ORGANIC CHEMISTRY. 19Organic C h e m i s t r y .Action of Hydrochloric Acid on the Olefines. By J, A. LEBE L (Cow@. retzd., Ixxxv, 852-854) .--From the action of hydrochloricacid on the butylenes, amylenes and hexylenes, the author has deducedthe following law :-“ The olefines of the constitution CH2YCRR‘, andCHRZCR’R”, in which R,R‘, and R“, arc different or the samealcohol-radicles, combine with hydrochloric acid in the cold, whereasthose of the constitution CH,ZCHR, andprobably CHR = CHR’, arenot attacked thereby.”This law requires to be verified by further examples.L. T. 0’s.6 20 ABSTRACTS OF CHEMICAL PAPERS.Butylene and its Derivatives. Gy E. PUCHOT (Compt. rend.,lxxxv, 757--760).-Butylene [iso-] is prepared by the action of 100parts of sulphuric acid on 100 parts of butyl alcohol in presence of amixture of 40 parts of potassium sulphate and 160 parts of calciumsulphate.It is a gas which condenses at - 40" to a liquid, and rcJ-sembles ethylene in all its properties.By the action of chlorine on bntylene, first a homologixe of ethylenedichloride is obtained, viz., butylene dichloride, C4H8Cl2, in which. hy thefurther action of chlorine ir, direct sunshine, two molecules of hydrogenare replaced, yielding a body having the composition C4H4C16 ; and ifthe action be further continued in sunshine and over a fire, this last,body loses one molecule of hydrogen, which is not replaced by chlorine,the product having the composition CaH2C16.By the action of potash, the first body lost more than 1 molecule ofhydrochloric acid, and the author thinks it probable that by continuallytreating it with fresh quantities of potash, 2 mol.HC1 might be re-moved, leaving a chloride of carbon, CaCI,.The compound C,H,CI,, twice treated with potash, loses 4HC1,leaving C,CI,; and C4H2C1,, which is much more easily attacked byalcoholic potash, also loses 2HC1, and is converted into C4Cla.L. T. 07s.Liquefaction of Acetylene. By CAI L LETET (Cow@. r e d , IXXXV,851-852).-By subjecting acetylene a t 1 8 O to a pressure of 83 atmo-spheres, it is condensed t o a colourless, mobile, refractive liquid,lighter than water, in which it is soluble. It dissolves paraffin andmany fats.The relation which exists between the tensions of the vapours ofacetylene, ethylene and ethane, is as 1 : 2 : 3.Ethane at a temperature of 4' liquefies under a pressure of 4.6 at'mo-spheres.L. T. 0's.Valerylenes from Isobutylcarbinol. By F L A v I T s K Y and K R I-LOFF (BuZl. SOC. Chim. [a], xxviii, 347--348).-By the action ofalcoholic potash on amylene bromide (b.-p. a s 0 ) , a valerylene is ob-tained boiling at 28-30°, and forming compounds with copper andsilver. The latter has the composition C5H7Ag. The product yieldedhy this hydrocarbon on oxidation, together with its mode of formation,lead the authors t o regard 7% as isopropylacetylene.The bromide of trimethylethylene, treated in the same way, yieldsamylene monobromide, and a small quantity of a volatile hydrocarbon,which exhibits no tendency to form compounds with copper andsilver.This valerylene boils a t 34".These researches are not yet complete. c. P. c.Fomnation of Ethers, at Low Temperatures, by means ofHydrochloric Acid. By E. DEMOLF: (Deut. C'lzem. Ges. riel-., x,1790-1791) .-The author has extended the observation of Priedcl,relating to the formation of ethers by the action of hydrochloric acidupon a, mixture of an organic acid with phosphoric anhydride, in preORGANIC CHXMISTRY. 21sence of an alcohol, a t temperatures from SO" to 200", to temperaturesrelatively low. At 0" this reaction between acetic acid and ethyl alcoholis complete : so also with amyl alcohol. The author finds, further, thatby t'he action of dry hydrochloric acid gas upon a mixture of glacialacetic acid and phosphoric anhydride a t 0", acetyl chloride is formed.This is direct evidence in favour of Friedel's view of the production of'ethers by the above reaction being due t o the formation of a chlor-anhydride, which decomposes the alcohol to form a mixed ether.c. I?. c.Boric Ethers. By CONST. COUNCLER (De7ct. C'1Len.L. Qes. Uer., x,1655-1657) .