, andthe calcium salt, C9HiN04Cn + 3H,O. are white, crystallinc pow-ders ; the copper salt, C9H7N01Cu + ;3H,O, is a dark-green aniorph-ous powder.G. T. M.Constitution of Diazo-fatty Acids. By T. CURTICS (Ber., 23,3036- 3US 7) .-€€ydmz.ine 01- It ydrazopropion ate,rH>CMe*COOH,N2T-r4, NHis obtained from hydraziiie hydrate arid pyruvic acid as ,z colourless,uystalline powder melting a t 116".Meihyl a-hyd~.rrzo~l.oiwioizate, > CMeeCO OMe, is prepased in aNHsimilar manner from met,hyl pyruvate and hydrazine hydrate ; i tmelts a t 82", and on treatment! with niercuric oxide yields a methjla-diazopropronate, N,CMeCOOMe. which boils a t 1,:3--55" uiider apressure of 32 mm. Tho same cctmpound has previously been pre-pared i n small qnantities from methyl a-anlidopropionate arid sodiumnitrite. !Phis result proves coriclusi~~ely that in the diazo-fatty acidsthe tm7o nitrogen atoms are linked t o the same carbon atom.YHJ.B. T.Action of Bromine on Angelic Acid and Maleic Acid. ByR. F~TIIG (Anruden, 259, 1---40).-When Wislioeilus wafi engagedin developing his theoiy of the rotation of atomic configurations,there were on record various obsexations m:ide by the author andhis pupils which were riot in accoi dsuce with the n e w theory ; manyof the author's experiments were, therefore, repented by Wisllcenuswith results which agreed better with his t heoreticul views, bu40 ABSTRACTS OBI CHEMICAL PAPERS.which were totally at variance with those previously olitained bythe author.The author has repeated some of the experiments in question withthe utmost care, and has shown that his previous statements m eabsolutely correct in every detail.One of the most important points of difference which receivedattention was the inrestiption of the action of bromine on angelicacid. I t had been stated by Fittig and Pagensfrcher (Abstr., 1878,4.55) that angelic acid combines with bromine, yielding tiglic aciddibromide as principal product, ; a small quantity of another sub-stance, which could not be obtained in a pure condition, beingpmduced a t the same time.Wislicenus and Puckert (Abstr., 1889, 587) found, on the otherhand, that tiglic acid dibromide is not produced hy the ncsion ofInrDmine on angelic acid: they obtained a substance with totallydifferent, properties, the investigation of which proved t o their mintisits complete dissimilarity from tiglic acid dibromide.Now, as the author had obtained 27 grams of pure tiglic aciddibromide from 15 grams of angelic acid, and had proved the identity-of the product with the substame obtained directly from tiglic acid,not only by a general, but also by w crystallographic, examination,and as, furthermore, his observations had been contirmed by Schmidt(Aiznalen, 208, 252), Wislicenus' results were received with gre it,astonishment, and the reinvestigation of the subject, was commenced.In the first place, a sample of the so-called angelic acid dibromide,prepared by Wislicenus and Puckert, was examined by the author,and found to be want,ing in all the properties of a pure chemicalcompound ; it seenjed to consist principally of tiglic acid dibromide,mixed, howevein, with various substances, amongst others calciumcompounds and resinous matters.The author then began various experiments 011 the action ofbromine on angelic acid.The acid employed melted a t 44", anti as i thad been kept for 1'2 years, it would seem tlhat angelic acid does not,become converted into tiglic acid on keeping, as is supposed bySchmidt. The acid was very carefully dried, and then distilled ; itboiled a t 185", and underwent no change into tiglic acid, either whenboiled or when distilled with stearn. Wislicenus and Piickert'sstatement that w r e angelic: acid is coni-erted into tiglic acid onboiling with water cannot therefore be confirnied. The pure angelicacid was treated with bromine in carbon bisulphide solution a t 0" i ndiffused daylight, moisture being carefully excluded ; several experi-ments were made under various conditions, in some cases t)he solutionof the acid being added t o the bromine solution, in others trhe processbeing reversed.In all t h o experiments, which are described in great detail, a larqequantity of tiglic acid dibromide was obtainec1,and the identity of theproduct with t h e dibromide prepared directly from tiglic acid wasproved, by direct con~parison as well as by a crystallographic examin-a tion.These results show that the statements puhlished by the authormore than 12 J a r s tigo are absolutely correct in eve1.J- detail ; it mayORGANIC CHEJIISTRY.41therefore, be coiisidered as proved, that when angelic acid is treatedwith bi-omine in carbon bisulphide solution at 0" in diffused daylight,it is almost completely converted into tiglic acid dibromtde in thecourBe of a few hours.A number of careful experiments were also made in order to in-vestigate the behaviour of angelic acid with bromin5 in absence ofsunlight ; it was found that, whatever the conditions, the principalproduct is always tiglic acid dibromide, hut thnt another substauw,which is not produced €rom tiglic acid under the same conditions, isalso formed in small quantities.Although, then, the formation oftiplic acid dibromide takes place quickly in presence of diffused s u n -light a t O", and the yield is almost quantitative, in the dark thereaction takes place only very slowly, even at the ordinary tempern-ture, and a larger quantity of a more readily scluble compound isproduced.The preseiice of this readily soluble compound has greatinfluence on the behaviour of the tiglic acid dibromide ; i t makes it,much more readily soluble in all ordinary solvents, retards its crystal-lisation, and causes it to deliquesce with water. The nature of thisbye-product, could noh be determined, but i t is probably an isomerideof tiglic acid dibromide ; the snbstance prepared by Wislicenus aiidPiickert evidently contains both these compounds.After referi-ing to several minor errors in the statements andresults published by Wislicenus, the author criticises Wislicenus'experiments on the action of bromine on malei'c acid, and points outt h t the coiiclusions drawn therefrom by Wislicenus are directlyopposed to the present theories.i n conclusion, the author protests against the way in whichWislicenus is nwustomcd to trust, to his memory alone in referring tothe literature of chemistry ; in rnauy cases, the author iind others aremade to st,ate and affirm in their papers, the refereuces to which areall given, just what Wislicenus hiniself believes a t the time, whereasthe actual Statements are sometimes the exact contrary and some-times do not appear at all in the articles referred to, but exist solelyin Wislicenus' imagination.F. S . K.Syntheses of Nitriles and of ,&Ketonic Ethers. By L.BOUVEAULT (Cowpi. rend., 111, 531-533) .--It has previously beenshown (Abstr., 1889, 841) that the products of the action of sodium onpropionitrile jn presence of ether contain the compoundNH:CE t.CMeNa.CN,and it follows that the mixed compound oht'ained by the action ofsochrn on the two nitriles R*CH,.CN and R'.CI)U' ( J .pyakt. Chem.['L], 39, 188, 230,245) will have the constitution NH:CR'.C:RNa.CN.If this derivative is treated with an alkyl iodide, as in the case oEpropionitrile, it will form the compound R'*C(NH)*CR"R.CN, whicliwill be converted by hydrochloiaic acid into a 6-ketonic nitrilcli'*CO*CR"R.CN. These nitriles can readily be converted into alkylsalts by dissolving them in the corresponding alcohol and saturatingthe solution with dry hydrogen chloride.Xethylic weth y7pr01)io111/7acc.tate, COEt-CHMe.COOMc~, boils at 185"42 ABSTRACTS OF CHEMICIAL PAPERS.arid is identical with Israel's met,hyl propionylpropionate* (dnnrrleir,23 I, 197) ; methyl di~mrtliylpro~ion,ylacettcte, COEt.Chfe,*COOMe, isa colourless liquid which has a camphoraceous odour and boils a t188-188.5" (corr.) under a pressure of 760 mtn.These changes me quite general, and all the /3-lcetonic alkyl saltscan he obtained from their nitriles.Met h y 1 me thy Ip ropiony 1 acetate shows powers of condensationsimila: to those of ethyl acetoncetixte ; it coritbines with aniline toform arnetEiylethyloxyqniiioliiie melt irig a t iL95", aiid insoluble iiiether ; water, methyl alcohol, and carbanilide are formed a t the sametime.The @-ketonic nitriles, when heated in sealed tubes with hydro-chloric acid, yield ketones.a reaction discovered by E. v. Meyer.The nitrile COR.CR'&".CN will yield the ketone CO R*CHR'R", andin bhis way7 all the ketones can be obtaiced in which the two atomsof carbon ;nit,ed to the cxrboriyl are not botl-1 tertiary.C. H. B.Syntheses with Ethyl Sodiocarbamate. By F. KRAFI' (BY.,23, 278%?78i) .-When ethyl car.bama,te is treated with fiuely-divided sodium i l l ethei-eal solution, it is converted into a white,ailiorphous sodium compound, NHNa-COOEt, which is very hygro-scopic, has an alka,line i.eactioii, and is reconverted by dilute acidsinto ethyl cat-bamste. The displacement of sodium by methyl doesnot take place very readily, it being necessary to beat the mixture ofethyl sudiocarhamate and methyl iodide diluted with ether, a t I l O " ,in a sealed tube.The product, after heparating the sodium iodide andevapoi ating the etlier, is fractioriated, and yields regenerated ethylcarbarxiate and ethyl methylcarbawlate, NHMe*COOEt, boiling at 1 70".Ethyl chlorocarbonate acts on the sodium compound snspeuded inether a t the ordinary temperature. After the reaction is over,suflicient water is added to dissolve the sodiam chloride formed, thesolution is extracted with ether, and the extract, after evaporation oCtlie ether, is fractionated. At 110", a solid substance commences toseparate, but a t 210--215" an oil passes over, leaving a solid residuewhich consists of cyanuric acid. On refractionating the oil, morecyanuric acid is obtained, but ttie greater portion passes over at 215',and solidities after a time to a crystdline mass closely resemblinq<:thy1 carbamate, and having the same riielting point of 50", but i tboils 35" higher, and does not volatilise on remaining in the exsiccator.Its mxilysis agrees with the formula ChH,,NO1, and it is therefore, asexpect e 2, ethi'! imidoilicadoa y late, N H (C 0 0 E L ) 2.H.G. C.Methyl Cyanosuccinate and Cyanotricarballylate. By L.B A ~ ~ T H E (Compt. rend., 111, 343--345).-Methyl sodiocjanacetate isprepared by the ixctiori of sodiiim methohide on methyl cyanacetate iitpresetice of excess of metliyl alcohol, the product being heated in awntev-bath for several hours with methyl rnoriochloracetate. Theliquid is then mixed with water, and the reddish oil which separatesis dissolved in ether, dried, aud distilled.'l'he fraction which boils a t 196-204' under R pressure of45 mm.is methijl cywosuccittatr, COOJ4e.CH;CH(CnT)*COOMe, aORUANIC CHEMISTRY. 43oily, colourless liquid, insoluble in water, but soluble in methyl andethyl alcohols and in alkalis. The fraction boiling at 215" under thesame pressure solidifies after some hours, and is purified by re-crystal I isation from methyl alcohol. It is methyZ cyaizotricics"bulZyZut~,C .V*C (CH,*COO Me),-COOMe, and forms white, prisma tic crystals1vhicl.i melt a t 46*5-47*5", and are soluble in ethyl and methyl alcoholsand in ether, but insoluble in water and alkalis. It is formed in thesitme manner as ethyl cyanotricarballglate (Abstr., 1888, p.937), andcan, in fact, be obtained by the direct action of methyl mono-chloracetate on methyl sodiocyanosuccinate. C. H. B.Ethyl Allylcyanosuccinate. By L. BARTHE (Coinpf. ?.end., 111,348--343).--20 grams of ethyl cyanosuccinate is mixed with asolution of 2.3 grams of sodium in 60 grams of alcohol, 16 gra>ms ofally1 iodide is added, and tjhe liquid is heated in a water-bath forabout 30 hours i r i an ampparatus with a reflux condenser. The product,alter separation of the alcohol by distillation, is extracted successivelywith water arid ether. The latter dissolves the ethyl allylcyano-succinate, which is obtaiiied as a colouyless, oily liquid boiling at'Lo?--~I(J" (coi-r.) under a pressure of 35 mm.The so-called Sulphite Liquor" and the Rotation ofGlyconic, Galactonic, and Rhamnonic Acids.By F. WELD,C. H. B.J. B. LINOSAP, W. SCHNELI,E, and B. 'YOLLENS (Be?.., 23, 2993-2993).-The so-called " sulphitr-liquor " obtained in the cellulosc works isa very slightly milky liquid, which, besides calcium sulphate andpotassium sulphide, contains much organic matter. On distillingthe liquid with sulphuric or hydrochloric acid i t yields furfur-aldehyde and fiirfuramide, showing che presence ( f pentoses (xylose).The quantity of the latter is small. If the liquid obtained afterhydyolysis with sulphuric acid he separated from gummy matters byprecipitation with alcohol, it yields, on treatment with phenylhydraz-i n e, considerable quantities of niannoseph eny lhy drazone.By theaction of nitric acid, the evaporated liquor yields rriacic acid, showingthe presence of galactan or galactose, and the presence of vanillin hasalso been shown hg the phluroglucinol reaction.The specific rotatory power of certain acids of the sugar group,and of their calciiim salts, has also been examined, with the followinqresults (see also Fischer, Absti.., 18'30: 1398) :-Gluconic acid.-Withcal(.ium gloccnate, [a],, = +7". Tf' this salt is dissolved in waterand a n equivalent, quantity of hjdrochloric acid, it shows, after10 minutes, a, specific rotatory power of +2--3", calculated as freegluconic acid, C6H,,O7 ; after 5 days, the rotation remains constant,[aJn = +9*8-10*4°. If the mixture of calcium glucoriate andhydrochloric acid is heated a t first for half an hour.at lC)O",[aID = +19", and this rotiltion is reduced to one half in two to threeweeks. Gnlactonic acid.-Caicium galact onate, and an equivalent ofhydrochloric acid, gave, a t first, [alD = -10*56", and after 2--3 weeks,[aID = -4G.82". After henting for half an hour on the water-hath,LaJn = --57.84", which, after r2maining for 14 days, sank to -53.36"Crystallised galactonic lactcne gave, a t first, [aIu = -58.29, wbic44 ABSTRhCTS OF CHEMICAL PAPERP.scarcely altered on being kept for a time. Rhnmnonic acid.-With greatclificulty, strontinm rhamnonate, (CsH,,06)2Sr + 7 or 7+H20, rmd anammonium salt were obtained in a crystalline condition. The former,when dissolved in hydrochloric acid, gave. at first, [aID = -7*67",and after 5-6 days, the constant number, [ a ] D = -2!3*21", and afterheating, -34*:30", which sank in 5-6 days to -;30.12".Rharrinoniclactone gave, immediat,ely after solution, the result [ a ] , = -34.26,calculated like the foregoing, for rhaninoriic acid, C6H,,06. In threedays the rot'atioii had scarcely altered. H. G. C.Constitution of Benzene and Naphthalene. By ,4. CLAUS(.7. pr. Chem [2], 42, 458--469).-A reply t9 the critkisms whichHamberger has recently pasked on Claus' formulz (compare thisvol., p. 1299). A. G. B.Substitution in Aromatic Hydrocarbons. By 0. S RP EK(Nonutsh., 11, 429-432).-With the object of obtaining parabromo-benzyl chloride, bromine (126 grams) was slowly added, in the dark,to a mixture of benzyl choride (100 grams) and iodine ( 5 grams).The solid product, after many recrystallisations from alcohol, meltedat 59", and coiisisted of a mixture of parabromobenzyl hrornide, whichmelts a t 61", with a small quantity of a compound containing chlorinein both the nucleus and tlhe side chain.A similar result was obtainedwhen chlorine acted on parabromotoluene in direct snnlight. Thecrystalliiie product obtained melted a t !i2", and consisted chiefly ofparabromobcnzyl bromido. The formation of this compound is easilyacci bunted for if one supposes that clilorobenzyl chloride is sitnultane-ously formed ; examination of oily bye-products points to such beingthe caw. G . T. M.Derivatives of Orthodibromobenzene. By P. SCHIFF (Monntsh.,11, 329-349) .-A more satisfactory method of obtaining orthodi-bromohenzene than those described by Riese (this Journal, 1873, 63j,and Korner (ibid., 18i6, i, 214), is as follows:-Bromobenzene isadded gradually to 6-7 times its weight of well-cooled nitric acid ofsp.gr. 1-53, and the resulting nitro-compounds crystallised fromalcohol, when the chief product, paranitrobromobenzene, me!ting at126-127", first separates (yield 80 per cenr. of tlieory). On heatingthis compound with the corresponding quantity of bromine and ferricchloride for 50 hours a t 85-90' (cornpare Scheufelen, Aostr., 1886,340 j, para-orthonitrodibromobenzene, niel ting a t 58-59' (yield90 per cent. of theory), is obtaiced, and this, on elimination of tbenitro-group, is converted into orthodib~~omobeazene, which, when pure,boils at 224", solidifies a t - 5 O , and melts at -1 O (compare Meger andWursfer, %his Journal, 1874, 757, i 5 9 j .Pure metadibromobenzene,after being frozen in a mixture of solid carbonic anhydride and ether,melts a t 1-9".When dibromonitrobenzene is treated with ten times its weight ofconcentmted nitric acid, of sp. gr. 1-53, and t h e mixtnre is warmedin a water-bath f o r 12 hours, two dibrcmodinitrobenzenes (a- and /3-ORGANlC CHEAlISTEtT. 43are formed, and may be readily separated by fractional crjstallisationfrom acetic acid.a-Dib,.o?nodinitrobenz~ne is less soluble in acet,ic acid and i n nl(:oholthan t8he p-compound. It crystnllises from alcohol in rieedles meltinga t 114-115". On iaeduction with uiii and Iiydrochloric acid, i t is crm-1-erted into dibromodiamidobenzene, which crjstallises from dilutealcohol in needle8 melting, with decomposition, at 157".On treat-ment with alcoholic ammonia a t 110-120", i t gives a, dibromonitro-anilirie, crystallising from alcohol in orange-yellow needles me1 ting a t204--205", and this, by elimination of the amidogen group, is con-verted iiito the original nitrodibromobenzene, and seems to beidentical with the dibromonitraniline melting a t 202", obtained fromdibromaniline, [Br, : NH, = 1 : 2 : 41, by acetylation, nitration, andsubsequent elimination of the acetyl group ; a-dibromodinitrobenzenehas, consequently, the constitution (Brz : (NO?), = 1 : 2 : 4 : 51.p-Dibi-omodiniti*obenzene is very soluble in alvohol and in acetic acid,a n d crptdlises from the former in needles: and from the latter and fromcarbon bisulphide in small, rhombic plates [a : b : c.= 1 : 0.854 I. : 0.57001.O n treatment with alcoholic ammonia, it gives a dinitrobrumaniline,which crystallises froni alcoliol i n yellow needles melting a t 153" ;this is identical with the compound obtained by Leymann (Abstr.,1882, 1057) by the brominntion of metadinitmniliae [l : 3 : 41. Thecompound has, consequently, the constitution [Br, : (NO,), =On diazotising the dibromaniline above-mentioned, dibromophenol,[Ur, : OH = 1 : 2 : 41, which may be readily suhlinied, and crystal-lises from water in needles melting a t 79-80', is obta'ined.1 : 2 : 3 : 5 ] .G. T.M.Change of Propyl into Isopropyl in the Curnine Series. BJ-0. WIDMAK (Rer., 23, 3080 - 3O88).--;P~~~tr - ethyZpropyZbei/zer/e,C6H413tPra, prepared by liea ting a mixture of parabromopropyl-benzene and ethyl bromide with sodiiini, bolls a t 202-205" (corr.),and has a specific gravity of 0.867 at' 19'. It yields terephthalic acidas sole produce of oxidation with alkaline permaugnnate soln tion,\I hilst with dilute nitric acid, propylbenzoic acid, together with alittle ethylbenzoic acid, is formed.By the action of sulphuric acid on ethylpropylbenzene, a mixtureof two sulphonic acids is obtained: these are converted into sulphon-amides, and sepnrated by repeated cry stallisation from alcol~ol.1' cwa- et h ylpp1'opyl b e w e m - a-su 1ph muwid e,C,H,EtPPSO,NH, [Et : Pr : S = 1 : 4 : 61,crystallises from dilute alcohol, or from a mixture of benzene and livhtpc'troleum, in long, flat needles meltiiig a t 112-113" ; on oxidihtionwith chromic acid solution, it yields sulphonamidethyl benzoic acid,[Et : COOH : S = 1 : 4 : 6).P a r a - s t h ~ l ~ ~ r o ~ ~ ! ~ l b e n z e t i e - ~ - l - s z l l t , i ~ e , [Bt : Pr : S = 1 : 4 : 51, isdeposit2d in cubical crystnls which melt a t 108", and on oxidation,wive sulphonamideprop~lbenzoic acid.The oxidation of an ethyl46 ABSTRACTS OF CHEMICAL PAPERS.proup in the para-position does not, therefore, bring about the changeof piwpyl into isopropyl ; i n this respect the ethyl group resembles therro~)yl, isopropyi, and acetyl groups ; consequently, the rearrangrmentto isopropyl appears to take place exclusively in the paramethyld eriuat ives.J. B. T.Behaviour of Phenols and Hydroxy-acids towards the AlkaliHydrosulphides. By F. FUCHS (Monatsh., 11, 363--372).--Theaiithor has previously shown (Abstr , 1889, 496) t>hat the hydroxylicI drogen of hydroxr-acids and phenols, derived from aromatic 'ly tgdrocarbons, is not displaced by metal, on treatment with an alkalihydrosulphide. The h \ droxy-acids of the fatty series, such as malic,citrir., and tartaric acids, behave in a precisely similar way; tetra- andlwnta-metbylphloroglucinols decornpose hydrosuiphides as if theywere monobasic acids, an action which the presence of carbony1 groiipsmav possibly deteiinine ; on the other hand.tetra- and penta-ethyl-pbloroglucinols have no such action, although the substitutioii ofbrorniiie in 1 he /?-position brings abont, deconiposition of the hydro-sulphide. This difference in the behaviour of methyl and ethylderivatives appears to depend on the relative weights of themolecules.Ortho- and meta-nitrophenols have no action on sodium hydro-sulphide, whilst paranitrophenol decomposes it. The sutstitntion ofa nitro-group in the ortho- or meta-position in a phenol seems,therefore, not to affect the replaceabilitv of the hydroxylic hydrogen,whilst, its substitution in the para-position does. This view is con-firmed by the beh.aviour of nitroeugenol, in which the nitro-group isort ho- to the hydroxyl.Tiibromoresorcinol behaves as a nionobasic acid, only one ofthe hydroxylic hydrogen atoms beiiig displaced by soditim frorn theIiydro~ulphide. Wben one hydroxjl group is displaced by ethoxyl.nosuch substitution occurs. The action of some other nitro- andhalogen-substit uted phenols on Fodiuin hydrosulphide has been deter-niined, and the msults depend both on the number and the position ofthe substituted groups, although no general conclusions can yet bedrawn. G. T. M.Constitution of Thymol and Cymene Derivatives. By G.MAZZARA (Chzzetta, 20, 140-149) .