-Ally1 borate combines directly with 6 atoms of bromine.The he&-onde is obtained by gradually mixing solutions of the twosubstances in carbon bisnlphide, distilling off excess of bromine andbisulphide, and passing dry carbon dioxide over the residue. It is athick brownish liquid decomposing below its boiling-point ; non-inflam-mable ; colours feebly luminous flames an intense green. I t s composi-tion agrees with the formula (C3H,Br20),B.When left in contactwith water, it is resolved into boric acid and dibromopropyl alcohol, abody which Markownikoff obtained by direct addition of bromine toally1 alcohol.Ally1 borate reacts with zinc ethide to form a colourless highlyrefractive liquid, boiling a t 110-120", the composition of wliich is notyet made out.Boric anhydride reacts with isobutyl alcohol, when the two areheated to 160-170" in sealed tubes, to form isobutyl borate,(C4H,0),B, a colourless mobile liquid, burning with a green flame,boiling a t 212", and gradually decomposing in contact with water.Boron trichloride, acting on benzyl alcohol, forms dibenzyl.J. R;Action of Certain Oxides on the Chlorhydrin of EthyleneGlycol.By 31. KASCHIRSKY (BtcZZ. Xoc. Chi?n. [el, xxviii, 350).--The author infers from many known reactions the possibility of con-verting the oxides of the olefines into the corresponding isomericaldehydes. By the action of the oxides of zinc and lead upon cthylenechlorhydrin, acetic aldehyde is formed and not ethylene oxide, as isthe case with the alkalis. To determine the influence of temperatureupon the formation of the one or other of these isomeridcs, the authorhas subjected the chlorhydrin to the action of potash at 160-180."Ethylene oxide is the product of the reaction. c. F. c.Solubility of Sugar in Water. By H. COURTONNE (Conyt.relad., lxxxv, 959--961).--The author confirms the results of Berthelotand Scheibler that-At 12.5" 100 grams of water dissolve 198.647 grams of sugar.,, 45" 9 , 7, 245 7, Or-A saturated solution a t 18-5" contains 66.5 per cent.of sugar.9 7 45" 7 7 71 7 7 L. %. 0,s22 ABSTRAOTS OF CHEMICAL PAPERS.Influence of the Alkalinity of Different Substances on theRotatory-power of Sugar. By H. PELLET (Bull. SOC. Chiiiz. [el,xxvii, 250) .-The author demonstrates that there is no relationbetween the action of alkalis on the rotatory power of sugar and theirequivalents; the same is true for different bodies having alkaliliereaction. P. P. u.Iodide of Starch. By L. BONDONNEAU (Compt. Tend., 671-673).-When excess of iodine is added to a solution of starch, iodide of starchseparates out as a blackish-violet substance, which, when washed anddried, exhibits a coppery lustre.When heated to 100" it loses 16-18per cent. of hydriodic acid and water, and at 1'30" the loss amounts to46 per cent., and the colour changes to black. This black substanceyields on oxidation saccharic and oxalic acids; sulphuric acid con-verts it into glucose. When the iodide is heated under pressurecarbon dioxide, hydriodic acid, and iodine are evolved, and when heatedto 1C)O" with water under pressure, it partly dissociates into iodine andstarch, and partly decomposes into glucose and hydriodic acid. Waterat the ordinary temperature slowly decomposes it into a-dextrin andhydriodic acid, I t is decomposed by diastase into glucose, p- and 7-dextrin, hydriodic acid, and an organic iodide not yet separated. Itstaste is insipid.The different analyses give results from which theformula (C6H,o05)5 I is deduced. L. T. 07s.Chloral Hydrate. By C. 0. CECH (Wie~z. Akad. Bey., lxxv, 299-312). This paper, containing an account of chloral anilide, chloro-toluide, &c., and of the derivatives of chloral cyanide-cyanate hasalready appeared in this JournaZ (1876, i, 376; ii, 184; 1877, i, 67).The grounds for regarding chloral cyanide-cyanate as a molecular com-pound of hydrocyanic