-3.3awitrolthymyl benzoate,CBHMePr(N02)2.0Bz [I : 4 I 2 : 6 : 31,prepared by heating the coirreaponding dinitrothymol with benzoicchloride for about two hours a t 160" to 180", crystallises from alcoliol illyellow, rhornbohedid plates, melts a t 1 2 7-128", and dissolves readilyin light petroleum and benzene.MeNH, /'\ NArnidob emarniclot hymol, I l o / %I%, prepared bF reducing\/ HPORGANIC OH EMISTRY.47tile preceding compound with tin and hydrochlwic acid, crystallisesfrom alcohol in yellow plates and from light petroleiim in prisms,melts at 106-108", and is tinged faintly violet by light. It is notaltered b7 boiling with hpdrochlorjc acid or with dilute (20 per cent.)snlphul-ic acid. The platinochloride crystallises from alcohol in yellowneedles which decompose at! 215".MeNEIBz /'Renzo~laml:dobe~eamidoth~n~ol, I I N\)CPh, prepared by"\/ OPrheat,ing a solution of the preceding cornpound i n benzene with benzoicchloride, crystallises from alcohol in bulky, wlrite needles and meltsa t 174--17;".It may be boiled with hydrochloric or dilute sulph-uric w i d without change.The formation of the above benzenjlamido-derivatives is i naccordmre with the hypothesis that in dinitrothynol one of thenitro-groups is in the ortho position with respect to t h e hodroxyl.The anthor i s n l h o investigating the actlion of acrtic anliydride ont h e corresponding a m i d d e r i v a t i v e with the view of obtaining aflirther confirmat,ion of this constitution by the formation of a nethen y 1 d e rivnt i ve.pre-pared by heatinq dinitrotjhFmol with acetic chloride, crystallises from:ilcohol in prismatic tufts, melts at 85", and dissolves i n light petro-leum. ether, and chloroform. The author considei*s t h a t the di-nitrocymene melting at 54", previously described (Abstr., 1890, 753).haq the constitution [Me : NO, : Pr : NO, = 1 : 2 : 4 : 61 and that theliquid and solid dinitrobromocymenes prepared by Fileti arid Crosa(Abstr., 1889, 493) hare respectively the constitutionsU;nitrothymyl aretafe.C,HMePr(NO,),.OAc [l : 4 : 2 : 6 : 31,[Me: Br: Pr :NO,: KO2 = 1 : 2 : 4:5: 6 and = 1 : 2 : 4: 5 : 31.S . H. A. A.Constitution of Thymoquinone and Carvacrol Derivatives.By G. MAZZAKB (Gnzzetta, 20, 183--19O).--l,initrocn/.rtaci"ol,C,HMePr( NO,),.OH [ 1 : 4 : 3 : 5 : 21 ,prepared by Carstanjen (Abstr., 1877, 614), erystallises from lightpetroleum in tufts of yellowish needles which turn red even indiffused light, and melt a t 11 7".The.LeiixcyZ derivative, C6HMcPr(NOJ2-OBz [l : 4 : 3 : 5 : 21, preparedlike t8he corresponding thymol derivative, crystalliscs from alcohol inlarge, Fellow, p r i s m ~ t i c plates which melt at 98-100", and turn brownwhen exposed too the light'.DiarnidocaruacwL C6HMePr(?TH2).2-OH, is prepared by heatingdinitrocarracrol (15 grams) for aboot an hoar, with tin (47 grams)aitd fuming hydrochloric acid (145 grams). The hydmchlo&e formswhite plates which are coloured violet by exposure to light; the baseis a red powder which softens at about 190".It, dissolves in dilute ~lcohol.Nitroarnidocurvacrol benzoate,C6H&tePr(NO2) (NH,)*OBz [1:4 : 3 : 3 : 2348 ABSTRACTS OF CHEMICAL PAPERS.is prepared by heating dinitrocarvacrol benzoate (10 grams) forabout an hour with tin (22 grams) and fuming hydrochloric acid(70 grams).It crystallises in rose-coloured scales which have ametallic lustre. I h forms R white sublimate a t 200". softens at, 230",and melts a t 280-283". The platinocldoride, (C17H,~N204),,H2PtCl,,crystallises in yellow needles which lose part of their acid at 30-40".The physical propert>ies of this cornpound and the absence of atiynitrobenzenyl derivative, together with the formation of a benzuyl-derivative (not yet described) with benzoic chloride, indicate that theIiitro-grnup in this compound is in the urtho-posit#ion with yegard tothc liydrox~l.MePrdinitrocnrvacrol benzoate with t i n and hydrochloric acid for 5 hours.It crystallises from alcohol in violet prisms which soften a t 125" andmelt a t 130-132O.The formation of a benzeriyl derivative fromdinitrocnrvacrol benzoate arid of a hydroxythymoquinone by theoxidation of the aruido-derivative shows that in dinitrocarvocrol one ofthe nitro-groups is in the ortho-pnsition and the other in the pava-position with respect, to the hydroxyl.Phenylazo- and phenyldisnzo-carvacrol (Abstr., 1885, 1 132), whichrespectively yield thymoyuinone and hydroxythymoquinone on oxida-tion, will accordingly have the constitntinns [Me : OH : Pr : N2Ph =I : 2 : 4 : 51 and [Me : OH : NzPh : Pr : NJ'h = 1 : 2 : 3 : 4 : 51.S. B. A. A.Action of Chloral on Resorcinol and of Aldehyde on Pyrogal-101. By H. CAUSSE (IjuZZ. SOC. Cliim., [ 3 ] , 3, 861-867).-Resorcinol(1 00 grams) and sodium hydrogen sulpliate (20 grams) are dissolvedi i i water ( 1 1iti.e) and c-hlural hydrate (50 grams) is added to themixture, which after some time deposits colourless, oily crystals ; ifwarmed a t loo", yellow crystals are deposited resnlting from thedehydration of the former.. The colourless cr;ystlals are insoluble illwater and in benzene, but dissolve in alcohol or ether, whilst theirsolutions in alkaline hydroxides exhibit. a remarkable fluorescence.At, 25d0, they become yellow, and decompose without fusion.With;wctic anhydride, this substance yields a crystalline diacetyl derivative,whic'h melts a t 2 5 2 O with decomposition. Analysis gives the formula,CI4Hl2Os, and the satne compound resulting from the heating at 103"of equal parts of resorcinol and of glyoxylic acid points to its havingthe constitution COOH-CH (O*CsH,.0B)2.P~rogalfol (50 grams), sulphuric acid (5 grams), aIdehyde (25 C.C.o f a 10 per cent.solution) and watw, (500 grams) are heated at 100"f o r several hours and successive quantities of 10 per. cent. sulphiiricacid are added, when crystals separate out, and by the addition ofmore aldehyde and acid further crops are obtainable. Froni themass of crystals. the colvurlcss a r e alone separatd and recrystallisedf'mm alc,)hol, separating as smibll, colourless needles having the corn-position CeHsOs, containing 2 niols. HJI, which are successively losORGANIC CHEMISTRY. 4 9at 39' and 80". The substance is insoluhle in water, benzene, andchloroform, slightly soluble in alcohol and ether, but is dissolvedemily by alkaline hydroxides.At 260", i t decomposes, and yieldspvrogallol a t a slightly elevated temperature. It has the constitutionCHMe:02'CGHJ.0H ; with acelic anhydride, i t forms a monacetylderivative whicli crjstallises in white prisms which melt a t 280".Formation of Ethereal Salts and Amides in presence ofWater and Alkali. By 0. HINSHEKG (Bey.. 23, 2962-2965).-1thas been shovn by Bnnmann and his pupils (Abstr.. 18S7, 2%;lbX8, 1296 ; 1889, 370) that benzoiu chloride may be used for detect-ing the hydroxyl-, aniido-, and imido-groups in certain cornpouridsby acting on them wit,h that reagent in aqueous solution in presenceof alkali. This reaction was, however, first employed for the pre-paration of benzoyl compounds by Schotten (Abstr., 1885, 176).The author has further examined the action of other acid chloridesaiid of acetic anhydride under similar conditions, and finds that cum-plete acetylatiori of the primary and secondary amido-bases and the:irotnatic diamido-bases readily takes place on shaking them withacFtic anhydride and iced water.Pheaylace tic chloride acts onnionhydric alcohols and pheno's, and primary and sccwrldary amido-hases belonging to both the fatty and arama,tic groups in the samemanner as benzoic chloride. Iliamines m d polyvalent alcohols,such as glucose, can also be readily converted into phenylaceticderivatives.Phenylsulphonic chloride is wi h i i t action on tertiary amines, butacts on botlh secondary and primary amines very readily.Thefk)riiler yield solid or viscous products. insoluble in acids and alkalis,whilst the latter form sulphonarnides which are readily soluble inalkalis. This reaction may therefore be employed to asvcrtainwhether an amido-compound belorigs to the primary, secondary, ortertiary series, and also forms a ready method for the separation of amixture of members of the three classes.I f the tertiary Lase is vo1;itile with sheam, the mixture of basesafter treatment with phenylsulphonic chloride and alkali and appt ox-imiite neutralisation, may be distilled in R current of steam. Thesulphonamide of the secondary compound then remains as an in-soluble precipitate in the residue, and may be filtered off, and the1)rimary cornpound obtained from the filtrate by precipitation withhydrochloric ticid.If the t e r t i a r j base is not volatile with steam,the mixture is extracted with ether and the tertiary base separatedfrom the sulphonamide of the secondary base by shaking the etherealsolution with dilute hpdrochloric acid. The sulphonamide of theprimary base is obtained bg precipitating with hydrochloric acid theirqueous solution reiirairiing after the extraction with ether. To recon-r e r t the sulphonamides into the bases, they are heated with hydro-chloric acid in a sealed tube a t 160".The reaction with phenj lsulphonic cliloride is not given by nmidocompounds whicli already contain an acid o r other strongly negativeradicle, such as the acid amides and halogen and nitro-derivatives ofthe arnido-bases.On the other hand, complicated substance; such asT. G. N.VOL. r,x. 50 ABSTRACTS OF CHEMICAL PAPER!!.fibrin and peptone yield white products, soluble in alkalis, whichliztve, however, not a t present been obtained in the crystalline form.:EX. G. C.Polemical. By 0. RKBGFFBT (Gazzettn, 20, 122-1 23) .-A con-troversial note in 1-efwence t o the papers piiblished by A. BischoE(Be?., 22, 1774) R.tid A . 13ischoff arid A. Hausdorfer (&id., 1795) ont h e action of aniline on chloracetic acid. S. B. A. A.The Condensation Products of Aromatic Aldehydes withAromatic Amines. Ry A. HAXTZSCH (Be?-., 23, 2773-2776).-Thehe condensation products, c-f which t h e best known i s benzylidine-aniline, CHPh:NPh, resenihle the oximes, innsniuch as thc>y contain acarbon and a nitrogen atom united togrt,lier by double linkage, and itseemed, therefore, important to determine, if possible, wliether thesealso exist in isomeric forms.An atternpt was first made to convertben7ylidine-aniline into an isomeric compound by treating it withbromine, under which conditions the plane symmetrical tolane di-bromide is converted into the axial symmetrical isomeride. The reactionwas c-arricd oiit, i n carbon bisulphide solutiou, and a yellow. amorphoiiscompouud obtained, which was shown by analysis to he hwzylidi?ze-anilin: dib?-oj/jide, C,,H,,NBr,. J t melts with decomposition at nbont142", is insoluble in wilter and ethor, but dissolves in cold alcohol.It is very readily decompnsed, but, instead of re-forming benzylidine-aniline, it splits u p into lserizaldehyde and parabrrmnniline.This takcsplace most readily on heating with ppidine. Wit,h reducing agents,i t loser; hydrogen bromide and n c t bromine, and is converted bysodium hydrogen siilphite into t,he additive product, 2C,H,*CHO +2C6HJBr-NH, + SO,. corresponding with the aniline compound de-scribed by Sohiff (Abstr., 1811. 304).Beiizylidine-aniline also yields a di-iodide. CI3Hl1EI.?, ohtained bymixing the fo~qiner n i t h iodine in benzene solution. It forms well-developed, dark brown needles, which melt a t 110" with decaoni position,do not yield iodaniline 011 heating with pyridine, and on reduction1-e-form benzylidine-auiline.No isonieride of the latter can, therefore,be obtained i n this marinerAttempts were also macic t o obtain isomeric condensation productsfrom substituted benzaldehydes and substituted aniliues, but withoutsuccess. H. G. C.Orthohydroxybenzylamine. By F. TIEMANN (Eel.., 23,3016-3018 ; cornpaw Goldsrlimidt and Ern+ Ahstr., 1890,141 I).-SaZicyZ-?netirhyl7rcrzobenzoic acid, OH.CsH,*C~:N*LlH.C~H~*COOH [OH : CH =1 : 2 ; NH : COOH = 1 : 31, i s prepared frorn salicylaldehyde andmetahSdrazInebeiizoic acid ; . it, crystallises from dilute alcohol inneedles, melts a t 195", and is insoluble in water. On treatment withzinc-(lust and dilute sulphui.ic acid, ol.tholrydrox!jbenzylanzine,OH-C6H4*CH2-NH2, and metamidobenzoic acid are formed ; they maybe separated by adding a slight excess of sodium carbonate to t h eacid solution, and ext,rncting with ether ; after evaporation, theresidual amine is puri6etl by dipsolving it in benzene, and precipitatingwith lightl petroleum ; light, yellow crystals separate, which melt a0 RGANlC CHEMISTRY.51l25", and sublime at a much lower temperatnre. It is soluble inwater, alcohol, ether, benzene, and alkalis, and gives a deep violet-blue coloiir with ferric chloride. Characteristic salts are obtained beytreatment with acids. The o x d a t e crystallises in lustrous, whiteplates. The arnine may also be prepared by the reduction of salicylicoxime with sodium amalgain in dilute sulphuric acid solution.Possibility of Existence of an Asymmetrical NitrogenAtom." By F.KriAFr (Bey., 23, 2780-2i81.).-Aacording to thehypothesis of Hantzscli aiid Werner, i h is possible that nitrogen com-pounds of the genera1 formula NXYZ may exist, in two opticallyisomeric. forms, and the author has, therefore, investigated derivativesof ammonia, hydrazine, and hydroxylamine, with a view to obtainings uvh i someirides.For the ammonia derivative, ethylbeneylamine, NHEt*CH,Ph, waschosen, as it yields a crystalline tartrate. It was prepared by heatingethylamine with benzyl cliloride and a little alcohol i n a s m i e d t u h ea t 110", and forms a colourless oil which has an ammoniacnl odour,and boils a t 194" (corr.). Its pZatinochZor;de, (CqH,,N),,H,PtC1,,crystallises in prisms. I n addition to the seconrlary base, a quantityof rtl/yZil,ibe7izuZnmin~, NEt(CH,Ph)?, is also obtained ; i t is anoily liquid boiling at, W6", whose platinochloiicle, (C,,H,,N),,H,PtCl,,i R a pale yellow, amorphous precipitate. The attempt to separateethyl heiizjlamine tartrate into two isomerides both by addition ofconiine tartrate and by fi.actioiia1 crystallisation, was without success.Negative results were also obtained in the case of paratoljlhydrazinetartriite. T'lie conclusion cannot., however, be drawn from these facatsthat optical isomerides of these compounds d o not exist, for thet;Lrtrate method is not always successful even with coinpoiinds con-taining ail asymmetrical carbon atom.Thus, the autbor finds that,a-phenyletlrylnrriine, CHMe*Ph.NH,, obtained by the reduct ion ofacetophenonoxime, cannot be split up into its optical isomerides bythis met hod.Finnlly, it is shown that both benzilenximes, on reduction, yieldone and the same di phenylh y droxyeth y l amin e, NH,.CHP h*CHPh*OH,previously obtained from the a-monoxime by Polonowskn (Sbstr.,1887, 492).H. G. C.J. B. T.Action of Amines of the Benzene Series and of Phenyl-hydrazine on p-Ketonic Nitriles. By L. BOUVEAULT (Compt. veazd.,111, 572-~74).-Meth~lpropion~lacetorlitrile combines with ortho-toluidirie to form ;L well crystallised compound, which melts at 125",and dissolves in alcohol, but is insoluble in ether 0:' water. Withp-nrtphthylarnine, tho nitrile yields a compound which crystallises inneedles melting a t 121", arld dissolves in benzene, but is almostinsoluble in ether.Mesitline jields a similar product melting a t114-115". Methylaniline does not; combine with r~iethylpropio~iyl-acetonitrile, but, 011 the other hand, tlie hicher homologue of thelatter combines readily with ortliotoluidine, forniirig a liquid boilingaf; 266", but analogous to the products already described. Fromthese results, the author concludes that the aniline derivative has thee 52 ABSTRACTS OF CHEMLCAL PAPERS.constitution PhN:CF:t.CHl\iIe*CN, and he calls it pheitylimidoi,iet7zyZ-propionylucetonifrile. The reaction is general, and the nitrilesR-CO-CR' R"*CN yield derivatives of the formula R"'N:C R*CR'R"*CN.The action of plienylh-j-dt.azine depends on the constitntion ofthe nitrile; if the latter belongs to the type R-CO-CR'R''.CN, ahydrazone is foriiied, NkIl'h*N:CR.CR'R''.C~, but if it belongs to thetaype R.CO.CHR'.CN, R derivative of pyrazole is obtained.Possiblyin the secoiid case tbere i s intermediate forniation of n hydrazone.Methyl propionylacetonitrile yields p l ~ e i z y l e f h ~ ~ l ~ n e t h y l u ~ a ~ ~ ~ p ~ L 1 : 3 : 4 : 5 1, wliich crystallises in large,colourless, hexagonal prismsniclltiug a t 81", and hoilinq a t 330" wittiout decomposition. T t is verysolnlle in most of the neutral solvents, but not readily in benzene oryetrolentn. Tt is a stronger bnse than the preceding compounds, andits acetate is only partially deconiposcd by water. When heatedwith llydrochioric acid in sealed tubes a t 120", the base undergoesno change.With sodium nitrite and hydrochloric acid, it yields ayellow diazo-derivative, whicli, when boiled with alcohol, yields i hephenylethy lmethylpyraxole previously obtzlined by Claisen :I ndNeyerowitz. If water is used instead of alcohol, the correspondinghydroxFpj-razole is obtained, melthg a t 104". The diazo-derivativeforms crystallisa ble colouring matters with phenols and amines.C. H. B.Carbonylorthamidophenol and Thiocarborthamidophenol.By 8. CHELMICKI (c7. pr. Chem. [a], 42, 440-445 ; compare Abstr.,1887, 477).-When carbon~lorthamidophenol is heated with aniline in;t sealed tube a t .200--2!0", arid the product treated with sulphuricacid, decoloriserl by animal charcoal, and crystallised from alcoliol,white, brittle needles of the formula C,,Hl,N,O are obtained.Thisnew substaiice mel's, with decompohition, a t $noo, and dissolves inmost solvents exrept water ; strong hydrochloric acid a t 160" decom-poses i t into ortiiatriidophenol hydrochloride, aniline hydrochloride,a n d carbonic anhydride ; chloride of lime converts it, i n acetic acidsolution, into a chloro-delivatire, C1,HI8CI2N20, melting a t 276O. Thissu bstaiice is isomeric with Kalck ho fT 's anili docarbamido phenol (,A bstr.,1883, 1 l l O ) , :md must therefore be C6H,<E:>C:NPh.Nit,.occirbonylorthanziclophenol, [NH : 0 : NO, = 1 : 2 : 41, crystal-lises in long, yellow needles melting a t 240-241" (uiicorr. ; Bender'snitrt-L11tiydro-orthamidophenyl carbonate melts at 256", Abstr., 1887,38). When this compound is trealcd with potash, it is convertedinto nitrocatechol, [OH : OH : NOz = 1 : 2 : 411, melting a t 170"(168".according to Weselsky and Beiiedikt, Abscr., 1878, 575).OH.C6H4*NH*C SON H-C3H3,is obtained by mixing ally1 ibothiocyanate (1 mol.) with orthamido-phenol suspended in alcohol, and leaving the mixture a t rest for sometirile. It foriris white crystals whicii melt a t 99', and are more orless soluble in all the usual solvents. When i t is heated with hydro-chloric wid iit 130". it is converted into thiocarborthamidophenol.Thiocarborthainidophenol evolves Iiydrogen sulphide when heatedabove its melting point.; with awmonia act 'LOO", i t is decomposed intocarbaiu\dophcnol, carbonic ntihydr.de, arid ammonium sulphide. WlieuOi*th ohydroxypht ngllr l l y lt hiocarbwmideORGAN CC CH EN ZSTHT.53an alcoliolic solution of iodine is added t o thiocarborthaniido~~henoldissolved in sodiiim hydroxide as long as t h e iodine is decolorised,Y crystals of the bisiilphide S2(C<b>CtiH,), (Abstr., 1887, 477) areformed; this snbstance melts at 110", and dissolves in most solvents.A. G. 13.Derivatives of Carbonylorthamidophenol and of Thiocarb-orthamidophenol. By P. SKIDEL ( J . p. (Ihrm. [ a ] , 42,445--4.57).-KalckhoWs anilidocai*bamidopheiiol is more easily obtained thanChelmicki's compound (preceding abstract) ; this i u evidence th;ttcaa;bonylorthamidopheiiol is C,H,<- o>CO, for the doubly-liiikecloxygen atom might, be expected to be more difficnlt to displacethan the group -SW.T'he ethyl compound, C,H,<"T>CO, - can-not be made to react with anilirie. The crystals of carbonylortli-amidophenol 50011 lose their lustre in air, being changed to stnallneedles ; the author sugg i s t s that the unstable crystals areC6B4<;>C*OH,NHNH and the stable crystals, C,H,<-O>CO. The crystals of thiocnrb-ortliamidopheuol do not change, aild this is in accord with the generalbelief that the stable form of this compound is C,H,<O>C*SH, aformula supported by t h e fact that by trefitrnent of orthamidophenolv i t h thiocarbonyl chloride, the same thiocarborthamidophenol isobtained as that obtaiiied by the action of ca14)on bisulphicle oncarbonylortha midop henol.By the action of ethylorthamidophenol (ni.p. 107.5", not 167.5" asqiven by Fiirster, Abstr., 1880, 464) on thiocarborryl chloride: a thio-;.ar.bon!,Zethilanzid~~l~enoZ is obtained x h i c h melts a t 112", and boilsundeconiposed above 300" ; i t is different froin Chelmivki's ethylderivative (Abstr., 1887, 477). This compound is deooinpooed bystrong hydrochloric acid at! 170" into ethylorthsrmidophenolcarboiricanhydride and hydrogen sulphide, showing t h a t its constitutioii isNEt C,H,<-O>CS. By heating this derivative w i t h aniline and leadoxide, an anilide is, with some difficulty, obtained free from sulphurnnci homologous with Chelmicki's anilide (previous abstract) ; t h edifficulty with which it is obtained confirms the double linking of thesulphur.to the carbon and, therefore, t h c above formula.'I'o obtain niethSlortIiamidopheno1, orthainidophenetoii was inethyl -ated with methyl iodide in the cold, by which means the hydrioditlesof me th j - I o r t h m i do phenetoi'l, dime t h 1 I orthainidophene to'il, and or tli-a rn i do p h ene toil, and mnidophenetoi It?