acid and cyanic acid with chloral, and not as atrichlorinated lactylurea, are the following :-This compound is formedby the direct union of chloral-cyanide with cyanic acid. It is decom-posed by solution in cold aniline, hydrocyanic acid being given off, andthe cyanic acid splitting up into carbon dioxide and ammonia.Chloral-anilide obtained by the action of aniline on chloral cyanide-cyanate isidentical with the anilide prepared directly from chloral hydrate. Thisshows that the chloral molecule remains inbact :-C4H,CI,P\T20, + CGHYN + H,O = CBH,Cl,NO + HCN + CO, + NHdClChlord cyanide Chloral nnilide.cyanate.C,Cl,HO + C,H,N + CNK = C,H,Cl,NO + HCN + KCl.Chloral. w. c. W.Ammonia Derivatives of Chloral. By R. SCHIFF and G.TASSINARI (Deut. Clze.;rz. Ges. Bey., x, 1783--1787).-The objects ofthis investigation are to determine,-1. Whether the property ofuniting with the amides of the fatty and aromatic acids is common toall chlorals and bromals. 2. Whether the addition-products thuORGANIC CHEMISTRY. 25obtained are in all cases identical with the compounds obtained byreplacing a hydrogen-atom of the amide group in the chloral-ammoniasby the corresponding acid radicle; and 3.The mode of action of thealdehydes upon the chloral-ammonias. The authors establish theidentity of the product of the reaction of acetic anhydride uponb~yl-chloral-ammonia with that of acetamide upon butyl-chloral ; ineach case acetyl-butyl-chloral-ammonia-CCl,y(CH,),.CH.(OH).NH.C2H30is formed. By the action of benzamide upon butyl chloral, benzoyl-butyl-chloral-ammonia, CCl,,( CH,),CH( O€€)NH.C0.C6H, is formed.It is insoluble in water, soluble in alcohol and ether; it melts at132-133". The action of benzoyl chloride upon butyl-chloral-ammoniafails t o yield this body in a condition fit for analysis.By the action ofbromal upon acetamide, acetyl-bromal-ammonia,CBr3.CH(OH).NH.(CaH30)is formed. This compound is soluble in alcohol and ether; thecrystals melt at 160". These facts lead to an affirmative solution ofthe first two problems.Acti0.n oJ'tlie Aldehydes u p o n ChZoraZ-a?.lzmo.nin.--With the aldehydes ofthe methyl series unsatisfactory results were obtained. By tlie actionof benzaldehyde upon chloral-ammonia, however, a well-defined crystal-line product is obtained, which melts at I B l " , and analyses asC2,,H2,C18N,0. The authors withhold any conclusion respecting theconstitution of this and similar bodies until they are in possession ofthe results of a more complete investigation. C. F. C.Acrolein Hydrochloride.By M. K R E s T O w I N K o FF (BUZZ. XOC.Chim. [2] xxviii, 350). The result of this investigation is to showthat Geuther's acrolein hydrochloride, C3H@. CIH, is the aldehyde ofP-chloropropionic acid, this acid having been obtained by oxidizingthe hydrochloride in questlion with nitric acid. C. F. c.Glyoxaline. By. G. WPSS (Dezct. Chem. Ges. Ber., x, 136s-1375). In continuing his research (ibid., ix, 1543) on glyoxaline,C3H4N2, and glycosine, C6H6N4, the bases which Debus obtainedby acting with ammonia on glyoxal, the author has found Lubawin'sprocess for tlie preparation of glyoxal advantageous. Into glasscylinders, each of a liter capacity, are poured, by means of a funnel tube,and without mixing, separate portions of 160 C.C. 50 per ccnt.alde-hyde, 20 C.C. of water, and 64 C.C. of nitric acid (sp. gr. 1.37) mixedwith 2.5 C.C. fuming acid. The vessels are allowed to stand un-disturbed. I n summer the reaction is complete in four or five days,and the contents may at once be evaporated on the water-bath. Theresidue consists chiefly of glyoxal (according to Lubawin, from100 grams aldehyde 45-100 grams of the compound of glyoxal withsodium bisulphite may be obtained). To prepare glyoxaline, theresidue is treated very gradually with strong ammonia in slight excess,the temperature being kept down. Glycosiiie then separates as abrown powder, which may be filtered off. The filtrate is boiled wit24 ABSTRACTS OF CHEMICAL PAPERS.lime to expel ammonia, and evaporated to a syrup.This is exhaustedwith absolute alcohol, and the alcoholic solution fractionally distilled.I n the (Russian) paper from which the process is taken, Lulsawinshows that formic acid is really generated by the action of ammoniaon glyoxal, thus confirming Debus’s explanation of it-Acetyl and benzoyl chlcrides and acetic anhydride are entirely with-out action on glyoxaline, even when heated with it, or, at least, formonly addition-products. From this it might be inferred that glyox-aline is a tertiary base. But, if glyoxztline be boiled for some hourswith ethyl bromide, the syrup remaining after evaporation on thewater-bath taken up with water, the bromine removed by freshlyprecipitated silver chloride, and platinic chloride added to the con-centrated solution, there gradually separates a salt having thecomposition [ C3H3NZ( C2H,.C2H,C1)], + PtC14.From the brom-ethylate, by treatment with moist si1-i-er oxide, the hydroxide may beobtained as a strongly alkaline liquid, which, when dried in a vacuumover sulphuric acid, changes to a deliquescent crystalline solid.Benzyl chloride acts on glyoxaline in a perfectly similar way. Fromits behaviour with these ethers, in conjunction with its indifferencetowards acid chlorides, it may be concluded that glyoxaline containsone NH group, and one atom of nitrogen united by three affinities tocarbon.Glyoxaline is quite unaffected by chromic acid, and by reducingagents of all kinds, but potassium permanganate oxidizes it, com-pletely.When concentrated solutions of glyoxaline sulphate and potassiumnitrite, or of the hydrochloride and silver nitrite, are heated for a longtime, the mixture evaporated, and the residue exhausted with absolutealcohol, a nitroso-derivative, possessed of acid properties, is obtained.The alkaline salts of this body are reddish-brown, and give withsolutions of metallic salts amorphous variously-coloured precipitates.TribromogZyozaZine, C3HBra2, is produced, together with glyoxalinehydrobromide, by the action of bromine on an ethereal OY (better)aqueous solution of glyoxaline. I n the latter way a bright brownprecipitate is formed, which may be crystallised from much boilingwater.Readily soluble in alcohol, it is slrnost insoluble in cold water,and sparingly soluble in ether, chloroform, and carbon disulphide. Itpossesses the remarkable property of being soluble in alkalis, andprecipitated by acids.With the exception of hydrocyanic acid, it is, infact, the only known organic acid not containing oxygen. Most ofits salts are insoluble. The silver-compound, when boiled with ethe-real solutions of methyl or ethyl iodide, gives methyl and ethyl tri-bromoglyoxalina tes, well crystallised bodies, insoluble in water andalkalis, soluble in alcohol and ether. Treated for some time in warmalcoholic solution with sodium-amalgam, the bromine in these twoethers is displaced by hydrogen, and methyl and ethyl homologues ofglyoxaline are obtained, as oily soluble bases which form deliquescenthydrochlorides.Formic acid and GO2 were the only products demonstrated.Only the platinum salts were analysedORGANIC CHEMISTRY.25SiZve~.-glyoxaZi~e is obtained as a granular insoluble precipitatewhen silver nitrate is added to glyoxaline solution-2CsHiNz + AgNO, = C,H&gN, + C,HJV,.HNO,,or better still by adding caustic soda to a mixture of glyoxaline andsilver nitrate. The reaction of acetyl chloride on this body gives un-satisfactory results ; methyl and ethyliodides, however, act upon itin the cold, giving, besides small quantities of the above-mentionedhomologues, insoluble doughy compounds, as yet uiiinvestigated.To explain the formation and properties of glyoxaline the authorattributes to it the constitution N k I \x. Its incapabi~itj-of yielding an acetyl-derivative with acetyl chloride is no proof of theabsence of an imide group, since, amongst others, the phenylatedguanidines exhibit the same peculiarity.Assuming this constitution,some of the above bodies may be thus formulated:-CH H\CH--CH~CH CZH HNJ I Y N + C2H5C1'CH-CHChlorethylate of glyoxaline. Tribromoglyoxnlinic acid.Silver glyoxaline.CH CH,N J I I \N'CH-CHMethyl glyoxaline.Glycosine has been as yet but little examined. Ch. R.Decomposition of Hydrochloride, Hydrobromide, and Hy-driodide of Trimethylamine by Heat. By C. VINCENT ( C ~ m p t .rend., lxxxv, 666- 671) .