-imet h y lammonium iodide wereobtained. The last-mentioned crystallises in nacreous, violel,-tintedleaflets, freely soluble in hot water. The niixture of t h e throemet,hylorthamidophenetoils waA heated with strong hydrochloric acidat 1 iO", ttiicl t I ~e iiiixed nie th~lortl~itl~li~c,plrenuls thus o b h i i d wereT54 ABSTRACTS OF CHHXICAL PAPERS;.treated with thiocarbonyl chloride.This treatment' yields fhiocarh-o ~ a y l ~ i a e t h y l o r t h ~ ~ i z ~ ~ o ~ h e ~ z o l in colourless needles which melt a t 128",and boil uiidecomposed above 300" ; stilong hydrochloric acid at l i 0 "decomposes it into methylortharnidophenol, carbonic anhydride, a dhydrogen sulphide, 50 that its constitution is similar to that of thio-carbonylethylorttiamidophenol (see above).Methylorthanlidophenol crystallises i n colourless leaflets whiclisoon oxidise and become brown in air ; it melts with decompositiotiat SO".C~cyboi.tha?izido(phennZ chloyide, C6H4<E>CCl, is obtained whentliic )carborthamidophenol and phosphoyic chloride are mixed togetherand the product distilled ; thiophosphorgl chloride passes over belowl3Oo, and t h e portion t h a t distils between 13U" and 205" separatessfter a time into crystals and a n oil ; the crystals were not investi-gated.The oil is carbol.ttiarriidopheno1 chloride ; it boils a t 201-202".solidifies in a freezing mixture, and mtilts a t 7" ; i t is a feeble baseforming a we!l- crrstallised ni tml e and hydrochloride ; i t is decorrr-pnsed hj- w;Lter into cnrborthamidoplienol and hydrochloric acid.With phenol, it yields two cottipoiinds, one of mliich is a cai*bo~th-ai~iclophei~id pheny 1 etkey-, C,H,<~>C.OPIi. melting a t 56" andboiling a,t 310°, whilst the other melts a t 190" and boils at a muchhigher temperature. With aniline, ca~borthamidophenol chlorideyields Kalckhoff's anilide. Carborthamidopl~ei~ol chloride is alsop 1'0 d u ce d w h en met h y 1 and e t h y 1 t hioc arb( my 1 o 1- t 11 am i do p he ri 01 s areheated with phosphoric chloride.A. G. B.Preparation of Anhydrous Diazo-salts. By E. Kso EVKPI'AGRL(Ber., 23, 2994-29!18) .-Up to the preaent time very few-diazo-saltshave been obtained i n the arihjdrous condition, the most, irnpui-tantexceptions being diazohenzene sulphate and nitrate. The authorfinds thatl all the salts may be readily prepared in t h e anhydrons con-dition by treating the amido-compound i n acid alcoholic solution withamyl nitt ite. To prepare diaxobenzene sulphate by this method,15 grams of aniline is dissolved in 9-10 parts of absolute, or- at least95 per ctnt. alcohol, and 20 grams of concentrated sulphuric acidcarefullj added ; aniline sulphate separates a t tirst, but redissol\-es oiladding the reinaincler of the acid.When cold, 20 grams of amylnitiite itre added, and t h e mixture well c.?oled, ice being pre-ferably employed in the preparation of large quantities. After10-15 minutes, diazobenzene siilphate usually separates in beautifulneedles, the whole mass solidifying tr, a crystaliine magma, which, onfiltering and ~ a f i b i n g with alcohol and ether, yields the cL)mpouiid inail almost pure condition. If t h e sulphate does not separate after10-15 ininiites, t h e addition of a few drops of ether causes animmediate crystallisation, and a further quantity of t h e salt may beobtained by adding ether t o the mother liquoi.. The diazobenzenesnlpliate t h u s obtained has all the properties assigned f o i t by Griess,and is tnoi-e reatlily 1)repnred in this manner thrtn bj- his method.Diazobeiizene iiittate is most reildi 1)- pi*elmred by adding wt trcORGANIC CHEMISTRY.5 f5more than the theot.eticil.1 quantitg of amyl nitr:te to a cold saturatedalcoholic solution of a ~ i l i n e nitrate containing a little free nitric acid,cooling well with ice. On the addition of a small quantity of ether,diazobenzene nitrate separates in beautiful needles, which explode,when dry, very v i o l ( d y , either on heating or by percussion.Diazobenzene chloride, which h a s hitherto notl been obtained in thesolid condition, is easily prepared in a similar. manner to the nitrate ;very cai$’ul cooling is necessary on adding the amyl nitrite, as thediiizotisation of aniline chloride proceeds very rapidly. After a sho1.ttime, the salt separates in almost colourless needles, which are col-lected, washed with a little alcohol and ether, and dried over sulphuricacid in a vacuum.The yield is almost quantitative ; tjhe determina-tion of chlorine and nitrogen gave nunibem agreeing closely with tlieformula C,H,*N,Cl. Diazobeiizene chloride decomposes on heatingwith a slight explosion, but only gives a slight detonation bypercussion. It is soluble in alcohol, but insoluble in ether. benzene,aud light petroleum ; water dissolves i t with great aviditv, and itdeliquesces in moist air, undergoing considerable decomposition, b u tis fairly stable in dry air, especially in the dark.‘Yhe following diazo-compounds have also been obtained in theanhydrous condition by this method :-The diazo-sidphates of ortho-t,ol uidine, paratoluidine, paraphen e tidiii e, pitrani sidine, ai i d metarii ty-aniline ; tlte ciiazo-nitmtes of ortho- a n d lmra-ttoluidine ; the dirczo-chlor.ides of pard,toluidine, paraphenetidiue, atid paranisidine.H.G. C.Action of Alkalis on Acid Salts of Diazobenzene : EthylDiazobenxoate. By T. Cumus (Ber., 23, 303:3--30.36).-B5heating diazvbenzene sulphste wit ti th:: calculated quantity OF bariumliycl~*oxide and extracting with etter, a very volatile, feebly basiccompound is obtained whicii is volatile with steam, melts a t -3”,N Itd bas an odour resemblirig that of rose water; a1 though no evolu-tion of nitrogen could be detected, ancLlysis sliows that only 2 atomsof ititrogen are combined with 3 benzene nuclei.A correspondirtgcompound may bs prepar\d in tlie same manner from ethyl meta-cliazoberizoate sulphate. No hydrazine could be detected in themot her liquors, and only in one experiment, with duminium aridalkalis, was any formed by the reductiou of the compounci it1 eitheracid o r alkaliue solntions. Attempts to prepare tliazobenzene, bythe action of silver nitrite on di-y aniline hydrochloride dissolved insome indifferent medium, were urisuccessf ul, diazosmidobenzenebeing the sole product, and, in a similar mariner, ethyl metamido-benzoate yields ethyl diazoamidobenzoats. Diazoamidobenzene maybe prepared by mixing very dilate, cold, aqueous solutions of anilinehydrochloride and sodium nitrite ; after washing with cold water, theproduct is quite pure.The potassium and silver salts of diazo-benzene, prepared according to the met‘lod described by Griess, werefound on analysis to coritaiii only two-thirds the tlieoretical quantityof nitrogen, the proportion being 6 rttonis of earl1011 to I of nitrogen.The quantity o f nietul present agreed closely with the theory. Theauthor is unable to assign any formula, t o these compounds.J . B. T5 6 ABSTRACTS OF CHE3IIOAL PAPERS.Hydrogen Nitride (Azoimide). By T. CLTRTIUS (Ber., 23,:312:?-3O33) .-Hpdi.oyeu m'tridp, q>NH, is formed, under certain Nconditions, by the action of sodium nitrite on hydrazine hydro-chloride: the reaction is strictly anallogous io the formatSon ofnitrogen from ammonium chloride am1 sodium nitrite. To obtain itin this manner is, however, R matter of considerahle difficulty, and itis best prepared from hkppzwy Zhydyaziiae in the manner describedbelow.Renzoy Zhydi-mine, NH,*NHBz, is formed on mixing molecular pro-portions of ethyl benzoy lgClycollate and hydrazine hydrate ; it crystal-lises from alcohol in large, lustrous plates, melts at 112", redncesalkaline copper solution in the cold.and dissolves in cold water, biitis only sparingly solohle in ether. It is not) changed on boiling bitliwater., but is Iiydrolysecl by the action of dilute alkalis. The samecompound is also obtained by the action of hydrazine hydrate onethyl benzoate.Benzo!/ZbenzaZh!ldl.nzinP, NHBz*N:CHPh, is prepared by addingbcnzaldc, hyde to beuzoylhydraziiie i n molecular proportion, and istleposited from alcohol in long, colourless crystals which melt at 203",are very spariiigly soluble in ether, and insoluble in water.S p metrical di benzo y ih y draz iiae, N HRz -N HBz , is obtained byboiling benzoylhydrazine ; it CI-ystallises from alcohol in silky needlesmelting at 255O, and is hydrolysed by treatment with acids oralkalis.On heating a cold aqueous solution of benzoylhydrazine with a nequal molecular proportion of sodium nitrite, and acidifying withihcetic acid, benzoylaxim ;de (7w)rroic nifyide), I I >NBz, scparate~ as anoily liquid which solidifies after some time.It crystallises in colour-less prisms which melt a t 29-30', explodes on heating, and is volatilewith steam. Ry treatment with alkalis, it is hydrolysed, but under-goes no change on boiling with acids ; i t reduces ammoniacd silversolution, but has iio action on alkaline copper solution; it has itpowerful odour resembling that of benzoic chloride, arid rapidlyattmks the skin.Hythceiriacetic acid (amidoglycocine), NH,.NH*CH,-COOH, is p1.c-pared by acting with ethyl benzoylglycollate (1 mol.) on hydrazinehydrate (2 mols.) ; the benzoylhydrazine which firht separates i qremoved, and after. some time the acetic acid derivative is depositedfrom the mother liquor ; it, is purified by repeated recrystallisatiun fromalcohol, and forms large, lnstrous platvs, tvliicli melt a t 93", and are in-soliible in ether. It has a sweet taste, gives with alkaline copper solutioiia deep violet colour, and, on warming, a precipitate of cnprous oxide.A red colour is yiwduced with neutral ferric chloride solution, airdammnniacal solution of silver is reduced in the cold.The compoundis hydrolysed by war.ming with scids or alkalis. Benzalhydmzine-acetic acid, CHPh:N.NH.CH,.COOH, is formed by the action ofbeuxaldehyde on the previous compound, and crystallises from alcoliolin silky, lustrous ueecl1c.s nielting a t 156.:)". Hzppui yEb~r~zLcZl~~dl.azi,~e,NORG-4NIC OHEMIS'L'RY. 57NHBz-C H2*CO-XH.XH,, is prepared by adding the calculat,ed quantityof hjtlrazine hydrate to an alcoholic solution of ethyl hippurate ; itcrystallises from alcohol in coluurlcss, lustrous needles which melt a t162.5, and are sparingly soluble in ether ; the yield is 90 per cent.nlknliiie copper solution, a green colour is produced, and after sometime reduction occurs.Hi23pu1.lllbe~iznlhycll.nzil2e,N HBz.CH,*CO-NH*N:CHPh,is formed by the action of berizaldehyde on the previous compound,and crystallises from alcohol in lustrous plates which melt a t 182'.Bg the action of acetic acid and sodium nitrite a t 0" on an aqueouqsolution of hippurylhydrazine, R compound is ohtained crystallisingfrom alcohol in colouy!ess needles which melt at, 98" ; i t is probablyeither nit,.u.sohippurllZl/~d~az~ne, NHBz-C H,*CO*N( N 0)-NH,, or nitmso-hydraxifie hippzoic acid, NO.NH.PU':CPh.P\TH.CH,~~O~~ ; by treat-ment with acids or alkalis, azoimide and hippuric acid are formed ; onboiling with water, an iudifferent gas is produced, together. with avery insoluble substance that has not yet been investigated. Theni troso-conipoiind readily dissolves in alkalis or ammonia, and thesolution exhibits a beautiful blue fluorescence.On adding silvernitrate to the ainmoniwcnl solution, a nhite, explosive, silver salt isprecipitated.Azoinzide may be obtained from benzoyl hydrazine or hydmzine-acetic acid, but is best prepared from the liippuryl compound bydissolving it in dilute soda, and decomposing the boiling solutionwith dilute sulphuric auid ; the azoimide distils over with the steam,and is passed into neutral silver nitrate solutioii, the precipitated silversalt is collected, washed wit)h water.dried at 60-70", and treated withdilute snlphuric acid. By repeatirig this procsss, a solution is obtainedcontaining 27 per cent. of azoimidr; on bringing the solution intocontact with ammonia, thick, white vapours of the ammonium saltare formed. Azoimide itself is a gas, having a part,icularly nauseousodour, and resembling hydrogen chloride in its general properties.It is very soluble in water, and on distillation a concentrated solutionpasses ovey ; the distillate gradually becomes weaker until equilibriumis established, a solution of defiilite strength being obtained whichboils constantly. A piece of blue litmus p,iper held orer the solutionturns iaed.Iron, zinc, copper, aluminium, and magnesium readilydissolve in a 7 per cent. solution of the gas, hydrogen beiiig evolved.Gold and silver also al)penr t o be attacked. Azoinide is liberated bytJic action of dilute sulphuric acid on aiiy of the salts ; with coneen-tianted sulph uric acid, the azoimide is itself decomposed, Bwiu 112nitride, K6Ba, is obtained in liishrous, hard crystals which are readilysoluble in water, and explode with a green flash on heating. Silvrrnitride, NdAg, crystallises in prisms which melt at about 250" wit11 aviolent explosion. J . B. T.r 7 1 he compound rednces amnioniacal silver solution in the cold ; withAction of Acid Chlorides on Acid Amides. By A. PICTET(Ber., 23, 301 1--3016).-l3enzsnilide and acetic chloride are formedon heating bciizoic clrloridt! nncl acetanilide a t 140" ; the same result i58 ABSTRACTS 0" CHILJZICAL PAPERF.obtained if the compounds are dissolved in toluene.This reaction isf o u n d to be a general one, both for the aromatic and fattyamides aridchlorides ; and the author explain., i t by assuming that an additivecompound is first formed which then decomposes, the radicles containingthe least number of carbon atoms combining with the chlorine, whilstthe higher carbon derivatives unite with the nmide complex. Theproduction of benzanilide, for example, mould be preceded by theformation of the hypothetical compound acetobenzanilide hydro-chloride, NHPhBzAcCI. These observations confirm those of Yaaland Otten (compare Abstr., 1890, 1415).J . B. T.Action of Sodium on Acid Amides. B y T. Gun-rrus (Ber., 23,3037-3041) .--Sodium benzamidr, CO€*h.NHNa or ONa-CPliNH, isprepared by boiling a benzene solution of henzamide with rather lessthan the calculated. quantity of sodium. The operation takes about 30hours, the precipitated salt is separated, treated repeatedly with ether inan extraction apparatus, and dried over sulphuric acid and quicklime.T t is a white, crystalliiie powder, insoluble in ether, chloroform, orbenzene ; it is very readily decomposed by water, or by dissolving inalcohol, but is not hygroscopic, and on distillation, yields benzene, sod:^,amimiiia, and a little benzonitrile.Sodium diberzxamide, NBz2Na, is obtained by dissolving dibenz-amide in xylene: and boiling the solution for 30 hours with a slightexcess of sodium ; no evolution of amnioiiia occurs ; the pi oduct c r ptallises trom ether iii small, white, Iiiotious plates whicli melt a t 150":ind resolidify on heating t o 230", and then do not melt at 300".Thesolid is readily soluble in I\ ater. On distillation, sorlium dibenz-amide yields only ti*aces 9f benzene ; it, is much more stable tlian thebenzarriide salt, and a recently prepared aqueous solution gives pre-cipitates with tlie salts of many of the heavy nietnls.By tlie action of sodium or1 acetamidti, consider,ible quantities ofammonia are evolved, aiid a viscid liqiiid separates, which after sometime becomes cr)stalline ; i t contains uitrogeii, and is possibly sodiurrhd iacetuwbide, NhczNa.By the action of iodine on finely divided sodium benzamide, 01'sodium dibeiizamide suspended in ether, additive compounds arel'ornied which readily wystallise, but do not show a constant composi-tion.Benzamide and iodine give the compound NH2BzI.NH,BzI (?),crjstallising in long, slender, olive-green prisms, which exhibit pleo-chr-oism arid melt at 110-118" without deconiposition. The com-pound is stable in air, and insoln1)lc in water, but readily dissolvesin glacial acetic acid; cn shaking with mercury, beiizamide andiuermric iodide are formed, whilst by distillation, or on boiling withwater or alcohol, it is decompose+ into iodine and benzarnide.Iodine and dibenzamide give a compound, NB4Bz,12, which crystal-lises in large, green prisms melting a t 118-180" ; i t is readily solublein chloroforrri, aiid resembles the preceding s:i bstnnce i n properties.Tribenaamide, NBz,, is formed together with dibenzamide by treatingberizauiide with exuess of benzoic chloride ; it is very sparingla-soluble iu alcohol, and is deposited ill s~lky, lustrous needles 15 hiclORGXSIC C HEMISTR T.59melt at 202", sublime without decomgosition, and Iield benzoic acidand ammonia when boiled with soda. J. B. 1'.20, 172-178) .-When benzonitrile is treated with concentratedsulphuric acid (sp. gr. = 1-82), an energetic reaction takes place, anda-toliconiide (phenylacetamide) is formed. An almost theoreticalyield is obtained if the proportion of the acid used contains thequant'iiy of water t,heoretically necessary for the transformation.ChZoralp7Let/ylncetnmide, prepared by heating a mixture of anhydrouschloral and pherylscetamide in molecular proportion for half an hour,crpst,allises from alcohol in minute, nacreous scales which melt at145", and dihsolve in alcohol arid in boiling ether and benzene..Phen!/lacet~i/lhydrazine, CH,Yh*CO*NH*N HPh. - Phenylacetamidereacts w itki phenylhydrazine like fvrniarnide, acetarni(le, &c., accord-ing to Justus' equation RCONH, + NH,*NHPh = R*CONH*NHPlr + NH,.A rnixtnre of the amide and phenyllrydrazine in molecularproportion is heated at 120-130" ; the product cry~tsllises fromid~~oI~01 in colourless scales which melt a t 175-176", and are mode-rately soluble i n Wiirm alcohol.When I~henylac.etamide is heated with aniline in molecular propor-tion, at, about 150", ammonia is evolved, and the product, after repeatedpyecipi tation with water and recryst~llisntion from alcohol, yieldsnac~'eoiis scales which melt a t 116-117", and are readily soluble inalcohol.This compound seems to be identical w i t h Holmann'sa-toluylanilide.Phen ylacetylparatoluididr? is obtained by heating the smide with para-toluidine a t 160--180" uiitil the evolution of animoiiia ceases. Itcrystallises in small, transparent tables whiuli melt at, 135-126", middissolve readily in alcohol and ether.(Re,;, 23, 2917--2919).-lt has been shown that imido-ethers &reformed by the action of hydiogcn chloride on a, mixt~ure of an alcoholand a nitrile. Further exper%nents have shown, however, that certainzyomatic nitriles, in which a carbon atom, in the ortho-positioniselatjive t'o the CN group.is linked to another carbon atom, are in-capable of forming iniido-ethers. It is also found t h a t orthodicyanideRonly form moninii2o-ethers. The first of these conclusions is formedfrom a study of ort hocyanot oluene, paracj anotoluene , pai*acyano-xylene, a-cyanonapl;tbalene, and mctacyano-xyleiie [Ble : Me : CN =1 : 3 : 41, whilst the second is deduced from the investigation ofmctadicyanotoluene [Me : CH : CN= 1 : 3 : 41.compare Abstr., 1890, 496) .-Ethyl berLsa?izidylcarbu?nate,NH:CPh*NH*COOE t,is prepai-ed by the action of aqueous soda and ethyl chlorocnrbonateon benzamidine hydrochloride ; it cr-j-strtllises from alcohol in thick,Ivhite prisms which melt at 57-48', and are almost insoluble in water.Ou heating the compound to about 150", decompositioii takes place,a-Toluamide and its Derivatives.By A. PURGOTTI (G'ozzetta,S. B. A . A.Conversion of Nitriles into Imido-ethers. By A. PINNERJ. B. T.Diphenyloxycyanidine. By A. PINKER (Bey., 23, 2919-2922 r;o ABSTRACTS OF GHENICAL PAPERS.alcohol and ethyl carbmnate are eliminated, and diphenyloxgcyanidi nc(m. p. 289") is fornicii. Ug th3 action of alcoholic ammonia on thelatter substance, i t is convcrted into beiizamidine and ethyl carbamnte,whilst with aqueous aEmonia, benzamide and urethane are formed.UibensamidyZca?.Snlnide, CO (NH.CPh:NH),, is obtained by theaction of carhony! chloride on benzamidine ; diphenyloxgcyanidine isalso produced during the reaction, and tlio two compounds cannot becompletely sepwated ; it crystalli*es from alcohol in prisms which aresoluble in soda, and melt at 229" with evolution of ammonia.Thecompoud is conip1et)elj- converted into diphenylcyaiiidine on heatingabove its meltiug point. Expel-imeiits with propionarnidine were un-successful. By the action of ci~rhot~yl chloride on capronamidinec2ic~l.pr~nct1rzidi~~ebiicrct, NH(~i>.SH.C',H,,:NH>,, is obtained, crys-tallising from alcohol in stellate groups of slender, white needlesmelting a t 236". J. B. 1'.Amidines. By A. P r m E i t ( B ~ I - . , 23, 2923-2927 ; compare Abstr.,1889,1004).-Eth~nyZdip7lenl/lu~~~~~~, NHPh*CO*N:CMs*NH.CWNHPh,is for!med by the action of pheiiyl cyanate on acetamidine ; it wystal-lises from acetone in sinall, sleridthr iieedles, melts at 169", aiidyields acetylpheny1caPbanii~e on boiling with 6-8 parts of 50 percent, acetic acid solution.P~opr,nyZ~~i2Clh'n1/lurrid, N HPli*CO*N:CEvNH*CO*NHPh, is prepai-edfmm propionamiditie in a similar manner to the ethenyl derivatives,and crystallisrs from acetone i n slendor, white needles melting at169-1 7b".On distillation, i t yields diplienylcarbamide, whilst onboiling with dilute acetic acid, propionjlphenylcarbamide is formed.Actio M of A1 d eh y des o n Be71 zanz idine. -Further i lives tigat i onrenders it probable that the compound obtained by the actioiiof benzaldehyde on berizamidine (Zoc.tic.) is d i p h y l dicyaitide,CIIHIOXJ?, and not honzvlidenebenzamidine, C14HlrN2, as shted.Lophirie is also foriced in a very small quantity during the renct,ion.A yellow, amorphous product of the formula C,,H,,N,O, is obtaiiled bythe action of acetaldchyde on benzamidine ; it melts below IOG", issoluble in nlcoliol, ether, aiid chlorofor.m, but insoluble in wu6er orlight petroleum. It yields an amor.phous platinochloride, which niel tsa t about L08". On henting the base nt 130°, and treating the productwith h~.drocliloric acid and platinum chloride solution, an amorphouspZal'inorhZor*;cle is f-oimied which rrielt,s a t 1813" wit,h decomposition, andis probably R purer preparation of the above lower nieltiag corripoiind..J.B. 2'.Action of Benxamidine on the Ethereal Salts of AromaticOrthohydroxy-acids. B.y A P~NNEIL ( Ber., 23, 29:34--2941) .