-On heating trimethylamine hydrochlorideto 285", trimethylamine and methyl chloride are evolved, whilst aresidue of the hydrochloride of monomethylamine and trimethylamineremains ; a little above 305", ammonia and methylcliloride escape ; andfinally at 325" the whole decomposed.I n a similar manner the hydrobromide and hydriodide of trime-thylamine are decomposed, the former between 230 and 300°, and thelatter between 210 and 280".By the above methods chloride and bromide of methyl may be pre-pared in large quantities ; but, owing to the energetic action of iodideof methyl on trimethylamine, it is impossible to obtain large quanti-ties of the iodide. L.1'. 0's.On Acid Acetates. By A. V I L L I E R s (Con@. end., lxxxv, 755-757).-The author admits the correctness of Lescceur's formula forsodium biacetate. He has prepared hydrated calcium biacetate,CaH3CaO4.C2H4O2.H20. Neutral acetates when exposed to an atmo-sphere saturated with acetic acid, absorb it in the same manner asanhydrous salts absorb water, to form hydrates. L.T . 0'52 li ABSTRACTS OF CHEMICAL PAPERS.Metallo-aceto-acetic Ethers. Bv MAX C ONRA n (Liebin'sAni.zaleiz, clxxxviii, 269) .-The cojqx.?r-kceto-ncefic ether of GeuthLr,Cu(CH. ( ~ ~ : ~ ~ o . c , R 2, is easily obtained by shaking an am- ) maniacal -copper sulphate solution with aceto-acetic cther ; it isinsoluble in water, but readily soluble in hot benzene, alcohol, carbondisulphide, ethyl iodide, and bromobenzene, crystallising unchangedfrom these solvents. The brilliant green needles thus ohtaincd par-tially sublime without alteration when carefully heated t o 178' ; a t182" they melt, and a t higher temperatures are decomposed with pro-duction of metallic copper. L INickel aceto-acetic ether, Ni (CH { ,, is similarly ob-tained by employing a solution bf nickel salphate, chloride of ammo-nium, and ammonia; it is soluble in hot benzene and ether, crystal-lising in microscopic elongated tables readily decomposed by Gater.Cofialt aceto-acetic ether, Co CH C0'CH3 is identical in pro-perties, excepting that it is rose-red in colour, whereas the nickel-compound is green.( 1 CO.O.C,H,/,'CO.CH, Magnesium aceto-acetic ether, Mg ( CH { CO.O.C,H,): may betained in the same way, only acting on aceto-acetic ether with magne-sium amalgam ; it crystallises from h o t benzene in shining.plates,and melts with decomposition at 240'. Alzc7ninium acefo-ncetbc ether,A1 (CH { gg:g%H5 3) is obtained in slender, shining needles, whenpotassium aluminate and aceto-acetic ether are mixed and the solution iallowed to stand; it melts at 76" without decomposition, and onheating evolves brown vapours containing aluminium ; by.cantiouslyheating it can be distilled unchanged, the distillate soliddying to acrystalline mass melting at 76". The zinc and lead compounds ob-tained similarly could not be crystallised, and contained excess ofbase; the silver compound readily decomposes, even in the dark;platinum, gold, tin, and chromium compounds could not be prepared.Freshly precipitated mercuric oxide evolves heat on treatment withaceto-acetic ether, forming a white insoluble mass.These derivatives are quite analogous t o the acetyl-dichloraceticether formerly obtained by the author ; the ready formation of thesesubstances indicates that the hydrogen of the methylic group of aceticether, CH3.C0.0.C2H5, is easily replaceable both by electro-positiveand electro-negative elements and radicles, when some of that hydrogenhas been already displaced by a negative radicle such as acetgl ; thisdisplacement, consequently, is possible only with the a-acetylatcdcompound ethers; thus, the P-acetylated propionic ether of the author (inwhich the acetyl is not in union with the carbon-atom already con-nected with the CO.O.C,H, group) does ,mot give rise to such dsri-vatives, nor could Hellon and Oppenheim form a mercury-compoundof propionyl-propionic ether.C. It. A. WORGANIC CHEMISTRY. 27Ethylic Ethylmethylaceto-acetate, Ethylmethyl-acetic Acid,and a-Ethylmethyl-P-Oxybutyric Acid. By I3 I c H A R D S A u R(Liebig's Annalepz, clxxxviii, 257) .-Erlenmeyer and Hell did not suc-ceed in preparing ethylmethyl acetic acid, CH( CH:,) (C,H,) .COOH,synthetically, by the action of metallic silver on a mixture of methyliodide and bromobiityric ether, CHBr(C,H,) -CO.OC,H, (from theaction of bromine on kmentation butyric acid), as this reactiongave rise only to an inflammable gas (ethane ?) and ethyl suberate,; but as the other four theoretically possiblevaleric acids are all different from optically active valeric acid, theyconsidered this latter to be ethylmethyl-acetic acid.To test the correctness of this deduction, the author has preparedethylmetJhyl-acetic acid from ethylic sodethyl-aceto-acetate, and me-thyl iodide, and comparing it with other valeric acids: in boilingpoint and other properties, and notably in the formation of an uncrys-tallisable barium salt, it agrees absolntely with the active valeric acid ;but as far as minute amounts of material enable him to decide, theauthor finds that it has no action on polarised light : this point, however,is under further examination.I-c:thylic ethylaceto-acetate boiling between 192 and 196" was dilutedwith about its own volume of pure benzene, and then treated withsodium so as to form ethylic sodethylaceto-acetate, which was thendecomposed by the equivalent quantity of methyl iodide.Aftel. purifi-cation, the ethylic ethy 1'172ethyZaceto-acetate, Iobtained, boiled at 198" (not corrected), and had the sp. gr. 0.974at 22", compared with water a t 17.5" ; it is not miscible with water,but readily mixes with alcohol, ether, and benzene ; sodium does notact on it, and ferric chloride colours it violet.I n distilling it with sodium ethylate (freed from excess of alcoholby heating to 200" in a stream of hydrogen), acetic ether and alcoholare formed in quantity greater in proportion to the amount of theether compared with the sodium ethylate ; equal numbers of' moleculesgive very little, but when the ratio is 4 molecules to 1, considerableamounts are formed. Besides these, ethylinethyl acetate of ethyl,CH(CZH5)(CH3) -C0.0C2H,, is formed, boiling at 132-133", and ofsp.gr. 0.86'35 at 22", compared with water at 17.5' ; it is not soluble inwater, but is miscible in all proportions with alcohol, ether, and ben-zene.Alcoholic potash saponifies this ether, forming potassium methyl-acetate, obtainable as a highly-deliquescent crystalline crust by pass-ing carbon dioxide into the fluid, evaporating to dryness, extractingwith absolute alcohol, and evaporating in a vacuum. By distillationwith dilute sulphuric acid, et~~Lyl~iaetl~~l-aceiic acid itself was obtained,boiling a t li3" (not corrected) and of sp. gr. 0.938 at 24", comparedwith water a t 17.5", it seems to retain water energetically, probably asthe hydrate CkH,.C(OH),: in water it is sensibly, but not verysoluble.The silver-salt forms feathery needles when crystallised fromCH (CzH5). C 0 . 