-Bythe action of sodium hydroxide (2 mols.) on ethyl salicylate andbenzamidiite liydrochloritle, crystals are obtained froin which benz-umidine salicylate may be separiltsed by treiitment with acetone ; it isdcposited in large prisms which melt a t 2U2", and ?re readily soluhlcin water or alcohol. The residue remaining after the extraction wii,liacetone forms slender, yellow needles melting a t 246". It is insolublein organic media or i n aqueons soda, ant3 gives a red colour withconcentrated sulphuric acid. The sariie coinpouiid may he prepareORUX-VIC: CHENISTKY. G lin larger quantity by heating an ethereal solution of benznmidinewith ethyl salicylnte at 40" for 10-12 hours ; the ether i s evaporated,wmd the residue boiled out with water. The substance has theformula CzlHliN30, and is formed by the elimination of water,alcohol, and ammonia from i mol.of ethyl salicylate and 2 mols. ofhenzsmidine. The acetyZ compound, C:21HEIPN,0*A~, is prepared bytreatment with acetic: anhydride and zinc chloride, and crystallisesfrom alc*ohol in colourless, lustrous prism.; melting a t 146-142".On adding hydrochloric acid t o the alkaline filtrate obtained afterthe separation of tlie berizuniidine salicylate, be?zzanzide salicy late isprecipitated ; it crjstallises from bol water in silky, lustrous plateswhich melt at 120". The compound had been previously prepared(compare Ahstr., 1889, l O O 4 ) , but its const,itut,ion was unknown.Hy the action of bemamidine on t,he methyl salts of the hydr-oxytoluic acids, corripoiirids are obtained corresponding in propertiesand constitution to the above salicylic acid product.The derivativeof orthoh-droxytoluic acid [COOH : OH : Me = 1 : 2 : 31 melts at214" ; that, of rnetsliydroxytolnic acid L1 : 2 : 41. a t 235' ; whilst theproduct from Farahydroxytoluic avitl [l : 2 : 51 melts a t 202". Alltlicse compoundh are insoluble in acids and alkalis, and a r e exceed-ingly difficult to burl?. Paradihydroxyberizoic acid [COOH : OH : OH= 1 : 2 : 51 also condenses with heiizaniidine; tlie com1)oiind istlrposited from benzeiie in small, nodular crystals, melting at26:) --266", with previous softetiing at 250".The formation of the above conipounds probahlj- takes place in twostages ; in the case of salicylic acid, the hypothetical interniediateproduct has one or other of the formulaeainmonin is then climinatrd, the constitubioii of the filial product beiiigrepresented by t,he forniulzOn hcating ethplphloro~lucinoltricat~boxylic acid with benz;tmidinefor two hont-s a t l:JOo, 2 mols.of carbonic anhj dride arc eliiuinated,slid a compound is formed to which the forniulitC,H@H)2<C(OH) N:cPh>N [OH: N : C = 1 : 2 : 31i s given. J. B. T.Imido-ethers. BJ- A. PISNSK ( h r . . 23, 29&--d956).-1~1uo-LTH EKS FROM 'I'RIMWHYLENE ~~ARiT)E.--TrimethylC'ile cyanide is pre-p r e d by mixing trimethylene bromide witlr 2.5 parts of 85 per cent,;llt.ohol, and adding Q part of finely divided potassium cyanide ; afterboiling for 5-6 hours, the proJuct iH filtered, the greater part of the;Ilcohol removed, the residue dissoli ed in water, and extracted wit11ether; after.distilling off the ether., the crude product is fr.actic,Il-iLteL1 ; the Sield is 85 per cent. of theorp. 7'he hyd?*ochlorides of glutar-all~itlyl ethyl ether- and glutitrumitlyl methyl e t h w are unstable. GlpttaT62 ABSTRACTS OF CHEMICAL PAPERS.amidyl i s ~ b ~ t y l ethw IiydroclrloritEe, C3H6[ C (NH ).C)*CH2.CHMe,. HCl],,is readilg soluhle in water or alcohol and crystalli~cs iu plates. Bythe action of wat >r, ammonia, is eliminated, and I : s o ~ u / ~ J Z glutartrte,C,R,(COO.CH;CHilile,),, is formed ; i t is a viscid liquid hoilinc a t270".On heating the imirlo-ether hydrxhloride, it softens at, l l O o ,and at liigher tenipwaturzs deconiposcls into glntarimide, isobutylchloride, and isobut.~larniiie iiydrochloridc. By the adion of aqueousammqnia, it, i s converted into gZictammide, C,H,(CO.NH,),, which i ssoluble iii water or alcohol, and melt., a,t 176" with evolution ofatninonia. On ti.eatment witjh alcoholic ammonia, isobiityl alcoholand ammonium chloride are eliminilted, aiid a n additive compound isformed consistirig of the hydrochlorides of glntaramidine and glutqr-imidine i n in,)lecular proportion ; on dissolving it in watei-, the iniidineis formed, b u t i t could n o t be isolated on account of its great solubility.Or1 evaporating t,lie mothei.liquor friJm t h e above additive com-pound, large rhornhic crvstals of ~ Z ~ ~ t c ~ , ~ c n ~ n i ~ ? i i i ~ hydrochlorl'dr,C,H,[C(NH)NH,,HCl], + 2H,O, are obtained, which are readilvsoluble in water or alcohol but cmnot be recrystallised ; the hy(1ratedsalt melt? at 7Y", and t,he antiyclrous compound at lt39O. The plntirho-chlo~iclr is deposited in flat, yellow prisms which melt a t 214" withdecoinposi tio I I . Gluf(r r i m i d y l ac-ttcfe, C, €3, [C( N H) OAcj2, is preparedby tlie itc:tioll o f acetic anhydride and sodium acetate on glutaramid-iiie hydrochloride, and crystallises in smal!, lustrous needles meltiirga t 210 -211".By t h e action of primnry aniines on the hydrochlorides of glutar-i [ I t ido-ethers, s u bst itnt ed glutariniidines are form?', the hyd 1'0-chlorides and platinoclilorides of which are ercrssively unstable.lei Ii y Ig lu tar inzitdi t i e plccf h o c h lo ride ( c5 H, N, E tz) ,, H,PtC 16, i s o b tai t i edin yellowish.red crystals which meit at 179".Secondary amines yieldtetra-substituted glutarimidines ; neither the free bases nor the hydro-chlorides could be obtained in a pure state.Tetramethy lglutarinaidim pl(~tinoc7doi+I~le,is deposited in dark-red, cubical crystals which darken a t 190". andmelt at 810" with decourposition. The corresponding tetrethyl com-pound crystallises in long, dark red needles, melting at 141". T'hetetncpropyl derivative forms reddish-yellow crystals meltirlg at I;$".D i byo n i o ~ e t i * a p u p y 1 y lut arint i d ine h y drob t-o ,n ide,is prepared by the action of bromine on the hydrochloride, andcrystallises in long, reddish-yellow needles which melt a t 86", and arevery sparingly soluble i n water.IMIDO-ETHERS OF HYDROXYPBOPIONI'rHILE AND PHENYI,HYDRoxY,~cETo-NITRILE.---The meth!yZ and ethyl ethers of hydroxypropiruide a r e veryunstable ; the hydrochloride of t h e prcyyl efher,0HGHMe.C (NH)OPra, HCI,forms long, colourless needles which melt a t 68--CY0 with decomposiORGANIC CHE:NISI'HP.63tion. The corrtsponding n;rn!yZ derivative is deposited in slenderneetiles melting a t 69". By the action of alcoltolic ammonia, h y d ~ o a y -ympamidiTze Iy7yoch7oride, OH*CHMeC(Pu' H).NH?,HCI, i s formed,c*rpstallising from alcohol in flat needles wbich niplt at 271".Thenitrate softens at, 78", and melts a t 84'.Uimetli y llncfninidiize Iiyrlrorhlo~ide, OH-CHMe*C(S Me)*NHMe,HCI,is prepai*rd hy tlhe action of methylamine on the iinido-am) 1 ether,and is deposited in colourless, rhombi(: crystals, melting a t 21.5".Attempts t o prepare 511 ai;ynimetricsl dimetliyl derivative by theaction of dime t1i yla mine wwe uni;n cceqs Eul.L)7:(Ice:ylpheiz~ll/beta?i/~, 7ine, OAc*CH Ph. C (KH).N Hdc, is obtainedon treating phenylhydroxyacetamidine with acetic anhydride andsodium acelate, and melts a t 210".Hy dror y he i i z 7~ ZnLe t h f j lh y dro. cyp yyirnid i 11 e,is fc)rm3(1 on mixing phenSlhyclroxyacet~midine, ethyl acetoacetate,and sodium hydroxide in molecular pi-oporfion : i t crjstallises frornamyl alwhol in long needles wllich melt a t 2;6', a,lld are sparinwl .y soluble i n water, alcohol, ether, 01' benzene, but rc:idi!y dissolve 111dilute alcoliol, alkalis, and acids.The hytll*ochl ,ride crystallises inneedles melting at 217- with pyevious softening atl 212". The picrateforms slender. vellow needles melting a t 175". The silzer salt is v wliite and sparingly soluLle.The cx.cetyl derivative, OAc*CHPh.~~~,(,,i>CH, -CMe is formedbJ the action of acrtic anhjdi idc ; i t meltr, a t liO", and yields a white,aitiorphous siZver salt. The picrute forms slender, yellow needles whichmelt a t 160" with decomposition ; the lqd~*ocl/Zoride melts a t 188",N=CMe The benzoyl derivative, 0Rz.C HPh-C< ,N.C(OB)>CH, is formed bythe action of bmzo;c chloride on the pyyimidine, and melts a t205-20t3".1'1 1 e hydrochloride crystal I ises fr( hm glacial ace tic acid instellate groups of small needles melting at 240". Hydro rybemyl-p l z e ~ i y l h ! ~ d ~ o x y p ~ r i ~ ~ z i d ; n e , OHSH Ph*C<:.ggg>CH, is preparedtrom the amidine and ethyl henzoylaceta te ; .it crystallises in fineneedles whicli melt a t 318", with previous softening a t 212". Hydroz>y-b en; y ldir I I e t h y I h y dq-ux!/py r iin i d in e is formed from e t hg 1 met h y 1 ace to-acetate and melts at 155". I t yirlds a white, amorphous silver salt.The acetate crystallises in stellate groups of lustrous needles, whichdecompose at 100". Hydrox~benzylmethyleth~jlhydrox~~py~~.irr~itline,C)H.CHi>h.C<KyCMe N C(0H) >CEt, from ethyl ethylacetoacetate, crystal-lises in small needles which melt a t 148-152".t?fJLoxybenzonitl-ilr:.OEt*C,H,*CN, is a yellow, viscid, bitter liquid, wliichboils a t 258", is volatile with steam, and miscible with alcohol, ether,O r light petroleum. The preparation of the pure imido-ether is amatter of some difficulty ; the nitrile is therefore treated with alcoholIMIDO-ETRERS FRO51 OWI'HO- AR'D PARA-Er~HOXYBENZOlr'I'1'ii1LE.--rtltoti4 ABSTRACTS OF C1-1EAlICXL PAPERS.aitd hydrogen chloride. and the product converted into ortho-pthomy-bcnzaonidiw e hi! clwch lot i d c , 0 E t* C6H,- C ( N H N H2, HC1, h y t h c) actio I tof a,lcoholic ammonia ; i t is deposi t d in bhoyt, colourlcss, hcsagonalcrystals melting at 21s". Oyfho-et hoxyphenylmethy lh!/d/.o:,.yl)!/"i?l"id;iLP,0 E t * c 6 H ~ * C < ~ .~ ~ ~ ~ , >CH, is formed from the amidiiie and ethylacetoacetnte, and melts a t 146".Para- etl/,oz!,b~w.zoii ityile i s depopited in long, yellow, rholnbic c r p t 31swhich melt at 69") boil a t 25S", and I-esemble t h e ortho-compound inpropcrtics ; tlte pi-epai-at~ion was not quitc pure. Pnrci-ethna*!/bcnz-iniidoet h y Z et h P r 1) y di.oih 1 o ~ i d r , 0 E t -C6H ,* C ( S H ) 0 I3 t , HC' 1 , vry s t dl isesin white needles which dpcompose on heating into ethyl chloyidc ant1~inl.a-cthoa?/benzclnz,ide, ON t,.C,H,*CO*NH, ; t'iis same compound is a l s oformed by the action of soda on thcb winidine Ir-jdrochloridc.and isdeposited i l l lone crystals melting at, 206". Paru-ethozyherizn?nidii~~'hyd~ocMo~ii?e, OEt.C',Hi*C( ISH).l\'H,.Hfl, is prepared by t h e actiniio f akoholic arnmonia OIL the crude im;do-ether, and is dcpositulfrom alcohol in long, hexag,ronal crystals meltiny at, 260". On treatingthe free b a s e with e t t-l y 1 R ce t oac e t ' i t e , p a /*a - e t li oxpphe rL y 1 11 i e f la y l Ii y d rox IJ -p y~iw~icJine, OE t C,H,* C <GN. c: > C H , is obtained , cry s tall is i 1 I g NC= klc, I from alcohol in short, white prisms which melt at 204'. The samecompound is formed by the action of ethyl acetonialonate on tltcaniidine, carbonic anhydride being eliminated. Pur.a-et~~on.~//)lLcizy2tli-?iieth~llLydi,o2!jpy).z?nic?;?Le, ~~~t*CsH,*~<y.c(OII), Tu'= cIMerc\ l f r , is prepaiwlfrom ethyl mc.thglacctoacct;~tt~, and crystallises from alcohol in smallprisms melting at 22 16".Ethyl ethylacetoacetate yields the correspond-formed from ethjl be117;~lacetoacetate, and crystallises from alcohol,i t 1 which i t is v e r j soluble, in lustrous necdles melting at 242". E'CCIYI-ethozydiphenylliyd~~o~~~p~r.imidi~ie, OE t*C6H,*C<N.C,oH)>CH, N x C P h f i'oiriethyl benzoyhcetate, crystallises from alcohol in broad needles wllic*hiuelt a t 2r4'. ~'arcc-ethoxyteniamidilze ptcl.a-ethuxyphe?zylhlldl.ory-~~?.i?iaidinec.al.box~late,i s formed by the action of ethyl oxylate on the amidine, and iscleposited from alcohol in long, white, lustrous crystals melting at..L@\.,", witti previons softelring at 275".Tlic: f w e acid crystallises fromalcohol in short needles which meit at 248" with decompositiorl.J. K. T.Compounds containing the Group C,N,O,. By A. F. HoLi,EMAN(Ber., 23, 2998--3001).-1n the hope of obtaining compounds re-lated to the dinitrosacyls (Abstr., 1889, 50), the author kiss examineORGAXIO CHENISTRT. 65t h e action of benzoic chloride on mercuric fulminate. The results are,however, riot so simple a s was expected, two crystalline compounds ofu uite a different constitution being formed. Mercuric fulminate,obtained amorcling to de Bruyn's method ( B e r . , 19, 1370)' andwell washed with water, alcohol, and ether, was allowed to remainquietly in a cool place with an equal weight of benzoic cllloride for5-7 days ; after that time, the fulminate had disappeared, and wasi*eplaced by a hard, gre-jish-white mass, On adding water to thel:t.tter, carbonic anhydride is evolved, and mercuric chloride passes intosolut!ion.The insoliible matter, after washing w i t h cold water, isextracted with hot water, wliich takes up a white, crystalline com-ponnd, free from mercury, but containing nitrogen and rriclting at107". The residue is for the most part solnble in acetic acid, andcrystallises o u t on cooling ifi beautiful needles which melt a t 197".a n d have the composition C1.',H12N203, as shown by the results of theanalysis and molecular weiglit determination by Raoul t's method. Onboiling wit$h alkalis, it is converted into bt nzoic acid, ammoilia, andcarbonic anhydride, and i t is therefore probably dibenzoylcarbamitde,but whether it is the sjnimetrical o r asjmmetrical compound has notyet been proved.' h e conipound melting a t 107" is also being moreclosely investigated, and it is hoped that the formation of these sub-stances may throw some light on the constitution of fulminic acid.By t,he action of benzoic chloride on pntaqsium fulminate, a cotn-pound was obtained which also melts at 197", but is riot identic:ilwith dibenzoylcarbamide. It appears to be a mixed anhydride ofbenzoic and fulrninuric acids. H. G. C.Compounds of Phthalimide with Phenols. By 0. OSTERSETZER(Monatsh., 11, 424-428) .-The author has prepared the so called'. resorcinolph thalimidesulphonic acid " of Eeese (German PatentNo.44,268, 1887) by the action of sulphnric acid on i~ mixture ofphthalimide (1 mol.) and resorciiiol ( 2 mols.). The cornpound has the!'ormula C2,H130,Nd, but does apt ear to be a sulphonic acid. It yieldsu sodium derivative, C,,H12N07SKa + 7H1,0, which, whc n precipitatedfrom its aqueous solution by means of alcohol, f0rn.s dark-colouredcrystals ; and a diacetyl compound, C,,H,,O,N;S Ac,, which is solublei l l alcohol and cblorofbrm, and may be obtained as a yel'owisli-green,C I ystalline powder, by cooling a saturated solution in acetic acid.G. 7'. M.Dihydrobenxaldehyde. By A. EICHENGRUN and A. EIKRORN( 7 j e ~ . , 23, 2870-2887 ; compare Abstr., 1887, 741).-The compoundformed by the action of alkaliac carbonates on the salts of anhydro-ecgonine dibromide proves riot to be the analogue of orthobromo-cirinamene, a s stated, but is a mixture of methyl tetrahydropyridyl-rtcetyletie and dihydrobenzaldehyde ; the small quantity of bromiitt:previously found is due to the presence of unaltered anhydroecgoninedibromide.Methylamine is also formed in some quantity during thereaction.liibromanhydl.oecgonine dibroinide hydrobromide,C,NH,Me*CHBr*CHBr.COOH,KBr,Br,Br2 [Me : CH = 1 : 21,is prepared by heating anhydroecgoniue hydrochloride with 2 parts ofVOL. LX. 6 t i ABSTRACTS OF CHEMICAL PA1 ERS.bromine on the water-hatch for 3--4 hours. It crystallises in well-developed, red, rhombic prisms, which melt a t 34.5" with decom-position, and exhibit strong pleochroism.After remainining for a,few hours, the compound gives up bromine, and i t is also decomposedby dissolving in alcoliol, glacial acetic acid, or ethyl acetate. It is in-soluble in water, ether, chloroform, and light petroleum.Anhy d roecgonine dibroni id e hydro browbid elC,NH,Me.CHRr.CH B r*C 0 0 H,HBr,is obtained by the decomposition of the previous compound in a current,of stea,m ; it, is deposited from alcohol, glacial acetic acid, or water iiilong, monoclinic prisms melting a t 18i-188" with decompnsition.From dilute aqueous solution, tetragoiial double pyramids are de-posited, which contain 3 mols. H,O and melt a t 181-182" withdecomposition. On exposure t o air, these crystals become convertedinto the anhydrous niodificatinn.An?, y clroecyonine dibyomide hydrochlo ride,C,NH,Me.CHBr*CHBr*COOH,HCI,is formed by the action of silver chloride on the hydrobromide.Itcrystallises in long, monoclhiic prisms melting a t 173-1 74" with de-composition, and also in tetraqorial octahedra, which contain water ofcrystallisation and melt at 169-170". By tlie action of alkalis ovalkaline carbonates on the salts of anh-j-droecgoriine dibromide,methylamirie, carbonic anhydride, and hydrogen bromide are elimi-nated, and dihydrobenzaldehyde is obtained. If, hnwever, the actionis allowed t o proceed in the cold, several intermediate products maybe isolated.prepared by treating a salt of the dibromide with 2 parts of a satn-rated solution of potassium cai.boriate, or by the action of ammoniumhydroxide or sodium hydroxide at 0".It is extremely scluble inwater, insolnble in absolute alcohol, and cryscallises from acetone ins m a l l , cubical crystals which meltJ at about 150" with evolution ofcarboiiic anhydride. The hydrochloride is deposited from diluteaqueous solution in tetrngonal octahedra which contain 3 mols. H,O,and melt at 197-198" with decoriiposition ; the compound ciystallisesfrom alcohol, froin glacial acetlic acid, or from conceritrated aqueoiissolution in anhydrous, monoclinic prisms which melt a t 203-204"with decomposition. The hydrobromide is also dirnorphous ; theanhydrons, nionocliiiic modification melts at 179", and the tetra gcma1form melts a t 174". The azcrochZoride, C9H,,N02Br,HAuCla + 1+H,O,crystallises from water in t u f t s of long, golden-yellow needles whichmelt, a t 211" ; on exposure to air, the crystals become anhydrous andmt>lt at 215".The lactone does not yield a methyl salt ; on boiliiigwith water, carbonic anhydride is eliminated, and a cornpound of theformula C,NH7Me*C3H3(331€3Br is formed i l l very small quantity ; itcrystallises from dilute alcohol in monoclinic prisms melting at 173".C,NH,Me-CH:CH Br,is prepared by heating a glacial acetic acid solution of the lactone inw-Bromo-1-3-4-methy lte'rtr h ~ , ~ ~ o p y I - i d y l p t h y l e n e ORGANIC CHEMlS'I'HF. 67a sealed t)ube for 5 to 6 hours at 170" ; the product is poured into water,and the solution neutralised with sodium carbonate aiid extractedwi tJh ether ; on treating the ethereal solution with hydrochloricacid and auric chloride, the aurochloride is formed ; it crystallises inshort, yellow needles which melt a t 174".On boiling with water, theauric salt of met hyltetrahydropyriclylacetylerle is formed (see below).The sane base is also obtained by the fusion of the lactone, or byboiling it f o r some time with glacial acetic acid or acetic anhydride.On boiling dibromecgonine dibromide hydrobromide with aqueouspotassium carbonate, and distilling the solution in a current of steam,a yellow, oily liquid is obtained ; this is dissolved in ether and thesolution washed with hydrochloric acid ; the acid liquid is neutrnlisedwith soda and extracted with ether ; on evaporation, methy7tetmhydro-pyr'idylacety ZenP, C,NH,Me*CiCH remains as a colour~less, basic, viscidliquid.The aumchloride crystallises from dilute alcohol in brownish-yellow cubes or flat, yellow needles which melt at 177*5-178*5".CH *CH Dihydrobenzaldehyde, CH2<cH2: iH>CCHO, is formed, togetherwith the previous compound, fromwhich i t is separated in the mannerdescribed. It is best prepared by heating an aqueous solution ofanhydroec*gonir,e dibromide hydrobromide with 0.5 part of sodirmcarbonate a t 60" ; the product is distilled in a current of steam andthe distillate extracted with ether. After washing with a few dropsof hydrochloric acid, the ether is distillcd, and the residue fraction-ated in a vacuum ; the yield is 20 per cent. of the dibromide employed.Methylamine and anhydroecgonine hydrobromide are also formed.The aldehyde is obtained as a colourless oil which darkens on expo-snre to light, and has an intensely nauseous odour; i t boils at121-122" under a pr.essure of 120 mm., and is partly decomposedon distillation at ordinary pressures ; sp.gr. = 1 . ~ 2 0 2 at 14*5O,and 1*0:-27 a t 0". It forms a crystalline compound with ammonia,reduces ammoniacal silver solution and potassium permanganate solu-tion izi the cold, and also reduces Feliling's solution on warming ; itis not oxidised on exposure to air or oxygen, but becomes slowly con-verted into a resinous mass ; concentrated sulphuric acid decomposesit in the cold. The formation of the aldehyde is explained by assum-ing that hydrox\l is substituted for the bromine i n w-bromomethvl-tetrahydropyridylethylene ; the unstable group CH:CH*OH thenchanges into the more stable complex CH2*CH0, and, by the elimina-tion of methylamine, the hypothetical compoundCII<cH2*cH2> CH-O CH.CH,*CHOis formed ; this gives up the elements of water and yields dihydro-benzaldehyde.The aldehyde forms a crystalline compound on trca t-rnent with hydrogen sodium sulphite in the cold, which is readilysoluble in water, but insoluble in alcohol or ether ; on boiling withan alkaline carbonate, it is converted into benzaldehyde. Dihydm-benzylidene pherylhydrazone is prepared by the action of phenylhydr-azine on dihydrobenzaldehyde, and is deposited from alcohol in small,yellow plates melting at 127-128" ; the crystals exhibit stroiigpleochroism.Dihydyobertzoxime is obtained by the action of hydroxjl-f ; 68 AHSTRACTS OF CHEMICAL PAPEHS.arnine on the aldehyde. The oily liquid which is formed consists oftwo isomeric compounds, which may be separated by treatment withl i g h t pet,roleum (b. p. 40-50O) ; the soluble compouiid, which istermed the p-oxime, crystallises on cooling, arid melts constantly a t4-44" ; the a-hydroxirne is insoluble in light petroleum, and docsnot crystallise.Dihydmbenzoic acid, CHz<cr3 CH2'CH>C*COOH, :CH is prepared by theoxidation of the aldehyde with an ammoniacd solut,ion of silveroxide ; it is volatile with stcam. On cooling an nquvous solution, itis deposited in feathery crystals which melt at 94-95", and are morespnringly soluble i n water than benzoic acid.The compound has anngreeable odour, and reduces aminoniacal silver solution, but doe3 not1-euct with Fehling's soliltion. it is converted into beuzoic acid onstrongly heating. The siZ?,er salt readily decomposes on exposure tolight ; like the lrad salt, it is sparingly solnble in water. The salts ofhnriurn, awrrronimn, and the nLlrcr7i metal.. 