0 CZH,CH (CzH5). CO. OCZH, IC(CH,) (C2H5) ( C J W j,CO.0. C,H28 ABSTRACTS O F CHEMICAL PAPERS.boiling water ; these are scarcely affected by light ; the calcium saltis a crystalline mass of anhydrous needles, but the barium salt enhlbitsrzo trace of crystallisation, its solutions always drying up to varriishes :on comparing this salt with barium isovalerate (from isobutyl cyaiiide),the latter crystallised in long prisms to the last drop.When ethylic etliylmethyl-aceto-acetic is treated with water andsodium-amalgam, it becomes hydrogenised and saponified, forming thesodium salt of u-etl~yZmeZhyl (3-oxy Oidyric acid, thus :-C( CH3) (C,H,) (c', H@) I c 0.0 c,-I€H,+ 2H,O +Na, = NaOH + IIOC,L€s +C(CH,)(C,H,j.CH(OH).CH,ICO.ONaThe sodium salt is obtained pure by neutralising with sulphuric acid,evaporating to dryness, extracting with absolute alcohol, again evapo-rating to dryness, and washing the residue with very Zittle absolutealcohol ; crystalline nearly white nodules are thus left undissolved.Prom this the silver salt was prepared, readily soluble in hot andmoderately soluble in cold water, and containing C7H,,Ag03 : thecopper-salt is basic, being CiH,,Cu03.The free acid was obtainedfrom the sodium salt by decomposing with hydrochloric acid andtreating with ether; it is readily soluble in water, less so in salinesolutions ; over sulphuric acid it becomes first viscid and then solid,probably with formation of an anhydro-derivative.C.R. A. W.Salts of Tetracrylic and Diaterpenylic Acids. By OTTOKRAFT (Ueut. Cl~rm. Ges. Ber., x, 1659--1661).-Tetrscrylic a'cid isconverted, by prolonged heating of its sodium-salt with potash-ley,into an isomeric acid, of which the calcium salt, (C7H,,02),Ca, is moresoluble in cold than in hot water.The bariumsaZt, CsH,,BaO,, H20, formed by neutralising the acid with bariumhydrate, crystallises in groups of needles on evaporat'ing its solutioriover sulphuric acid. It is deposited from its aqueous solution onheating. The silver salt, C8H1,Ag205, is thrown down as a curdyprecipitate on adding silver nitrate to the barium salt. The ethyZicether obtained by heating the silver salt with ethyl iodide is solid atcommon temperatures, and has a peculiar odour when warmed.The salts of diaterpenylic acid are perfectly stable.J.R.Decomposition of Brassic Acid by Caustic Potash. ByG. GO L D s C K &i I E D T ( Wien. Akad. Ber., Ixxiv, 394-398) .-Afeyerhas shown that oleic acid and its isomeride, elaidic acid, both yieldacetic and palmitic acids on fusion with caustic potash (An/&. CYherua.Ph.awn., xxxv, 174). I n the same way, erucic and brassic acids aredecomposed by fusion with caustic potash into acetic and arachidicacidsORGANIC CHEMISTRY. 29These isomeric acids may be represented by the following for-inulce :-Oleic and elaiclic acids.H~ZC~GZCH-COZH I114 C 2- C 15H:ig- C 0,HErucic and brassic acids.H,oC,oxCH-C OZH H4C21.1 C,gH,,-C OZH.w.c. w.Distillation-products of Xanthates (Ethyl Dithiocarbonates).By A. FLEISCHER (Deut. Cham. Ges. Ber., x, 1293).-According toZeise, the so-called thial ether, C2H12S03, results (with other substances)when xanthates are submitted to dry distillation ; Conerbe fcundxanthin gas, COSH ; xanthil, C4HlOO, ; and xanthurin, CsHlsSO, ;wliilst Sacc obtained none of these, but instead, carbonic acid, sul-phuretted hydrogen, mercaptan, carbon disulphide, &c. The author andW. Hanke find that sodium and potassium xsnthates yield the samedistillation-products, from which carbon sulphide, the mono- and di-sulphides of ethyl, and carbon oxysulphide gas were separated whenanhydrous sadts were used ; and mercaptan, carbon disulphide, alco-hol, the two ethyl sulphides, and carbonic acid and sulphuretted hydro-gen gases, when salts containing water of crystallisation were employed.Lead xanthate furnishes the same products as the anhydrous alkalinexanthates. The ethyl sulphides in these experiments were isolated, anddetermined by means of their boiling points, by elementary analysis,and vapour-density estimation, and by their mercnro-chlorides andplatino-chlorides.In all these respects they corresponded with thedata hitherto published, but they differed in odonr, possessing a moreor less pleasant ethereal smell ; the garlic-like odour hitherto ascribedto them is, therefore, doubtless due to impurity. The carbon oxy-sulphide was distinguished by forming no precipitate in acid silversolutions, but a black one with ammoniacal silver; by producingcarbonate and sulphide of barium with baryts-water; and by form-ing