1-erldily dissolve i n water,n,nd crystallise from dilute alcohol, on the addition of ether, in silky,lustrous neecllw. The copper salt is soluble in ammonia with a gi-eenco10nr9 and is deposited in green, nodular crystals. OIL treatingdihydi obenzaltlehyde with almost any otlier oxidising agent, i t eitherremains unalterecl, or is completely dec-omposed ; with potmsiumpermangnnate, i t yields benzoic acid.By A.HANTZSCII (Ber., 23, 2776---27W).--'l'he further investigationof the oximes of pai.atoly1 plienyl ketone (Abstr., 1890, 1273) hasglhown that the a-oxime may be converted into tll;e ,&coinpound simplyby heating its alcoholic solution. Tlie transfonnation is, however,very incomplete, and a large amount of the ketone is re-formed.)getter results are obtained when the oxinie is mixed with an equalweight of hydvoxj lamine hydrochloride, hot even under tliese con-ditions a rnixtureoof tfie two oximes is always obtained. As previouslymentioned, the P-oxime is only slowly and incompletely convertedinto the benzyl ether on treatmeiit with benzyl chloride ; if, how-ever, the bromifle is emplo*yed, the readion procecds much morereadily, and a purer prodact, is obtained, which, after recrystallisationfrom amyl aJcoliol, tnelts a t 51".I t also crystallises horn etheri n sleiider, silky needles, and if pure is not acted on by hot water oralcoliol, or when 1~ydi.ogeri chloride is passed into its ethereal solution.The acetyl derivati\-e of the a-oxinie has already been described byAuwers (Abstr., 1890,503). If the8-oxime is dissolved inacetic anhydr-ide a t the ordinary tetrtperature, and the solution allowed to evaporatespontaneously, fJ-ucet!/lp"~ato7!/Z phenyl ketozir),e, CPh (N*OAc)*C;H;,crystaliises out. Tlie crystals reberlible those of the a-rxjmpourid, butare somewliat more acute. I t cannot be obtained quite pure, as itreadily passes into the a-acetyl derivative in the course of theusual processes of purificatioii, especially in alcoholic solation ; ifthe latter be warmed, t h e trirnsf'ormation is almost instantaneous andcomplete.This fact, explains why Auwers (loc. cit.) was unable t oobtain the /3-oxime, for lit: adopted this method of purification, andJ. €3. T.The Stereochemical Isomerides of Pamtolyl Phenyl KetoneORGANIC CHEMISTRY. 6 !)therefore only obtained the a-compound. Phenyl isocyanate actson Loth oximes, b u t with formation of one and the same additivecoinp~uiid, correspolrcling with the a-oxime and melting a t 180'. '1'11pisotnei-ic xcetyl det*ivatives and plienyl isocyanate addl tive conipoutitlsof par~Lbroniobeiizopirenone are much more stable than the above ;this, according to the author, is probably due to the influence oftlie methyl group.Constitution of Cumenylpropionic Acid.By 0. T;liIDaI.s ?i(Ber., 23, W i 6 - :3080 ; coinpare Ahstr , 1889).--o,-tl2(,I,,.o?t~ocuinelz!,I-UCUJZ~C acid, CHILIL.,.C,H,I~~.*C'H:CEI.G'OOH [CH:CHn/Ie:Er= 1 : '2:4],is prepared from the cqrresponding amidc-acid, but co~iltl not beobtained in r2 pure condition ; it crystallises flom dilute acetic. acid i i ilong, colourless needles melting at 154". On iduction with 113 driodic:acid and ph ospli oms, it yields orth oh ro/i/ oc 1 1 menylpwpic~ 11 ic ucitl,CHMe,.CsH,Rr.CH2.CK,.COOH, crjstiillisitig from light petroleum inlong, slendthr needles which melt at2 tp)3*50, a n d yield cunienyl propi-onic acid by the action of sodium ttm;~1gam.Crthocl~loi~oc~~rt~rnylccc~q~lic acid, CHhle,.C,H,Cl.CH:CH.COOH, crjs-tsllises from acetic acid in lusttvns plates nielting at 133-134".Hy the action of sorlinm iiitri te and 1~ydrol)roniic acid on amitloprop? I-ciniiamic acid, a conipoiiiid is obtained which melts at 128", arid oniwlnction with phospliorus ancl 11) driodic acid, yields tlie n b o ~ c:tlcscribed orthobromociinieiiSlpropionic acid (111.p. Z5.5"). An investi-gation of the orthnn~ido~~i~opylcinilamic acid showed it to bc a mixturtlof two-thirds o ~ t h ; ~ m i d o c u r ~ ~ c i ~ ~ l a c ~ i ~ ~ l i c acid (m. p. 161') mid oiie-third metamit-locnmenSlacr$lic acid. It follows, therefore, t h a t theso-called orthonitropropylcinnamic: acid is also a mixture of ortlro-atid rnPta-nitrocunienylaci.ylic acids.Cnnienylpropionic acid (ni. 13.i5.59") is thus finally proved to be an isopropyl derih ative.a. G. C.J. B. T.Perkin's Reaction. By 0. RI:WFF.ZT (Goazetfn, 20, 158-1 6 2 ) .--The conde~isation of alclehycles w i t h organic sodiuni >&Its is geiirr,~llysuirposed to take place without the acetic anhyclricle nsed taking ai1.ypart in tlie reactlion. The author finds that iu his syntllesis of' phenxl-citiiiainenj 1aci.ylic acid (Xbstr., 1S8??, 1137) from cinnam,zltlehyttc~,sodium phenylacetate ancl acetic anhydride, iE the 1-eaction is inter-rn))ted as soon as the solution l ~ n s been r;lised 10 the lmiling point, t i t i t ltlie product is thrown into cold watei..a n insoluble oil rcrriains, whi1.hlias the composition of ciwnu/i?yZidene ditrcetctfc, CHPh:CH*CH(OAc),,whilst the aqueous solution coiitttins tlie whole of tlie phenj-laceticacaitl used. l'he acerate crjstallises from alcoliol in large, colourlesh,nacreous plates, and melts a t 84-85". It is ciecorrlposed into cinnarti-alclehycle and acetic acid by distillatlion i t 1 steam, 0 x 8 by boiling w i t halkaline carbonates. It takes up 2 atoms of bromiiie forming anunstable compound, which, on steam distillatioii, yields Zincke's phenyl-/+hromacraldehyde (Ahstr., 1884, 1343). If left for a long time, i t i.;couvertecl into a yellow syrup, which smel Is of cinnniiialdehyde ant1acetic acid. 'l'he foregoiiig experinletit renders i t probable t h a t thefirst step in Perkin's reactioll is the foriiratioii of an acetate of tliealdehydic radicle.S. B. A. A70 ABSTRACT8 OF CHEMICAL PAPERS.Methylresorcinolphthaloylic Acid. By E. Q c ENDA (Gazzettn,20, 127--13~~.--~ethylr~eso~cinol~hthaloylic acid,COOH*CsH4*CO*C6H3( OH)*OMe,is obtained like the corresponding aniso'il and pheneto'il derivatives(see Grande, Abstr., 1890, 1128). A mixture of phthalic anhydride( I 2 grams) , dimethylresorcinol (24 grams), and alurninium chloride(16 grams) is heated for about three hours on the water-bath, theproduct thrown into excess of cold water, and the precipitated acidextracted with ammonium carbonate, and reprecipitated with hydro-chloric acid. It is then purified by repeated crystallisation fromtoluene and from water.l h e pure acid crystallises in light, colour-less scales, dissolves sparingly in boiling water, but readily in hottoluene and in ether. It melts at 164--165", forming a clea,r,yellom is'i-red liquid, and a t a liiglier temperature dense, white, irri-tating fumes are evolved. A neutral solution of the ammonium saltgives precipitates with soluble salts of copper, zinc, mercury, lead, &c.The silver salt, Cl5Hl1O5Ag., is obtained as a heavy, white precipitate,which is soon blackened and decomposed hy light. The barium saltcl-ystallises in anhydrous, yellowish nodules. S. B. A. A.Gallic Acid, Tannin, and Oak Tannic Acids. By C. BOTTINGICR(Anr/alen, 259, 132-136) .--The author's attempts to prepare cyan-hydrins and oximes from gallic acid and various tannins were unsuc-cessful, and 110 definite results were obtained.Action of Phenylhydrazine on Tannin Extracts.I3;y C.BOTTINGER (Annalerh, 259, 125-l32).--The true tannins combinewith phenylhydrazine, yielding amorphous compounds, which havenot been prepared in a pure condition, and which consequently havenot been analysed ; in their behaviour with acids, they show a certainresemblance to the osazones of the sugars.On boiling an aqueous solution of a tannin extract with phenyl-hydrazine, carbonic anyhydride is evolved, probably also nitrogen,and the phenylhydrazine is partially decomposed into ammoriia antiazobenzene, so that ammonia derivatives, as well as phenylhydrazinederivatives of the tannins, are formed.The following extracts wereexamined :-Sumach, vallonia, algarobilla, divi-divi, oak-wood, oak-h r k , and pine-bark.Manufacture of Decolorised Tannins : Zinc Tannate. By A.VILLON (Bull. SOC. Chim. [ 3 ] , 3, 784--786).-The liquor obtained byexhalisting the crude material in the ordinary way is cooled at 2" forhalf an hour, and after filtering off extractives and tannins insoluble inthe cold, 0.5 per cent. of zinc sulpliate is added. The tannin of the liquoris now titrated, and for each kilo. present in the s0lution~2.5 kilos.of zincsulphate, dissolved in 12.5 Iitres of water, is added, and the whole isplaced in a closed vat, furnished with a mechanical stirrer and steamcoil, into which is passed the ammonia resulting from the decompo-sition of 2.5 kilos.of animoniuni sulphate per kilo. of tannin present.After separation by a filter press of the precipitated zinc tannate, i tis decomposed by dilute sulphuric acid, and to the liq.ior bariumF. S. K.F. s. KOliQANIC CHEMISTRY. 71sulphide is Rdcled, uritil the zinc sulphate is completely precipitated aszinc sulphide and barium sulphate. On filtration, a liquor containing'L0-:30 per cent. of tannin, and almost free from colour, is obtained.1 he process is economical, siuce all the bye-products are capable ofDiphenylsuccinic Acids. By R. ANSCH~~TZ and P. BENDIX(AnnaZen, 259, 61-100) .-Diphenylmaleic: anhydride, prepared frombenzyl cyanide by Reinier's method (Abstr., 1886, 169), separatesfrotn ether in well-defiued rhombic crystals, a : b : c =0.69287 : 1 : 1.35838, boils a t 236" (15 mm.), and is readily solublein chloroform and benzene, but only spariiigly in alcohol and ether.9ttempts to convert this anhydride inlo dipheiiylf umaric acid wereunsuccessful ; when it is treated with hydrogen chloride in metliyl orethyl alcoholic solutiou, i t is partially converted into an alkyl saltidentical with tliat obtained from the silver salt' of diphenylmale'icacid, but a considerable quantity of the anhydride remains unchanged.DiphenyZrnaleGiiiZ.C,?H,,NO,, is easily obtained by heating thepreceding compouiid with aniline a t 120" ; it crystallises from alcc-holic chloroform in slender needles, melts at 174-175", and boils at2 9 3 O (14 mm.). On hydrolysis witti boiling potash, it is decomposedinto diphenylmaleic acid and aniline; the same change is broughtabout by boiling hydrochloric wid, but only very slowly.Theseexperiments show that diphenylmnleic anhydride is not converted into.diphenylfumaric acid under conditions which lead to the transforma-tion of maleic into fumaric acid ; it is douhtful whether the compounddescribed by hugheimer (hbstr.. 1886, 1698) as diplienylfuniaric acidis in reality this substance.Both a- and /3-diphenylsuccinic acids are formed when diphenyl-rnaleic anhydride is reduced with sodium amalgam in alkaline soh-tion, as described by Reimer (Zoc. c i t . ) , or with zinc and hydwchloncacid in alcoliolic solution ; the relative yield of the /%acid is greaterwhen tlie reduction is carried out with zinc and hydrochloric acid.The two acids are most conveniently separated by means of theirbarium salts.Barium a-diphenylsuccin~te, C16Hlz04Ba + 2H20, is obtained byprecipitating a solution of the ammonium salt with bariuni chloride ;it is soluble in 312 parts of water a t 17-18".A sparingly soluble>,alt containing 4 mols. of water is formed when barium hydroxide isadded to a dilute solution of the ammonium salt.Barium /3-diphenylsuccinate, Cl6Hl,,O4Ba + 7Hz0, separates in well-defined crystnls when a solution of the barium salt ot' the /?-acid isevaporated a t 100" ; it is soluble in 4.742 parts of water at the ordi-nary tempeisature.Both a- and /3-diphenylsnccinic acid form colourless silver salts,which, when dried a t loo", have the composition Cl6H~,O4Ag, ; whenflrese silver salts are treated with ethyl iodide a t IOU", they are con-verted into ethyl salts, identical with the compounds obtained byHeiiner (Zoc.cit.), by treating the corresponding acids with alcoholand sulphuric acid. The ethyl salt of the a-acid melts a t 34", that ofthe p-auid a t 140-141".1 1easy regeneration. T. G. N72 ABSTRACTS OF CEEBlICAL PAPERS.a-Diphenylsuccinic acid dissolves in cold acetic chloride with eroln-tion of hydrogen chloride, and, after evaporating the solution a t IOO",there remains an oily mixture of the anhydrides of the a- and fi-acicls,\jrhich gradually becomes crystalline ; this product separates fromether in well-defined crystals, melts a t 115--116", and boils at 240"(about 15 mm.), the dist,illate gradually solidifying.When boiledwith water, it yields about 96.5 per cent. of the a-acid, and 3.5 percent. of tlie ,&acid, even when in its preparation from t h e acid thetemperature is kept below 36' throughout the various operations ;when treated with potash, i t gives 85.8 per cent. of the a-rlcid, aiid14.8 per cent. of tlie /%acid. The same mixture of anhydrides iso't)t,ained from the barium salt of the a-acid in like manner.,!I-Diphenylsuccinic acid is not acted on by acetic chloride in thecod, but a t 100," i t yields a mixture of anhydrides which has thesame melting point and other physical properties a s that obtainedfrom the a-acid, but which, on boiling with water, gives '74.81 per ceii t.tjf the a-acid, and 18.5 to 26.1 per cent.of tlie Lj-acid. When silvei.or barium ~-diphenylsuccinate is treated with acetic chloride, amixture of the anliydrides is formed which melts a t L I O - l l l o , andon boiling with water, gives 65-70 per cent. of the P-acid, and35-40 per cent. of the a-acid.The mixture of anhydrides obtained by distilling a- or [j-diphenjl-succinic acid under reduced pressure (14 rnm.) melts a t 112-11:3"and in its behaviour with solvents, &c , it resembles that produced b jtreating the acids with acetic chloride ; when boiled with water, ityields about 90 per ceut. of the a-acid, and 10 per cent. of tbe /3-corn-pound.When the a-acid is heated ati temperatures ranging from 150 to 185",about 50 per cent.is converted into anhydride, and allout 50 per cent.into the /$acid ; tbe P-acid, on the other hand, does not lose waterbelow 185". These experiments prove the existence of two isomericdiphenylsuccinic anhydrides, but owing to the great similarity i nproperties, the two compounds cannot be separated ; the existence oftwo anhydrides proves, however, that t,he isomerism of the two acidscannot be explained by assuming, as Roser has done, that they havethe constitution I > and I respectively,and it seems more probable that the relationship between theni is thesame as th;tt which exists between the two bydrobenzo'ins.UiplLen?ll.Euccinanil, C22HliN02, is obtained when the anhydride, pix-pared either irom a- 01' P-diphenylsuccinic acid by means of aceticchloride, is lieated with aniline ; it can also be obtained by reduciiigdiphenylmaleanil.It crystallises from hot benzene in colonrlessneedles melting a t 0,26-28i0, and from glacial acetic acid in largerneedles melting at 230-231".Diphen ylsuccinnnilic acid, C22H19N03, is produced when the pre-ceding cotiipouiid is boiled with barium hydroxide ; i t crystallises fromdilute alcohol in colourless needles, and melts a t 220". I t is notchanged by warm concentrated alcoholic potash, but it is recon-verted into the ariil by glacial acetic acid, hjdrogen chloi,irie, andalcoholic sulphuric acid.CH P h. C (0 H) CHPh-COOHCHPh- GO CHPh*COOHF. S. KORGANIC CHEMISTRY. 73Crystallographic Proof of the Identity of Pyranilpyro'in-lactone and Citraconanil.By R,. ANsCiiijTZ ( J:w., 23, 2979-2981 ;see also Abstr., 1890, ll02).-By the slow evaporation of the etherealsolution of citraconanil obtained in different ways, the author hassucceeded in obtaining i t iu well developed crysta.ls. Hintze andJennsen have exarniried cryst8allogt-aphically preparations obtained( I ) from ,'3-anilidopyrotartaric acid (R'eissert's pyranilpyroi'nlrtctone),(2) from aniline and citraconic acid, (3) from pseudoitacoiianilic acid.The nieasnreirients show conclusively that the substances obtainedby all three methods are identical, the crystals belonging to themonosymmetric system ( a : b : c = 2.75i5 : 1 : 1.8152, /3 = -51" 17').The optical properties of all three were also found to be almostidentical, three corresponding plates giving the following numbers :-No.1. No. 2. No. 3.2Ha.. .. .. .. 11" 6' 11" 22' 11" 35'H. G. C.Paranitro-orthotoluenesulphonic Acid. By J. HAUSSER (BUZZ.SOC. C'him. [ 3 ] , 3, 797-799) .-Paranitrotoluene (200 grams) is slowlyadded t o sinlphuric acid containing 44 per cent. sulphuric anhydride(260 grams), the energetic reaction being modified by cooling withice, and tben completed by heating the mixture at 150". Theproduct is added to water (1500 grams), aiid after removing theexcess of sulphuric acid by calcium cai*boriate, the solution is con-centmted until the sulplionic acid cryst,~llises out, the yield being64 per cent. The autbor confirms Jennsen's researches (tois Journal,1874, 4791, and finds that the acid decomposes the sulphatcs of zincand copper forming uitrosulphonates and liberating sulphuric acid.Nitrotoluenemetasulphonic acid, which may be prepared in a similarmanner, is an analogous substance.Iodometaxylenesulphonic Acid.By C. RAUCH ( B e y . , 23,3117- 3 11 9).--The iodometaxylene~~ilphorlic acid prepared by Ham-merlich (Abstr., 1890, 1106) has the fomiula [Mez : I : SO,*H =1 : 3 : 4 : 61, sitice, on fnsion with potash, it yields a dihydroxy-deriva-tive which melts a t 146" and is identical with the compound obtainedby Wischin (compare following abstract). The sulphonamide, pre-piired after elirriiriation o f the iodine, melts at 137", and therefore hasthe formula [Me, : SOzNH2 = 1 : 3 : 41.Metaxylenedisnlphonic Acid.By R. WISCHIN (Ber., 23,3113-311 7).-ill~taxyZenedisuZ~lzon~c ac;'d, [Me,: (HSO,), = 1 : 3 : 2:4],is prepared by heating metaxylene with 4 parts of fumingsnlphuric acid a t 150" ; on pouring into water, small crystals sepa-rate which cannot be purified by crystallisation from dilute sulphuricacid. The disuZphochZoyide crystallises from ether. in needles meltinga t 129". The constitution of the compound is proved hy the produc-tion of dichlorometaxylene (b. p. 228"), on heating with I'hosphoruspentachloride a t 180". The sodium salt is readily soluble inwater. On oxidation with potassium permanganate, it yields adisuZp?iisophfhaZic acid, which is deposited from alcohol in small,T. G. N.J. B. T74 ABSTRAOTS OF GHERIIOAL PM'EHS.granular crystals melting a t 250'.The barium sulphonate crystallisesfrom water in plates. The sulplmnawzide is deposited from water iiisilky, lustrous needles which melt a t 249".Dihydroxyxylene [Me2: (OH), = 1 : 3 : 2 : 41 is obtained by fusingthe sulphochloride with potassium hydroxide, and may be purified hysublimation ; it is deposited in slender, white needles melting at 146",and is very readily soluble in water, alcohol, or ether; an intenseviolet colour is produced with ferric chloride; on heating withphthalic anhydride and dissolving the product in soda, a green fluor-escence is observed. Disu~l~airiine-iso~hthulic anhydride,is prepared by heating the disulphonamide with potassium per-manganate solution, and decomposing the resultiug potassium saltM ith sulphuric acid ; the anhydride crystallises from alcohol, melts at225", is very sparingly soluble in water, and exceedingly bitter to tlietaste.Mttaxylenedisulp'23~onethyZaniide7 from tho disulphochloride andethylstmine, crystallises from water in silky, lustrous ueedles whichmelt at 135".~ r i , ~ , ~ ~ x y l r r ~ e d i s u ~ p h o n i c acid [Mez : Br : (€€SOs), = 1 : 3 : 4 : 2 : 61is prepared by the action of fuming sulphuric acid on bromo-xylcne[Me, : Br = 1 : 3 : 41 ; both the acid and its salts crystallise withgreat difficulty.The sulphochloride is obtained from ether in long,white crybtals melting at 160". 'I'he su@horLamids is deposited fromwater in needles melting at 265".Bromodihydroxysylene, obtained by the fusion of the acid withpotassium hydroxide, forms white crystals, melts at 126', and givesa violet colour with ferric chloride.Chlo~.o-xyleneclisul~holLic acid resembles tho bromo-derivative i nproperties and constitution.The sulphocl~luride crystallises fromether in white needles melting a t 155". Ttie sulphowamide is deposit et-lfrom water in silky, lustrous needles which melt a t 270".Chlorodihydroxyxylene is obtained by sublimation in white needleswhich melt a t 10tjo, and give a violet colour with ferric chloride.J. B. T.Action of Thionyl Chloride on Secondary AromaticAmines. By A. JUICHAELIS and E. G o n c ~ a u x (Hey., 23,3019--3023 ;compare Abstr., 1890, 610).-~'hiclnyZ~iethyZuniline, SO(C&H1*NI~Me)2,is prepared by adding an ethereal solution of thioriyl chloride to amixture of aluminium chloride and methylaniline, dissolved in thesame medium ; the solution is well cooled and poured into cold water,the ether separated, and the aqueous solution filtered and treatedwith excess of soda ; the precipitate thus obtained is boiled with alco-hol, and the alcohol evaporated ; the residue is dissolved in chloroform,and, on adding light petroleum, it crystallises out in stellate groupsof colourless needles which melt at 154" and readily assume a blue tint.RiitrosothionyZnaet7yla~~ilane, SO( CsH,*NO&f e-NO),, is obtained by theaction of sodium nitrite and hydrochloric acid on the preceding comORGANIC CHEMIS'I'RY.75pound, and is deposited from alcohol in coloL~r1css needles melting at17l0.IThiornethyZaniZine, S ( CsH,NHMe),, is forrned by the reduction of thethionyl derivative with sodiurii in alcoholic solution ; it cr~stallisesfrom a mixture of ether and light petroleum in long, yellow, trans-parent needles which melt a t 60°, and are readily soluble in chloroform,ether, or alcohol.Nitrosotlrio?nethyZa~~iZine, S ( C6H1*NRlle.NO),, fromsodium nitrite and thiomethylaniline, crystallises in yellow, lustrousplates ~ h i c h melt a t 133d, and are very sparingly soluble in coldalcohol. J. B. T.New Synthesis of Indigo. By 1;. LEDERER (J. yr. Chem.[ a ] , 42, 383).-2 grams of phenylglycocine are stirred iuto 8-10grams of fused sodium hydroxide, itnd the fusion maintained untilthe colour becomes pure orange, wllen *he reaction is over.Theriielt is dissolved in much water, when pnre indigo-blue is aepa-rated. A. G. B.Synthesis of Indigo and Allied Dyes. By K. HEUMANK (Ber.,23, ;~04S-:~0$5).-Phenylqlycocine is heated i n absence of air with2 parts of potassium hydroxide a t 260" ; the fused niass becomesbrownish-orange; i t is allowed to cool, dissolved in water, and astream of air drawn through the solution ; an immediate precipitationof indigo occurs. Care must be taken not to continue tthe fusion toolong, or decomposition takes place ; small portions are therefore with-drawn from time to time and dbsolved in water, the heating beingimmediately stopped as soon as the formation of indigo is observed.Sodium hydroxide may be substituted for potassium hydroxide, butthe reaction takes place a t a much higher temperature.Kxperirnentswith other dehydrating agents were unsuccessful. The reaction mayhe explained by assuming that, by the e!irnination of water fromphenylglgcocine, pseudindioxyl, C6H4<NH> co CH,, is formed, andthat this yields indigo on oxidation. J. B. T.Desmotropy in Phenols. By J. HERZIG and S. ZEISEL (Moqzd~h.,11, 413-420; compare Abstr., 1888, 823 ; 1889, 2417 and 966). -Onheating diresorcinol (1 mol.) in alcoliolic solution with potash(8 11101s.) and ethyl iodide (8 mols.) in a reflux apparatus for severalhours, the authors obtained, as the chief producf, a viscid, brownishoil, insoluble in potash. Wheii shaken with cold alcohol, a portion oft h i s substance dissolves, and may be obtained on evaporation of thesolvent.After several recrystallisations from hot alcohol, it isobtained in scales melting coiistaritly a t 90-92", and is shown byanalysis to be ethg Zdiresorciwyl tetrethyl ether, C,,H,Et(OEt),. Onheating this ccmpound with hydriodio acid, ethyldiresorcinoZ,C12H513t(OH)4, is formed, but, owing to its instability, it cannot beobtained in a pure state. Y'etracetyZeth yZdiresoi-ci?LoZ, C12H,E tAcp, isreadily prepared by heating the product of the action of hydriodicacid 011 ethyldiresorcinyl tetrethyl ether with acetic onhyodride. Itcrystallises from alcohol in needles which melt a t 135-138 76 ABSTRACTS OF CHEMICAL PAPERS.That portion of the oil which is insoluble in alcohol consists ofdiresurcinyl tetmthyZ elhey, C,,H,(OEt),, and crystallises from hotalcohol i n scales which melt at 112-114" (compare Pukall, Abstr.,These results show that in diresorciuol two hydroxyl groups of abenzene nucleus occupy, relatively to each other, the meta-position,and that ethylation is induced by the mobility of their hydrogenatoms, i n the same way as the authors have previously shown (loc.d.) obtains in the case of other metaphenols.Diphenyldiethylene Derivatives.By 0. REHUFFAT (Gazzerfa,20, 154-157) .-L>~p~2enyEdiefhykne, CHPh:CH.CH:CHPh, synthe-tically prepared by the author (Abstr., 1883, 11 371, crystallises fromalcohol i n large, colourless, micaceous plates, melts a t 147-148", ariddistils uiialtered at, 2.50". I t is sparingly soluble in ether, but readilyin alcohol and carbon bisulphide.T~tl.abromodiphenyIdiethylene, prepared by treating an etherealsolution of the hydrocarbou with excess of an ethereal solution ofbroriiiiie, crystallises in white scales which are unaffected bg pro-longed exposure to air and light ; it blackens :tnd melts a t 230".The dib r-onzo-derivative, C HPh BrCHBi-CKCHPh, is prepared- bymixing the theoretical quantities of its constituents in etherealsolution in the cold, and allowirig t h e mixture t o I-emain. It formstufts of colourless, acicular crystals, and melts a t 147-148", decom-posing if not quite pure.It combines with some difficulty with twoatorns of' bromine forming the tetrabrominated derivative.When a solution of diphenyldiethylene in carbon bisulphide istreatsci with a solution of bromine in the same solvent in the propor-tion required for the formation of a tetrabromide, the liquid istlecolorised after some time, a small quantity of the hydrocarbonbeing deposited ; on distillation, the dibromo-derivative passes orertogether with a brominated compound, intermediate in compositionbetween the di- and tetra-bromo-derivatives.This substance crystal-lises from carbon bisulpliide in long prisms, and melts a t 158", pre-viously softening a t 190".Synthesis of Benzylcinnamic Acid. B y A. OGLIALORO (Gnzzetta,20, 162-164) .-Benzylcinnarnic Acid, C12H1402.-A mixture of sodiumhydrocirinamate and benzaldehyde in molecular proport,ion is heatedwith a'n excess of acetic anhydride for six hours a t 16C0, and theunaltered anhydride and the phenylpropionic acid are then removedby treating the product with ether and h o t water respectively.Theresidue, after being purified by extraction with boiling light petro-leum, crystdlises from absolute alcohol in large, white needles whichmelt a t 158". The iriost probable constitution for this compound isthat of a benzylcinnauic acid, CHPh:C (CH,Ph)*COOH.1887,1360-66 1).G. T. M.S . B. A. A.8. B. A. A.Naphthyl Sulphides. By F. KRAFF'I' and E. B o m ~ s o i s (Rer., 23,3045-3049 ; compare Abstr., 1890, 13 11) .--act- Dinaphthyl sulpliidemay be prepared from hromonaphthalene and the lead salt ofa-nrtphthyl mercaptitri i n the manner previously described, PhenylORGANIC CHEMISTRY.7 7a-nnphfhyl sulphidp, CloH7*SPh, is obtained in the same wayby heating a-bi-ornonaphthalene with the lead salt of phenyl mer-captan, a t 240" f w 2-3 hours ; it crystallises from alcohol in hard,coloiirless, lustrous prisms which melt at 41*5", and boil at 218" u1idc.ra pressure of 14 mm. The yield is over $1 per cent. of the lead salternployed ; on oxidation, the corr: sponding sulphone is obtained.Phemjl-[d-naphthyl sulplride, CIOH7.S1Jh, is tormed, together withdiphenyl sulphide and P/j-dinaphthyl sulphide, from monobromo-l~enzene and t'he lend salt of 6-naphthyl mereaptan ; it c r ~ s t a ~ l l i ~ e sfrom alcohol i n steliate groups of small, white needles, or in lustrousplates, which melt, a t 51*5", and boil a t 224" under a pressure of14 mm.The yield is 25 per cent. of theory, and the correspondingsulphone is obtained on oxidation. J. B. T.Action of Aromatic Bases on Naphthol Violet. I3y R. HIRSCHaiid El, KATXKHOFF (Ber., 23, 2992--2994).-A new colouring matterrelated to naphthol violet has recently been described lty Witt(Abstr., 1890, 1307), who regards it as being formed simply by theaction of heat 011 tlie last-named colouring matter. The autkiors h:tdalso previously observed that, under certain circumstances, prepara-tions of naphthol violet have an unusually blue shade. Accordingto present ideas, the colouring matkei. has the coristitutionC,,H,< >C,H,.NMe2,HC1, and is formed from nitrosodimethyl-aniline and p-naphthol according to the equationN0The h-j-drogen thus set free reduces anot'her portion of nitrosodi-methylaniline to amidodimethylaniline, and the authors regarded it asprobable that the blue colouring matter was formed by the furtheraction of the latter on naphthol violet, and they, i n fact, succeeded inthus obtaining a colouring matter identical in every respect with thatdescribed by Witt.I n place of amidodimethylaniline, other aromaticbases, and even ammonia, may be employed, well-defined colonringmatters being thus obtained. The compound from aniline cr~stallisesin brown needles which melt a t 256" and dissolvc in concentratedstilphuric acid with a violet coloration. The base from paratoluidineresembles it vevy closely, but.melts at 250", whilst that from a-naph-thy lamine has a yellowish-brown colour in sulphuric acid solution.The yield does not, a s a rule, amount to more than 50 per cent.The constitution of these colouring matters has not yet been ascer-tained, but they are probably formed in a similar manner to thequinoneanilides. H. G . C.Naphthoic Acids. By d. G. EKSTRBND ( J . pr. Chem. [2], 42,273-4043 compare Abstr., 1889, 52, 352).-This paper is largely areprint of what bas already appeared. The nitro-p-naphthoic ac!ds arebesf obtained as follows :-/3-Nnphthoic acid is gently warmed withnitric acid of sp.gr. 1.42 (two parts) until red fumes cease to appear, andthe product is washed with water, dissolved in soda, and the sodium sal78 ABSTRACTS OF' GHEMICAL PAPERS.crystallised ; the acids are then liberated from the recrystallised saltsby hydrochloric acid, dissolved in alcohol, and converted into theirethyl salts by dry hydrogen chloride ; the ethyl salts are separated bylight petroleum, in which that of the acid of m.p. 288" is sparinglysoluble, the residue from the mother liqiior being recrystallispd frombenzene, and the mixed tables (ethyl salt of acid OE m. p. 288") andneedles (ethyl salt of acid of m. p. 293") separated by hand.Nitro-p-naphthoic acid (m. p. 293", Abstr., 1885, 905) dissolves in660 parts of alcohol a t the ordinary temperatiire. The bat-ium saltcrystallises with 4 mols. H,O ; the calcium salt (with 34 mnls. H,O)dissolves in 930 parts of water a t the ordin3ry temperature.When t,heacid is oxidised by potassium permanganate, a non-nitrogenons acidis obtained which ci+ystallises in slender needles and melts a t 200" ; i thas not been identified, bnt its formation is a strong indicationthat the nitro- and carboxyl-groups are not in the same benzmenucleus. Nitro-P-naph thoic acid gives no dinitronaphthalene whentreated with nitric acid, whereas ni tro-a-naphthoic acid does. Whenamido-p-naphthoic acid (m. p. 232", Zoc. cit.) is heated with bariumoxide, a-naphthyhniine is ohtained ; thus the constitution of thenitro- acid is [NO, : COOH = 1' : 2 OY 4' : 2). Acetarnido-P-naphthoic acid crystallises in small tables melting a t 291".By the action of chlorine on amido-/3-naphthoic acid (m. p. 232")in hot glacial acetic acid in the presence of iodine, a substance in-soluble in water and alcohol is obtained, which crystallises fromglacial acetic acid in orange needles melting with inturiiescence a t235"; the analysis of this substance agrees fairly well with theformula OH-C,,H,Cl,*COOH ; if the treatment with chlorine is ccjn-tinned, the prodnct crystallises in pale-red needles which melt withintumescence a t 238".By chlorinating the amido-acid in the cold, andtreating the product with sulphurous anliydride, a substance contail)-ing less chloriiie is obtained ; it cr-ystallises in brownish tables whichmelt about 234"; when further chlorinated, it melts a t 237" ; i t sformula is uncertain, but a calcium salt (with 5 mols. H,O) has beenobtained in yellow needles.Two other chlorine derivatives, tht. onecrpstaJlising in orange-red tables and melting a t 220°, and the other,a brick-red powder meltirig at 277", have also been obtainrd.Dinitro-P-naphthoic acid (m. p. 248", Abstr., 1884, 1361) dissolvesin 61 parts of alcohol at the ordinary temperature. The am?nonium(with 1 mol. H,O), sodium (whh 4 mols. H20), barium (with 8 mols.H,O), and calcium (with 5 mols. H20) salts are described. Bytreating this acid with a large excess of hydr.Jgen sulphide in ammo-niacal solution, a dark-brown, infusible powder is obtained ; it cannotbe freed from sulphur, but it appears to be a diimido-p-naphthoicacid, COOH.C,,H,(NH), (compare Abstr., 1889,153 ; 1886, 948 ; 1887,373). From analogy with the dinitro-a-naphthoic acid (m.p. 2(;5"),the author ascribes the constitution [(NO,), : COOH = 1' : 1 : 2 01.4' : 4 : 21 to this acid.Diarrzido-[3-na~hthoic acid, obtained by reducing the above dinitro-acid with ferrous sulphnte in ammonia, crystallises in greenish-yellow iieedles which melt a t 2 0 2 O , and partially sublime ; the calciumsalt and the monohy&-ochlo?-icS;e, me1 ting above 285", were obtainedNitro-/I-naphthoic acid (m. p. 288, Abstr., 1895, 905) diswlves i n390 parts of xlcohol at t,he ordinary temperature. The ethyl saltmelts a t 121', not 122". The anzmonium, Farium (with 8 mols. H,O),and calcium (with 4; mols. H,O) salts are described. Oxidat>ion withpermanganate and treatment of the amido-acid with calcium oxidelead to the si-Lme conclusion as in the case of the /3-nitro-acid (weabove).Calcium amido-8-naphthoate crystallises with 4 mols. H,O,Acetami:do-P-naphthoic acid crystnl!ises in slender needles which meltat 258O ; the diacet!yl deri5afive melts a t 181". Nitrucetnwido-B-naphthoir, acid forms slender needltis melting a t 270". When theamido acid is treated with chlorine in glacial acetic acid in presenceof iodine, a product is obtained which crystallises in colourlessneedles and melt., with intumescence at 258" ; it would appear fromits formula, OH-C,,H4Cl4*C00H, to be a dichloride of a dichloroxy-/3-naphthoic acid. In another experiment, criloiirlew tables of theformula OH*C,,,H,CI,*COOH, and melting a t 237", were obtained.Dinitro-P-naphthoic Rcid (m.p. 22tj0, Abst'r., 1884, 1361) dissolvesin 57 parts of alcohol a t the ordinary temperature ; the amnaoniumsalt (with 1 mol. H,O) dissolves in 285 parts, and the calcium sult(with 4 mols. H,O) in 1740 pnrts of watey a t the ordinary tempern,-ture ; the barium salt (with 6 mols. B,O) is described.Nifranaido-B-n~~hthoic w i d is ohtained by treating an arnrnoniticxlsoliltion of the dinitro-acid (m. p. 226') with hydrogen sulphide,adding a c d c acid, digesting the precipitate with hydrochloric acid,and decomposing the solution thus obtained by ammonia ; it €armsshellate needles and melts a t 235" ; its hydrochloride forms slender,red needles.Diamido-/3-rLaphthoic acid is obtained by reducing the dinitro-acid(m. p. 226") with ferrous sulphate in ammonia; it melts about 230°,but with blackening, and forins small, six-sided crystals.Thecalcium salt (with 44 mols. H,O) arid the dihydrozhloride are de-scribed.The ethyl salt of a third nitro-acid remains in the mother liquorof the benzene solution in the preparation of the above nitro-acid(see beginning of the abstract). The nitro-P-naphthoic ocid corre-sponding with this ethyl salt crrstallises in stellate needle$ whichmelt, although not sharply, a t 285"; the ethyl salt melts a t 75".A. G. B.Dry Distillation of Terpenylic Acid. By C. AMTHOR and G.M ~ ~ L L E R ( J . p ~ . Chmn. [a], 42, 38.5-399).-By the dry distillation ofterpenplic acid, Amthor (Abstr., 1882, 44) obtained a syrupy acid,temcrjlic acid, a lactone boiling at 202 -204', and a lactone, C7HI2O2,boiling at 210-212" ; but Fittig and Kraft (Abstr., 1882,42) obtainedno lactone.100 parts of boiling ether dissolve 3.856 parts of terebic acid, andthe same quantity of cold ether dissolves 1.698 parts ; the Following istherefore a better method for separating this acid from terpenylicacid than that previoiis1.y adopted (loc.cit.) :-The mixed acids areheated to 8O--CO0, at which temperature most of the terebic acidremains unmeited, and is separated from the molten terpenylic acidby filtration through cotton-wool in a hot water funnel ; the terpenjlicThe authors have, therefore, reinvestigated the subject8 0 ABSTRACTS OF OHRMICAL PAPERS.acid is then crystallised from hot water, and again heated until mostof it is melted, when warm water is added and the solution filteredthrough cotton-m~ool ; some of the crystals which separate oncooling are then dried on a microscope slide, heated to 80-90", andexamined under the microwope for any still solid particles of terebicacid. The melting and solution in u-ater are repeated until no moreterebic acid is detected in the crystals exarniriecl in this way.Barium diterpenylate crystallises with 2 mols.H,O (Abst,r., 188.2,43), one of which is lost over sulphuric ;Icid, a8nd both at a hightemperature, although not with out^ partial decomposit>ion.The investigation of the products of the distillation of terpenylicacid was carried out on much the same lines as previously (Abstr.,1882,44) ; the acid was not perfectly dry when distilled, still contain-ing its water of crystallisation (1 mol.).The products isolated weretwacrjlic acid (b. p. 218O), a syrupy acid, and a very small quantity ofother acids; a very little heptalactone (?) (b. p. 210-213'); and1-aiious neutral oils, soluble and insoluble in water, among which wasan oxetone, C13H2,02.Fittig and Kraft probably overlooked the lactone produced i t 1 t h edistillation, having used too little terpenylic acid.Heptolactone boils at, 218" (Vittig and Kraft, 220" ; Anithor,202-204"). A. G. B.Methyldipyridyls. By A. HEUSKR and C. SrroEHn (J. p r . Chem. [el, 42, 429--440).-Anderson (iinnaleu, 105, 344) obtained a sub-stance, which he called parapicoline, by the action of sodium on(impure) picoline.More recently Ahrens, (Abstr., 1889, 59) obtained:L base which he called dipicolyl by tile same process, but his picolinewas not, free from higher tiornologues. The authors have obtained ttpnre product and designate it as aa-dimethSldipyridy1.ax-llimethyZdipt,ridyZ, C12H,,T4'?, is prepared by adding thin strips ofsodium (10 grams) to a-picoline (b. p. 128", 20 grams) in a flaskand gently x x m i n g the mixture, aftev 7-8 days, in a reflux appa-mtus. Water is ihen added to the reaction mass, an operationi-,>quiring great care as unaltered sodium is liable to remain enclosedi l l the mass and to cause an explosion, and the separated oil is distilled ;ammonia and unaltered picoline come off below 150", and then practi-cdly nothitig distils until 300".All that distils above 300" is redistilled,when the greater portion conies over at 303-306" ; this portion isdissolved i n absolute alcohol and converted into hydrocliloride by acarrent of dry hydrogen chloride ; the hydrochloride is recryhtallised,decomposed by aqueous sodium carbonate, and the free base extractedwith ether. This base crystallises from water in large, lustrous,white leaves, with 4 mols. H20, which are lost over sulphui,ic acid;the crystals melt at 37--38", and the anhydrous substance a t 84". Itdissolves i n most solvents ; like other pyridine bases, it is less solublein hot than in cold water, and is separated from its aqueous solutionby a l k a h ; it is specifically Ileavier than water, and has R (aharacteristicodour.I t s solutions give a yellow colour with potassium ferrocyanide,and brown-red tables gradually separate from the solution. The hydro-chloride cry stallises in cvlourless leaves, and dissolves easily in wateORGANIC CHEMISTRY. 81and sparingly in alcohol ; the picrate crystallises in sparingly solubleyellow tables, and melts with decomposition at 240" ; the stannochzorideforms prismatic, yellow needles which melt at 179-180"; the zincsalt and the platinochloride are described; the latter is sparinglysoluble ; the aurochloride €orms needles, darkens at 200°, and meltsat 209--210" (compare Ahrens, Zoc. cit.) : the mercurochloride crystal-lises in serrated leaves which darken at 210" and melt at 220".a- Methy Zd i p j ridy 1- a- carboxy lie acid, C,NH3Me*C,NH3*C 0 0 H, ob-tained by oxidising aa-dimethyldipyridyl with potassium permanga-nate, crystallises in pale yellow needles (with 5 mols.H,O) ; it isfreely soluble in hot water and alcohol, and its solutions give a red-dish-yellow colour with ferrous sulphate ; the anhydrous acid melts at193" giving off carbonic anhydride.mentioned carboxylic acid is heated with glacial acetic acid in asealed tube at 180-190" for 2-3 hours ; the acetic acid is evaporated,and the base liberated by sodium carbonate and extracted with ether.It is more soluble in water than dimethyldipyridyl, and melts at 94" ;it will be treated of in a future communication. A. G. B.a-MethyZdipyridyl, C5NH,Me*C,'NH4, is formed when the abovea-Picoline and dsobutylenepyridine.By C. STOEHR (J. pr.Chem. [ 21, 42, 420-428).-a-Picoline was obtained from animal oilby treating the hydrochloric acid solution of the fraction 128-133"with mercuric chloride and recrystallising the mercurochloride formed.It boils at 128". The platinochloride never contains any water ofcrystallisation, whatever the circumstances under which it is crystal-lised (compare Weidel, Abstr., 1880, 269; Seyfferth, J. pr. Ohern.[2], 34, 241;) ; it crystallises in monoclinic tables, a : b : G =0.6636 : 1 : 0.9078; p = 72" 46' ; it melts with decomposition at195", not 178" (Lnnge, Abstr., 1886, 256 ; and others), and is moresoluble in water than p-picoline plAinochloride. Impure a-picoline(b. p. 138-134") gives a platinoohloride which crystallises with1 mol.H20, melts at 195", and is nearly similar in crystalline form[a : b : c: = 0.9758 : 1 : 1.3270 ; p = 76" 47'1 to the platinochloridepreviously described as that of a-picoline (loc. cit.).a-Isobutylenepyridine, CSHIIN, is obtained by heating a-picoline (8grams) with acetone (5 .grams) and some zinc chloride in a sealed tiibeat 250-260'' for 10 hours ; the product is acidified with hydrochloricacid, extracted with ether, and, after heating to expel ether, distilledwith steam ; solid sodium hydroxide is then added and the liberatedbases distilled, dried by potassium hydroxide, and redistilled. Thegreater part of the distillate, boiling below 140", is unaltered a-picoline ;the rest is twice fractionated, and the portion boiling between 190--210"converted into mercurochloride, from which the isobutylenepyridine is1iberar;ed by potassium hydroxide.It boils at 2OW, is very sparinglysoluble in water, has a blue fluorescence and peculiar odour; itsaqueous solution becomes turbid from separation of the base at thetemperature of the hand, and i t is volatile with steam. Its sp. gr. at0°/4" is 0.9715. The hydrochZoride crystallises in prisms melting at140--141", and soluble in alcohol and water ; the platinochloride formsneedles or prisms (with 2 mols. H20), andbmelts, when anhydrous, atVOL. LX. 82 ABSTRACTS OF CHEMICAL PAPERS.163-164" with decomposition ; the aurochlm'de is unst,able, and meltsa t 135-137" ; the mercurochloride is sparingly soluble, and crystallisesin long, slender, lustrous needles which melt at 144-145"; thepicrate forms small, yellow needles, melts at 1 7 7 O , and is sparinglysoluble.A. G. B.Diethylmuscarinepyridine. By H. LOCHERT ( BZC ZZ. SOC. Chim.f 31, 3, 858-86 1) .-Dieth y hnuscarinep y r i d iize bro Pn ideC5NH,Br*CH2*CH( OEt),,is obtained by heating a mixture of bromacetal and pyridine, in mole-cular proportion, at 80" for 10 days ; on cooling, the compound crystal-lises out in deliquescent, nacreous scales which are very soluble in waterand in alcohol. With platinum tetrabromide, it forms a red, amorphousprecipitate, which is almost insoluble in water, completely insolublein alcohol.On treating diethylmuscarinepyridine bromide in aqueous solutionwith moist silver oxide, a colourless, strongly alkaline liquid is obtained,which neither crystallises on coilcentration nor forms crystallinesalts, concentration of the solutions yielding syrupy liquids.Di-ethyZmuscarinepyridine, OH.C,NH,.CH,.CH( GEt),, as thus obtained,precipitates the hydroxides of silver and of copper from solutions oftheir salts.Further communications on other muscarine derivatives are pro-mised, as also on the synthesis of muscarine itself by means ofhromacetal and trimethylamine. T. G. N.Tribromoquinolines. By A. CLAUS and P. HEERMANN (J. pr.Chem. [S], 42, 327-346).-The generic similarity between 3 : 4'-dibromoquinoline and the tribromoquinoline described by Claus andWelter (Abstr., 1890, 1320), and the fact that the latter can beobtained by brominating 4'-bromoquinoline, fiettles the orientation oftwo of the bromine atoms in this tribromoquinoline.The position ofthe third bromine atom is now settled, for the authors have succeededin obtaining the same tribromoquinoline by heating I : 3-dibromo-quinoline hydrobromide dibromide according to Claus' ar~d Col-lischonn's method (Abstr., 188'7, 158) ; this is therefore 1 : 3 : 4'-tribromoquiwoline. This conclusion is supported by the fact thatquinoline-3-sulphonic acid and quinoline-1-sulphonic acid both givethis tribromoquinoline when they are brominated, for it is knownthat the first bromine atom enters into the 4'-position. It is to benoted that Clam and Riittner (Abstr., 1887, 278) were not workingwith pure quinoline-1-sulphonic acid when they obtained a tribromo-quinoline of melting point 198", but with a mixture of this andquinoline-4-sulphonic acid, which by their method yielded only3 : 4 : 4'-tribromoquinoline ; that the tribromoquinoline obtained byClaus and Zuschlag (Abstr., 1890, 267), melting at 185O, is a mixtureof 1 : 3 : 4'- and 3 : 4 : 4'-tribromoquinolines; and that Lubavin's(Bedstein, 3, 749) tribromoquinoline (rn.p. 173-175") is impure1 : 3 : 4-tribrornoquinolineORGANIC CHEAIISTRY. 831 : 4 : 4'-TribrornoquiizoZine is obtained by heating the hydrobromidedibromide of 1 : 4-dibromoquinoline (m. p. 127", Abstr., 1890, 172),and fractionally precipitating the acetic acid solution of the residueby the method already given. It forms small needles when crystal-lised and large needles when sublimed; it melts at 168-168-5"(uncorr.), and dissolves in most organic solvents.Its salts with thestronger mineral acids crystallise well, but are dissociated by water.The pZatinochloride forms orange-red crystals, which are dissociatedby water and alcohol. Two nitro-derivatives, melting at 197" (uncorr.) and 157" (uncorr.) respectively,and soluble and insoluble in alcohol, respectively, have been obtained.This tribromoquinoline is also obtained by brominating 4 : I-bromo-qninolinesulphonic acid (Abstr., 1890,267) ; if too much bromine (above2 mols.) is used, a tetrabromoquinoline melting at 198" is also formed,and the constitution of this is evidently 1 : 3 : 4 : 4'-tetrabromoguinoZine.It is identical with the tetrabromoquinoline obtained by Claus andWelter (Abstr., 1890, 1320), and is perhaps the compound (m.p.198") obtained by Claus and Euttner, and described by them as atribromoquinoline (see above)Claus and Posselt (Abstr., 1890, 5221) studied the action of phos-phorm pentabromide on 1 : 4-hydroxyquinolinesulphonic acid at 130"and 160", and obtained substances which they described as a bromo-yuinolinesulphonic bromide and a tribromoquinoline, respectively.Closer investigation has now shown that both these substances stillcontain the hydroxyl group, being 1-hydroxy-? : 4-bromoquinoline-sulphonic bromide and 1-hydroxy-3 : 4 : 4'-tribromoquinoline respec-tively, and not the aforesaid compounds.1-hydroxy-3 : 4 : 4'-tribromoqzcino&ae crystallises in long, brilliant,lustrous, colourless needles, and melts at 172-173", not 168"; itsbasic properties are inappreciable, for it forms no platinochlorideor methiodide, but yields metallic derivatives with the alkalis and theheavy metals.When 1-hydroxy-? : 4-bromoquinolinesulphonic acid is treated withtin arid hydrochloric acid, the hydroxyl group is reduced, and theh ydroquinoline-4-sulphonic acid, CSNHlo*S03H, described by Lellmann,is obtained; it crystallises with 1 mol.HzO, and melts at 315"(uncorr.) ; its pofassium salt was obtained.By E. CARLTER and A. EINHORN ( Bw.,23, 2894-2897) .-2'-Quinolylacetaldehyde may be prepared by theelectrolysis of 2'-quinolyl-a-hydroxypropionic acid, or by the actionof concentrated sulphuric acid.On treating quinolylhydroxypropionicacid with a, glacial acetic acid solution of bromine, dibromoquinoZyl-acetaldehyde is formed, melting at 180". The phenylhydrasone crystal-lises from alcohol in prisms which melt at 168-169". The oairnecrystallises in white needles melting at 235-237". By the action ofphosphorus pentachloride on the aldehyde, 2'-w-dichZoroethyZquinoZine,C9NH6.CHz*CHC12, is formed, crystallising froin ether or alcohol inwhite needles which melt at 80".'L'-3'-DiquinoZyZ is prepared from orthamidobenzaldehyde andquinolylacetaldehyde ; it cryetallises from alcohol in white plates,No methiodide has been obtained.A. G. B.2'-Quinol~lacetaldehyde.a 84 ABSTRACTS OF CHENICAL PAPERS.melting at 175*5", and is identical with the compound obtained byWeidel by the action of sodium on quinoline.2'-QuinoZylucetic acid is formed by the oxidation of the aldehyde, orby fusion with potassium hydroxide ; it crgstallises from alcohol inwhite needles which melt at 275", and may be sublimed withoutdecomposition. The hydrochloride melts at 243'.The cukiunz suZtforms a white, crystalline powder; the silver salt decomposes onexposure to light, and yields quinaldine on distillation in an atmo-sphere of hydrogen; it is also formed by heating the calcium saltwith calcium oxide.2'- QuinoZyZpropionic acid, CgN*H6.CH2*CH2*COOH, is prepared bythe reduction of quinolylacrylic acid with sodium amalgam ; itcrystallises from water or alcohol in needles which melt a t 115-116".The ethyZ calt crystallises from light petroleum in needles whichmelt at 116".2'- Quinoly ldibromopro23ionic acid, CgNH6*CHBr.CHBr*COOH, isformed by the action of bromine 011 quinolylacrylic acid ; it cyystal-lises from glacial acetic: acid in white prisms which melt at 180-181".If this compound is dissolved in an alkaline carbonate solution, anddistilled in a current of steam, 2'-~z~inoZylucet~lene, CgNH6*CiCH, isformed ; this is an oily liquid, and yields 2'-qui~iolyldibro~?-~etlzylene,CgNH6*CBr:CHBr, which is deposited from ether in nodular crystalsmelting at 63-64".By the action of excess of bromine on thiscompound, a perbromide is obtained, which crystallises in prisms, andmelts at 195-196".2'- QZLirLoZy Zdihydrox~propiollic acid, CgNH6*CH( OH)*CH( OH)G 0 OH,is prepared by the oxidation of quinolylacrylic acid with a dilute solu-ticrn of potassium permanganate at low temperatures ; it crystallisesfrom water or alcohol in prisms which melt at 113" ; the ethyl saltforms prisms melting at 110.5".Nitro- and Chloro-derivatives of p-Methyl- 8-oxyquinazoline(Anhydroacetylorthamidobenzamide).By L. H. DEHOFF ( J . p.Chem. [2], 42, 346-360 ; compare Abstr., 1887, 1043).--Nitro-/3-i,zethyZ-6-oxyquiiaazoline is obtained by nitrating /3-methyl-8-oxyquin-azoline with nitric acid (sp. gr. 1.5) at the boiling point, and evnpo-rating. It crystalliscs from hot water as a white powder ; it beginst o darken at 230", but is not further changed till 28U" ; when heatedon platinum foil, it explodes feebly ; it dissolves in aqueous alcoholand alkalis, but not in ether or benzene.Its solution in ammoniagives a white silver compound when precipitated with silver nitrate,but is not precipitated by the salts of other heavy metals. It crystal-lises unchanged from hot strong hydrochloric acid. The methylc o ~ ~ p o ~ i n d forms small, slender, white needles melting at 165".No inonochloro-derivative has been obtained.Tetrachloro-/3-methyZ-B-oxyquinazoline is prod uced bey mixing theoxyquinasoline (6 grams) with phosphoric chloride (25 grams), dis-solving the mixtcre in phosphorous chloride (10 grams), and heatingfor 12 hours a t 170"; the excess of the phosphorus chlorides isdistilled off, and the residue washed with soda solution, and crystal-lised from alcohol ; the yield is 53 per cent.It crystallises in whiteNo other salts could be obtained.J. €3. TORGANIC CHEMISTRY. 85needles which melt at 124-125", and a.re insoluble in water, butsoluble in most other solvents.When the tetrachloro-derivative is evaporated with alcoholicpotash, and the residue dissolved in water, filtered, and treated withdilute sulphuric acid, a precipitate is obtained which crystallises fromalcohol in yellowish prisms melting at 206-207" ; the formula ofthis substance is C9H4CI,Nz-OH. The ethyZ compound, CgH4CI,N2*OEt,is obtained at tJhe same time, being left, undissolved by the water ; itcrystallises from alcohol in soft, lustrous, white needles melting a t75-76".The amide, C9H4C1,N2.NH2, is obtained by heating thetetrachloro-derivative wit,h alcohDlic ammonia a t 150-160" for 2-3hours; the reaction mass is washed with water, and heated withalcohol and animal charcoal ; the alcdholic solution is then precipi-tated with water. The amide crystallises in needles which blackena t 178", and melt a t 183-184"; it dissolves in dilute alcohol andbenzene, but not in ether, liyht petroleum, o r water; its h y d ~ o -chloride blackens and decompo,ces about 'LOO". A inethylaminederivative, C9H4Cl,Nz*NHMe, was obtained by heating the tetrachloro-derivative with methylamine a t 110" ; it forms white, microscopicneedles (with 1 mol. HzOj, which soften a t 149", and melt at 155".An anilide, CgH4Cl3N2*NHHh, was also obtained ; it crystallises (with1 mol.alcohol) in thick, white, rhombic tables.A consideration of the above compounds leads to the conclusionthat tetrachloro-~-methyl-6-oxyquinasoline contains one atom ofchlorine situated differentlv from the other three, and as this atom iseasily replaced, it cannot be in the benzene nucleus; the author,therefore, ascribes the formula C6HCl,< ccl:r to the tetrachloro-N r C M ederivative. The above-described ethyl and amido-compounds willthus be trichloro -P -methyl - 6- ethoxyquinazoline and trichloro - p-methyl-8-amidoquinazoline, respectively. It is, however, still an openquestion whether P-methyl-6-oxyquinazoline is really a hydroxy- oran oxy-derivative (Ahstr., 1887, 1043). When the tetrachloro-derivative is reduced with hydriodic acid, p-methyl-6-oxyquinazolineis obtained ; p-methylquinaxoline is probably formed, but oxidises a tonce to the oxy-compound.Papaveroline.By I(. KRAUSS ( J f ~ m t s h . , 11, 350-362 ; compareAbstr., 1869,166,167 ; 1887, lll6).-The hydriodide of this base hasbeen prepared by Goldschmiedt by the action of concentrated hydr-iodic acid on papaverine, in presence of amorphous phosphoriis,When a solution of sodium hydrogen carbonate, saturated withcarbonic anhydride, is added to the hydriodide, tlie free base,C16H13N04,2H20, is precipitated as an almost colourless, crystallinepowder, which, when dried in a vacuum, is perfectly stable, and con-tains 2 mols. HzO, which are given up at 100". Heated to 150°, itdarkens i n colour, and, on raising the temperature to 210°, becomesquite black, without having previously melted.The base dissolvesreadily in mineral acids, i n oxalic acid, and in alcohol, and is verysoluble in acetic acid and in glycerol. Dilute potash turns an alco-holic Bolution blue ; strong potash produces a dark-violet coloration.A. G. B86 ABSTRACTS OF CHEMICAL PAPERSThe hydrochloride, CI6Rl3NOa,HC1 + H20, crystallises in whit.eneedles, soluble in hot water ; the sulphate, ( C16H13NOa)2,H2S04 +8+H20, is only slightly soluble in water ; the oxalate,crystallises from water in spherical aggregates of needles.On distillation Tvith zinc-dust in a stream of hydrogen, the authorexpect,ed to obtain a-benzylisoquinoline. Instead of this, dibenzyldi-isoquinoline, (c16H12N)z, and a-methylisoquinoline were formed.Theformer is insoluble in dilute hydrochloric acid, dissolves readily inether, light petroleum, acetic acid, and benzene, and when crystallisedfrom alcohol, melts constantly a t 234-235"; the latter is an oil,which dissolves in dilute hydrochloric acid, and furnishes a platino-chloride, ( C,oH,N)2,H,PtC~6 + l$HzO, which, after liecrystallieationfrom water, melts at 229", and a crystalline picrate which commencesto sinter at 198", and melts at 209-210". G. T. M.Strychnine. By C. STOEHR (J. p ~ . Chenz. [2], 42, 399-415).-Most of the analyses of strychnine which have been made agree withthe formula C2,H2,N202. The author has prepared and analysedstrychnine hydrochloride (with 14 mols.HzO), of which he givescrystallographical measurements, and its platinochloride ; also strych -nine hydrobromide (with 1 mol. H20) and hydriodide (with 1 mol.H20) ; his analyses confirm the above formula for strychnine and thegenerally accepted formule for these salts. Pure commercial strych-nine melted at 265-266" ; by converting this into the hydrochloride,reconverting the latter into strychnine, crystallising from alcohol, andpulverising the crystals, a light powder was obtained which darkenedat 260°, and was a dark bl-ownish-yellow liquid at 269". Claus andGlassner give the melting point of strychnine as 284" (Abstr., 1881,747) ; Beckurts as 255" (uncorr., Abstr., 1885, 675) ; Loebish andSchoop as 268" (Monatsh., 6, 858) ; Beckurts as 265" (Abstr., 1890,1328) ; and Garzarolli-Thurnlackh as 262" (Monatsh., 10, 1).The author has again investigated the distillation of strychninewith lime (compare Abstr., 1887, 604, 682 ; 1888, 63), and has againfound that hydrogen, ethylene, ammonia, ethylamine, scatole, p-pico-line, and, probably, ethylpyridirie are produced.As the i3-picolinethus obtained seems to be identical with that obtained from othersources, it may be allowed that all /3-picolines at present known areidentical, whatever their source (compare Ladenburg, Abst'r., 1890,1432).To obtain trichlorostrgchnine (Abstr., 1887, 604) dry, powderedstrychnine hydrochloride is heated with phosphoric chloride(&5 parts) and chloroform in a reflux apparatus on the water-bathas long as hydrogen chloride is evolved ; water is then added, and thechloroform distilled off; ammonia is added, the liquid extracted withether, and the ether residue crystallised from alcohol containinghydrochloric acid. It gives much the same reaction as strychninewith potassium dichromate and sulphuric acid, and a similar colourwith nitric and sulphuric acids.When an excess of phosphoric chloride (7-8 parts) is used, ORGANIC CHEMISTRI'. 87higher chlorinated derivative is obtained ; after distilling off thechloroform, an insoluble mass is left which is extracted with benzene.This derivative crystallises in long, slender, colourless needles whenabsolute alcohol is added to the hot benzene solution ; its compositionis in approximate agreement with a pentachlorostrychnine ; it darkensand melts at 224"; it does not give the same reaction as trichloro-strychnine with nitric and sulphuric acids.Brucine.By L. BEREND and C. STOEHR (J. pr. Chern., 42,41 5-420).-De Coninck (Abstr., 1882, 739) distilled brucine withpotash, but obtained no homologues lower than lutidine.The gaseous products of the distillation of brucine with slaked limewere hydrogen, ammonia, and ethylene. The distillate was at first a,colourless liquid with a yellow oil suspended in it? but i t rapidlybecame brownish-red in air; it WHS acidified with hydrochloric acidand distilled in steam, whereby a few drops of scatole were obtained,but the bulkof the liquid did not distil. The liquid was shaken withether, and then solid potash was added t o it until all the oily baseshad separated; these were then dissolved in ether.The aqueousliquid contained ammonia and methylamine, while the bases irr theethereal solution were found to be mainly P-picoline and a lutidine,probably p-ethylpyridine, together with smaller quantities of otherpyridirie bases ; quinoline bases were absent. The ,%picoline boiledat 142-143', and was identical with that obtained from strychnineA. G. B.(previous abstract) ; its sp. gr. at 0"/4" was 0.9756 (Zanoni, 0'9771).A. G. B.Alkaloids of Veratrum album. By C. PEHKSCHEN (J. Pharm.[ 5 ] , 22, 265-269 ; from Pharm. Z e d . RUSS., 29, 339).-The rhizomeof the wild plant gives 0.57 to 0.66 per cent. of mixed alkalo'ids,whilst the cultivated rhizome yields only 0.29 per cent.Thepowdered root is macerated with dcohol during six days at theordinary temperature, and this repeated a second and third time, thelast time with the addition of acetic acid. The first alcoholic extractis faintly acid from the presence of jervic: acid. The alcoholic soln-tions are united, and the major portion of the alcohol is removed bydistillation under reduced pressure ; on the addition of 3 to 4 vols. ofboiling water, resinous substances are precipitated, which are re-moved by filtration. The remaining resinous and colouring mattersitre removed by agitation with ether. Hydrogen sodium carbonate isthen added to alkaline reaction, then ether, and subsequently chloro-form. When the ether and chloroform solutions are evaporated, themixed alkaloids are left, and these on being treated with absoluteether, give veratroidine and a minute amount of jervine in solution,whilst the insoluble portion contains jervine and a third alkaloid,pseudojervine. Veratroi'di?ze, C32H53N09, melts about 149", and charsabout 172".Atl 22.5", 1 part dissolves in13 parts of benzene, 5.9 of chloroform, and 9.09 of absolute ether. Itdissolves in alcohol in almost all proportions. Veratroidine yieldsamorphous salts with hydrochloric, hydrobrornic, sulphuric, nitric,oxalic, and acetic acids. Most of the general reagents for alkalo'idsgive with this base more or less of a precipitate, according to theIt is optically inactive88 ABSTRACTS OF UHEMICAL PAPERS.state of concentration.A hydrochloric solution of 1 : 5000 gives IZfaint turbidity with mercury potassium iodide, and a solution of1 : 3500 a turbidity with phosphomolybdic acid. With concentratedsulphuric acid, veratro'idine gives a jeliow liquid which passes throughorange-red to cherry-red, with a green fluorescencc, whilst concen-trated nitric acid produces a transient rose colour which soon passesto citron-yellow. Hydrochloric acid (11.0 per cent. is best) gives abeautiful rose coloration ; this serves to distinguish veratroldinc fromveratrine. Veratroidine, when heated at 120" with ethyl iodide in asealed tube for 40 hours, yields the compound C,,H,,NO,,'LEtI. Pseudo-jervine, CznH4,NOlz, forms large, rhombic crystals. The root does notconta,in more than 0.006 per cent.The alkalojid begins to turn yellow:it 215", and melts at 259" with blackening. It is optically inactive.At 22", 1 part of this base dissolves in 10.876 parts of light petroleum,in 372 parts of benzene, 1021 parts of absolute ether, 4.1 of chioro-form, and 184% of absolute alcohol. With phosphomolybdic acid, asolution of 1 : 10,000 gives a perceptible turbidity ; but with mercurypotassium iodide, the dilut'ion should not exceed 1 : 6000. The purebase gives no colour with either liydrxhloric, nitric, or sulphuricacids, the latter mixed with sugar or with other reagent. Whenmixed with minute quantities of jervine, it gives the colorationreactions described as characteristic of i t by Wright and Luff.Jervine, Cl4HzZNO2, crystallises from a boiling alcoliolic solution inbeautiful white needles.It melts a t 237*7", and is slightly levorotary.A t 25", 1 part of the base dissolves in 1658 parts of benzene, in268 parts of absolute ether, in 60 of chloroform, and 16.8 partsof absolute alcohol. The base is insoluble in light petroleum,and very slightly soliible in ethyl acetate, water, and carbon bi-sulphide. Beautiful rhombic crystals of the normal hydrochloride,with 0, mols. H,O, are obtained by mixing an alcoholic solution ofthe base with an alcoholic solution of hydrogen chloride ; sulphuricacid gives an acid salt under the like conditions. Jervine is cha-racterised by the violet coloraticn, passing to blue, which it giveswith sulphuric acid and sugar ; veratroydine, with this test, gives abrown coloration.J. T.Benzyl Derivatives of Piperidine, Tetrahy droquinoline, andPyridine. A New Method of Formation of Benzyleneimides.By E. LELLMANN and H. PEKRUN (ArznaZen, 259,40--6I).-Para~~itro-benzyZpiperidine, NOZ*CGH4-CH2-C5NHl0, is obtained when piperidine isgradually treated with paranitrobenzyl chloride in well-cooled alco-holic solution, the mixture then boiled for about an hour, and thehydrochloride thus produced decomposed. with water. It crystallisesfrom light petroleum in large, amber-coloured plates, inelts a t 34", andis very readily soluble in mineral acids and most organic solvents, butonly sparingly in water. The hydyochloride, ClzH16NzOz,HC1, crystal-lises from hot alcohol in light-brown prisms, melts a t 236", and isreadily soluble in water, but insoluble in ether, benzene, and lightpetroleum.The PZatinochZoride, ( C12H16NzO~),,H2PtC16, is a yellow,amorphous, unstable conipound.P a m m i d o b e ~ z y ~iperidine, C12HlsN2, is formed when the precedinORQANIG CHEMISTRY, 89compound is reduced with tin a n i hydrochloric acid ; the product is.distilled with steam and recrystallised from hot light petroleum, fromwhich it separates in colourless needles melting at 87". It is readilysoluble in most ordinary solvents except water. The hydrochzoride,CIzH18N2,2HC1, crystallises in yellow needles and is very readilysoluble in water.DimethyZanilineazobenzylpiperidine, NMe,.C6B,*N2.C6H4gCH2.C5NH10~is produced when a solution of paramidobenzylpiperidine in well-cooled concentrated hydrochloric acid is treated first with sodiumnitrite, and then with dimethylaniline. It crystallises from alcohol ingolden needles, melts a t log", and dissolves in dilute acids, yielding adark-violet solution, the colour of which changes to yellow on theaddition of water; it is readily soluble in the ordinary organicsolvents, but only eparingly soluble in water.The hydrochloridecrystallises from alcohol in small, bluish-black needles, and itsaqueous solution imparts to silk and wool a yellow coloration.ob-tained, mixed, however, with paramidobenzylpiperidine, when thebrown light petroleum mother liquors obtained i n the purification ofthe last-named compound are evaporated ; it can be purified by con-verting it into the hydrochloride.It crgstallises from light petr-oleum in colourless needles melting a t 76-76-5". The hydroch7oride,CI2H,,ClNZ,2HCl, forms yellow, well-defined, transparent crystals.Orthonitrobenzy723iperidine, Cl2HI6N2O2, prepared as described in thecase of the corresponding para-compound, is a thick, yellow oilhaving an odour recalling that of piperidine; it is soluble inmineral acids and most ordinary organic solvents. The hydrocAZoride,C12Hl,N20,,HCl, separates from hot alcohol in well-defined, yellowish-green, transparent crystals, sinters together a t 124", and melts com-pletely a t 209". The pZatinochlo~ide, ( Cl,Hl,N202)2,HzPtC16, is ayellow, amorphous compound.O r t h a m i d o b e ~ , z y ~ i e r i d i ~ e , CI2Hl8N2, crystallises from hot lightpetroleum in almost colourless, rhombic plates, melts a t 82*5", and isreadily soluble in mineral acids, alcohol, benzene, &c., but moresparingly in water.Metanit~oBenzy~iperidine, CI2Hl6N2O2, is an oil, and resembles theisomerides described above in its behaviour with solvents.Thehydrochloride separates from alcohol in yellow, rhombic crystals.The platinochZoride, ( C12Hl,N,0,),, H,PtCI,, is yellow and amorphous,Nr'etnmidobenzyZpiperidine, C,,H,,N,, ci-ystallises from light petr-oleum in colourless needles: and melts a t 112".Paranitrobenzyltetrahydi-oquinoline, N02-C6H4*CHP*CONH10, can beobtained by heating paranitrobenzyl chloride (1 mol.) with tetra-hydroquinoline (2 mols.) for 1 to d hours in alcoholic solution, anddecomposing the salt thus produced, with water ; it cr~stallises fromhot alcohol or ether in long, bright-red prisms melting at 102".Theplatinochloride, (C16~,,~z0z)2,H2PtC~,, is a sparingly soluble, yellowish-red compound. The corresponding ortho-compound crystallises inbrownish-red plates, melts at ill", and forms a yellow, amorphouspZatinochZoride. The meta-base crystallises from alcohol in short, redprisms, melts at 99", and is only moderately easily soluble in ether,Pur amidoch 1 or0 benz y lpiperidin e, NH3* C 6H 3C 1- C H2*C5NHlo, i90 ABSTRACTS OF UHEMICAL PAPERS.cold alcohol, chloroform, and dilute acids. The three nitrobenzyl-tetrahydroquinolines are only feeble bases, and their hydrochloridesare decomposed by water ; they give Konig's reaction for tetrahydro-quinoline with oxidising agents, and on reduction they yieldi thecorresponding amido-compounds, of which the meta-derivative,NH2-C6Hi*CH2*NC9Hlo, is crystalline, and melts at 82".Paranitrob enz y lp yridin P, chloride, N02*C6H4.CH2*C5NH5C1, is formedwhen paranitrobenzgl chloride is warmed with excess of pyridine. Itcrystallises from alcohol in yellow prisms, sinters together at aboutgo", melts at about 103", and is readily soluble in water, alcohol, ben-zene, and mineral acids, but only very sparingly in ether and lightpetroleum.The platinochloride, ( C12H11 N202C1)2, Pt C Ip, crystallisesfrom dilute hydrochloric acid in golden plates, and melts at 220-223"with decomposition.Paramido benz y 7p y ridin e chloride 72 ydrochloride, C12H13N2C1,HC1, isobtained in yellow crystals when the nitro-compound is reduced withtin and hydrochloric acid.It melts at 183-185", decomposes at200-202", and is only sparingly soluble in alcohol. When treatedwith alkalis, it yields a yellowish, resinous compound which does notmelt below 280", and when heated at 210-220" it is decomposed intothe hydrochlorides of pyridine and parabenzyleneimide. The platino-chloride, (C12Hl,N2C1)2,H2PtC16, is crystalline.Orthonitrobenzy ~ y r i d i n e chloride, Cl2Hl1N2O,C1, prepared by heatingpyridine with orthonitrobenzyl chloride, crystallises from alcohol andether in yellowish prisms, melts at about 76", and gradually decom-poses at a higher temperature ; it resembles the corresponding para-compound in its behaviour with solvents.The platinochloride,(C,2HllN202C1)2,PtC14, crystallises in yellow scales.Orthn?nidobenzy~~riai~ae chloride hydrochloride, C12H,,N2C1,HC1, is acolourless, semi-crystalline powder, wbich melts a t about 169" anddecomposes at a higher temperature, yielding orthobenzyleneimide ;the last-named compound is a reddish-brown powder which does notmelt below 290".Metanitro bennsy lp yridine chloride, C12HllN202CI, crys t allises fromalcoholic ether in yellow needles, sinters together at 60°, and meltsco tupletely at 100". The platinochloride, (C12HllN202Cl)2,PtC14,crystallises in small, yellow needles. Metamidobenzylpyridine chlorideir ydrochloride, C,,H1,N2C1,HC1, is a colourless powder which melts atabout 220" with decomposition.Metabenzyleneimide, C6Ha< bEi is obtained, together with pyr-idine hydrochloride, when the preceding compound is heated at230" ; it is a yellow, amorphous powder melting at 120-145". Theylatinochloride has the composition (C,H7N),,H2PtCl6.Molecularweight determinations by Raoult's method gave results which showedt h a t parabenzyleneimide is probably a, polymeride of a compound ofthe molecular formula C,H,N. F. S. K.Tropidine. By A. EINHORN (Ber., 23, 2889-2894).-By theaction of aqueous hypochlorous acid on tropidine, t w o compoundsare formed, and may be separated by recrystallisation from diluteNORGANIC CHEXISTRY. 9 1alcohol ; the one is deposited in long, lustrous prisms which melt at138" ; the second is more soluble, separates in white, nodular crystalsmelting at 108-log", and has the formula C,H,,N,HOCl.On heating tropidine with ft glacial acetic acid solution of hydro-bromic acid in R sealed tube at loo", the salts of two isomerichydrobromotropidine hydrobromides are formed, and may be sepa-rated by crystallisation from alcohol ; the more insoluble is termedthe a-compound, and the second the P-compound.a-Hydrobromo-tropidine hydrobromide, C,H14NBr,HBr, is obtained as the chief pro-duct if the heating is continued for 70 hours; it is very soluble inwater, and crystallises in transparent prisms which melt at 219-220".The f r e e base is liberated by the action of aqueous soda./3-?jdro-bromotropidine hydrobromide, CgH14NBr,HBr + H,O, is formed i f thereaction is allowed to proce'ed for only 24 hours ; it crystallises fromalcohol in lustrous, prismatic needles melting at 113-114" ; onheating to 105", the anhydrous compound is obtained, which differs,however, from the a-derivative. The frea base is formed by theaction of alkalis ; on treating it first with anhydrous sodium acetateand then with aqueous soda, a small quantity of a base is obtainedwhich yields a platinochloride melting at 200" ; tropine platinochloridenielts at the same temperature. The author suggests that the com-pound prepared by Ladenburg (compare Abstr., 1890, 1167), by theaction of hydrobromic acid on tropidine at low temperatures, is reallyideii tical with p-hy drobromotropicline.Tropidirhe &bromide, CsHr,NBr,, is prepared by treating a glacidacetic acid solution of tropidine with excess of bromine dissolved inthe same medium ; the oil which separates is washed with sulphurousacid ; on the addition of potassium carbonate, the dibromide sepa-rates.On adding water to the alcoholic solution, it crystallises out insmall, lustrous plates which melt at 66-67.5" with previous softening.On boiling the dibromide with dilute sodium hydroxide solution, a pene-trating, aromatic odour is produced which greatly resembles that. ofdihydrobenzaldehyde (compare this vol., p. 67). J. B. T.Aconitine. By A. LUIIBE (Chem. Centr., llr90, ii, 148-149 ; fromApoth. Zeit., 5, 321).-From the tubers of the Japanese plant Kusa-uzu, the author has extracted, by means of Duquesnel's method,a n alkaloid of the formula C33H44NOll,, which he considers t o be iden-t,ical with the alkaloid obtained from Aconitum napellus. Wright'sformula for aconitine is C3,Hf,,NO1,, whilst that of Jurgens is C33H47N0,2.Aconitine forms radially fibrous groups of crystds of the rhombicsystem. The crystals measured by the author had the followingfaces :-Obtained from the cold saturated solutioz, mPm, mP, OP ;from the hot saturated solution, mP, mPm, OP, Pw, P.At 110",it is partially decomposed; it melts a t 183-184"; [a]=, -34.46.The taste is not bitter, but prickly and burning. The most delicatereagents for acoiiitine are hydrogen iodide and potassium mercuryiodide. The hydriodide, even when present in very small quantity(0.02 milligram), appears crystalline under the microscope.Pseudo-aconitine could not be detected. The author finds that aconitine hasthe same physiological properties as are ascribed to i t by Lewins92 ABSTRACTS OF CHEMICAL PAPERS.acting on the extremities of certain nerves. It does not appearitself to undergo any change, nor does it in any way decompose theblood corpuscles.From the tubers of Langaard's variety, " Shirakawauzuware " ofAconitum sineme, the author obtained 0.02 per cent. of a crystallinealkalo'id and two amorphous bases. He considers the alkalo'id to beidentical with aconitine from Aconitunz napeZZus; it melts at 180.9".Pseudoaconit'ine could not be detected.J. IV. L.Hydrastine. By M. FREUND and M. HEIM (Ber., 23, 2897-29lO).-It has previoiisly been shown (Abstr., 1890, 532) that alkyl-hydrastines are formed by the action of alkalis on the additive corn-pounds of hydrastine and alkyl halo'ids ; aqueous ammonia, reacts in asimilar manner in the cold, but on boiling an alcoholic solution ofhydrastine methiodide with concentrated aqueous ammonia, a com-pound is obtained crystallising from alcohol in white, strongtyrefractive, rhombic plates which melt a t lSO", are almost insoluble 111water, and dissolve sparingly in ether, carbon bisulphide, o r benzene.The substance is a powerful base, arid decomposes ammonium salts ;it has the formula C2,H2,N206, and the author proposes to term it?nethyZh~cZrastamidL..It may also be obtained by the action ofammoiiin on methylhydrastine. The salts of the amide are somewhatdifficult to prepare, as they readily part, with the elements of water.The picrate crystdlises from alcohol in small, yellow needles. Thehydrochlode, C22H26N206,HC1 + 2H,O, is deposited in white needleswhich melt a t ll6--l1So.Meth~Zl2ydrastinaide, C22H24N205, is prepared by the action of diluteacids, or of concentrated potassium hydroxide solution, on the amide ;i t crystallises from alcohol i n slender, light-yellow needles whichmelt a t IW", and are insoluble in water. The hydrochloride,C,,H,,N,O,,HCl, crystallises from absoln te alcohol in slightly yellowneedles which melt at 227"; a hydrated salt melting a t 110-120"may also be obtained.The platinochloride crystallises from hydro-chloric acid in brown rhombohedra melting at 20.5' with decomposi-tion. The sulphate is deposited from alcohol in yellow crystals whichmelt a t 218". The nitrate, C22H2AN,03,HN0, + H20, crystallises i 3slender needles which decompose a t about 230".Hemipinimide, C,H,(o&fe)2<Co>NH, is formed by the oxida-tion of methylhydrastamide with dilute nitric acid.Ethy Zhydrastarnide, C23H2eN,06, is prepared by the action ofammonia on hydrastine ethiodide, and is more readily soluble inalcohol than the methyl derivative ; it orystullises in rhombic plateswhich melt at 140".EtAyZhydrustimide, C2:%H24N205, is obtained on treating the amidewith dilute acids ; it crystallises from alcohol in rhombohedra whichmelt at 150-151".Methylhydrastimide methiodide, C2,H24N,05,MeI + 1+H,O, is formedby the action of methyl iodide on methylhydrastanride cr methyl-hydrastimide ; it crjstallises from water in yellow, flat rhombohedrawhich melt at 240-245".cORGANIC CHEMISTRY.93The action of amines on the additive compounds of hydrastine andd k y l haloids is stlrictlg analogous to that of ammonia itself. Methyl-hydra.stometh~lamide, C23H?JYzOG, is prepared by heating hydrastinemethiodide with an alcoholic solution of methylamine in a sealedtube at 100"; it crystallises from alcohol in white rhombohedramelting at 182", and is not acted OLL b.y concentlrated aqueous potash.The hydrochzoride crystallises from alcohol in white needles whichmelt at 193".Hemipinomethylimide is formed by the oxidation of thebase with dilute nitric acid. 17lethylhydrastethylamide, C2AH30N206, isobtained by digesting hydrastine methiodide with an alcoholic solu-tion of ethylamine for several days; it forms white crystals whichmelt at 16d0, and yields hemipinethylimide on oxidation. Methyl-hydrastisoanzy7anzide, C27H36N20G, is deposited from alcohol in long,filender crystals which melt at 171". On heating this compound witha. large excess of dilute hydrochloric acid, methylh~dl.astisoamylimide isformed as an oily liquid; the platinochloride is a yellow, crystal-line powder . M e th y 1 h y d r ast a1 1 y Zanzide, Cz5H30N20 6 , cry s t allis es fro malcohol, and melts at 158'. By the action of dilute hydrochloric acid,the corresponding imida is obtained as a viscid liquid which yields acrystalline platinochloride. I n the authors' opinion, the above resultsall tend to confirm the second of the formula? proposed for methyl-hydrastine (loc.cit.) ; the action of ammonia on niethylhydrastine istherefore represented as being strictly analogous to its action onbenzylidenephthalide ; methylhydrastamide and methylhydrastimidewould consequently be represented by the formubNMez*CH,*CH,*C6H,( 0,CH,)*CH2.C0.CGH,(OMe),CO*NII,[CH, : H, : CH, = 1 : 4 : 5 : 6 ; (OMe), : CON€€, : CO = 1 : 2 : 3 : 41CO.P;IHrespec- C6Hz(oMe)2<-- C: CH*C6Hz( O,CH,)*CH,*CH,*NMe,tively. J. B. T.Hydrastine. By .M FREUND and A. PHILIPS (Ber., 23, 2910-291 7 ; compare preceding abstract) .-Hydrastine a1 l y l iodide,C?1HZlNOG, C3H.51,is prepared by treating an alcoholic solution of hydrastine withexcess of ally1 iodide ; it crystallises from water or dilute alcohol insmall, white needles which melt at 193". By the action of potassiumhydroxide (1 mol.) on this compound, allylhydrastine, CaH2JYO6, isformed, crystallising from alcohol and ether i n deep-yellow needleswhich melt at 116". Allylhydrastezne, Cz,H,:NO, + 1$H,O, is pre-pared by boiling allylhydrastine with concentrated aqueous potash,and is deposited from water in white crystals which melt at 136".AllyZhyclrastamide, C24H26N206, is formed b y the prolonged action ofaqueous ammonia on an alcoholic solution of hydrastine ally1 iodide ;i t may be recrystallised from dilute alcohol, and melts at 156".AIZylhyd~nstinvide, CzrHZ6N2Od, is preparpd by the action of diluteacids, or of ccncentrated aqueous potash, on the amide ; it is depositedfrom dilute alcohol in pale-yellow crystals which melt at 139". Th94 ARSTRACTS OF UHEMICAL PAPERS.hydrochloride is obtaiced from alcohol in pale-yellow crystals meltinga t 211". The subhate crystallises from dilute alcohol in small, deep-yellow, slender needles which melt a t 235". Allylhydrastirnide a1 1ytiodide, C27H31N2051, is formed by the action of allyl iodide on allyl-hydrastamide or ally1 hydrastimide ; it crystallises from dilute alcohol,and melts at 207'. On boiling this compound with concentratedaqueous potash, diallylamine is eliminated, and a substance of theformula C,,,H,,NO, is formed, t o which i t is proposed to apply t h eterm hy drastophthalimidine ; it is deposited in deep-yellow crystalswhich melt at 226", and is strictly analogous to the compoundspreviously described (loc. cit.) . Dibromohydrastopht?2alimidiii,e,C,,H,,NO,Br,, is prepared by treating the preceding compound withbromiue (2 mols.) ; and on the addition of light petroleum to itsbenzene solution, it crystallises in pale-yellow plates melting at 158".The constitution of the above compounds corresponds with that ofthe derivatives previously described (Zoc. cit.).Hydrobromanhydroecgonine. By A. EICHENGR~N and A.EINHOEN (Ber., 23,2888) .-Anhydroecgonine hydrochloride is heatedat 100" for 6-7 days with five parts of a solution of hydrogen brom-ide in glacial acetic acid, saturated at 0". The prodnct is allowed tocrystallise, and the crystals treated with hot water; on cooling,hydrobl.oritanhyclroec~o~ine hydrobmmide, C,H14N02Br,HBr, is depo-sited in strongly refractive prisms which melt at 250" with decorn-position, and are very sparingly soluble in water, alcohol, or glacialacetic acid. J. B. T.By E. JAHNS (Ber. 23, 2972-2978) .-The author has previously described the preparation of thetwo alkaloids, nrecolirze, C8H13N 02. and arecaihe, C,H,,NO,, from themeca nut (Abstr., 1889, 420), and mentioned also a third substance,obtained in small quantit,y, the nature of which could not tlhen beascertained. Further investigation has shown that this compound ischoline, which was identified by its pZatinochloride. The lattercrystallises from water in orange-red, anhydrous, monosymmetricplates, and not as stated by Hundeshagen (J. pr. Chem. [2], 28, 246),in rhombic crvstals. The statement of the latter, that the platino-chloride crystallises from dilnte alcohol in anhydrous, yellow octn-hedra is also partially incorrect, as the crystals thus obtained contain1 mol. H20. The anhydrous compound melts with evolution of gasst 225".When arecoline is heated in a sealed tube with hydrochloric acid,or boiled with hydriodic acid, potash, or baryta-water, a methyl groupis eliminated, and a new compound having the composition C7Hl,N0,obtained. This is isomeric with arecaiine, and may therefore betermed arecnSdine. It is most readily prepared by means of baryta-water or hydriodic acid, and crystallises from 60-70 per cent. alcoholin colonrless, four- or six-sided plates which contain 1 mol. H20. Itloses the latter at lOO", and then melts with evolution of gas at292-223", and carbonises on further heating. It is readily solublein water and dilute alcohol, almost insoluble in absolute alcohol,ether, chloroform, and benzene. Its solution is coloured red by aJ. B. T.Alkaloids of the Areca Nut.Choline aurochloride melts at 244-245"ORGANIC CHEMISTRY. 95trace of ferric chloride, and, like arecai'ne, which it closely resemblesin other respects, it is not poisonous.Its platinochzoride, (C7H,,N0,),,H,PtC16, crystallises in yellowoctohedra which melt at 208-209" with evolution of gas, and theazwochloride, C7HllN02,HAuC14, forms four-sided prisms which meltat 197-198".If finely divided areca'idine be suspended in methyl alcohol, andfthe 'tatter saturated with hydrogen chloride, arecoline is re-formed.If ethyl alcohol be substituted for methyl alcohol, arecaidine ethylether, or homarecohe, C91i,5N02, is obtained; this is a colourless,strongly alkaline liquid, miscible with water, alcohol, and ether,distils without decomposition, is volatile with steam, and haspoisonous properties very similar to those of arecoline. Its hydro-chloride crystallises in very hygroscopic needles which deliquescein the air. The other salts are also deliquescenf, and cannot beobtained in crystals. The picrate is an amorphous resinous mass, andthe aurochZoride an oily liquid, sparingly soluble in cold, readily inhot water. The pZat.inoclzloride forms an orange-red, amorphous masswhich has the composition (C9H,5N02)2,H2PtC16, and commences to.decompose at 100".The above reactions show that areca'idine is a monobasic acid, andthat both oxygen atoms are present as carboxyl. This is confirmedby the fact that no acetyl derivatives of areca'idine can be obtained,which should be readily formed it' the oxygen were present ashydroxyl. The formula for arecoline may therefore be partiallyresolved into C6HloN.COOMe. Experiments to determine the com-position of the group C,H,,N are now in progress. H. G. C.Action of Sulphurous Anhydride on Flour. By - BALLAND( J . Pharm. [ 5 ] , 22, 241--244).-The gluten of flour which has beenacted on by sulphurous anhydride loses its cohesion, so that, in placeof 28-30 per cent., not more than 6 or 7 per cent. can be obtained bythe ordinary process of washing, the remainder passing away with thewash water. The gluten is simply modified, not destroyed, as theflonr retains its nu ti-itive properties. Sulphuric and sulphurous acids,and alkaline sulphides, all affect gluten in this way, whilst certaincompounds, such as sodium chloride, alum, and copper sulphate,favour the aggregation of gluten. Perfectly sound and good breadcan be made from the sulphurised flour by mixing with fresh floiirand increasing the proportion of salt and yeast. Biscuit made fromthe defective flour is quite good. J. T.Formation of Carbamide from Albumin. By E. DRECHSEL(Bey., 23, 3096--3102).-The author has previously shown that amixture of several bases is obtained by boiling casein with con-centrated hydrochloric acid and stannous chloride ; the nitrate ofone of these bases forms with silver nitrate an additive compound ofthe formula ~6H13N302,HN03,AgN03, as the salt probably contains amolecule of water of crysta>llisation; the base, which the authorterms Zysatine or Zysatinine, is homologous with creatinine or wit96 ABSTRACTS OF CHEMICAL PAPERS.creatine, and, like the latter, it yields carbamide on boiling withbaryta-water. The author points out the physiological importance ofhis observations, which move. for the first time. that carbarnide mavbe obtained from album& by simple hydrolytic processes. .IJ. B. T