with alcoholic potash a crystalline mass of ethylmonothiocarbonateof potassium, K.C2H5.CO2S. Probably the xanthurin of Couerbe wassimply a mixture of the two ethyl sulphides, and his xanthin gas animpure carbon oxysulphide containing sulphuretted hydrogen andmercaptan vapour ; the discovery of carbon oxysulphide, therefore,belongs of right to Couerbe (1840), although he did not isolate it in apure state ; since then and up to 1867, however, carbon oxpulphidewas always regarded as simply a, mixture of carbonic acid and sul-phuretted hydrogen.C. It. A. W.Dipropyloxalic Acid. By M. W o R O N T s o FP (BUZZ.SOC. Chinz.[ 21, xxviii, 350) .-The author has prepared dipropyloxalic acidC.( C,H,),.OH.COOH, and is engaged in investigating its reactions.C. F. C.The Action of Bromine on Pyrotartaric Acid. By EDMD.BURGOIN (Ann. Chim. Phys. [5], xii, 419--429).-The action o30 ABSTRACTS OF CHEMTCAL PAPERS.bromine on pyrotartaric acid varies with the relative proportions ofbromine and acid.I f equal numbers of molecules of bromine and pyrotartaric acid areheated t9 120" in presence of water, the products consist (1) of a fcwdrops of an oily liquid, which appears to be monobromopyrotartaricacid, but has not been obtained in sufficient quantity to yield trust-worthy results ; and (2) bromocitrapyrotartaric: anhydride, which isdeposited in crystals from the solution. Prom this it appears that themonobrominated derivatives of pyrotnrtaric acid are more readily actedon than the acid itself.When two molecules of bromine act on one molecule of pyrotartaricacid, bromocitrapyrotartaric anhydride is alone formed, and not, asLagermark states (Zeit.fiir C?Lem., vi, 299)) bromoform,'oxybromoform,bromocitraconic anhydride, &c., with the last of which bodies, bromo-citrapyrotartaric anhydride is isomeric ; its formilla is thereforcC5H3Br03. I t s forrrjation is explained as follows :--First, an unstabledibromoderivative is formed : C5H804 + 'LBr, = C5H6Br20, + 2HEr,which loses one molecule of hydrobromic acid and water, formingbromocitrapyrotartaric anhydride, C5H,Br,O4 = C5H3Br03 + HRr +H,O.When heated with water under pressure, it decomposes intocarbon dioxide and water.By the action of four molecules of bromine on pyrotartaric acid,allylene tetrabromide, or some isomeric body, should be formcd, huthydrobroinide of ethylene tribromide, an isomeride of acetylene tetra-bromide, is actually obtained, carbon dioxide and water being a t thesame time evolved. It is a liquid solidifying at -1'1".L. T. 0's.Normal Pyrotartaric Anhydride. By V. MARKOWINKOFF(BUZZ. Xoc. Chim. [ 21, xxviii, 349--350).-The author details theresults of his researches on the formation of this anhydride, the objectof which is to ascertain the relation, if any exists, between the positionof the carboxyl group in isomeric acids, and the constitution of theirrespectire anhydrides.The results obtained in the endeavour to prepare the anhydride 5ythe dry distillation of normal pyrotartaric acid, both alone and togetherwith phosphoric anhydride, proving nnsatisfactory, the author availshimself of the action of acetyl chloride, in ethereal solution, upon thesilver salt of the acid.The pure anhydride thus prepared crystallisesin small colourless needles, which are soluble to some extent in cold,more readily in boiling ether; they are easily soluble in boilingalcohol and in glacial acetic acid ; soluble with difficulty in cold water,which slowly conrerts them into the acid. The pure substance meltsat 56-57', and boils with partial decomposition a t 282-285'. Pyro-tartaric anhydride presents, therefore, considerable analogy to succinicEthenyltricarbonic Acid.By At. ORLOVS KT ( B d . Snc. Clu'm. [a],xxviii, 348--349).-The author has prepared the wid, C,H,. (COOH),,homologous with and intermediate between m€then,y7-tricarbonic nci(1,CH. (COOH),, prepared by Pfankuch, and aZly Ztricarboizic acid,C3H5. (COOH),, which Simpson prepared by converting monobromo-anhydride. c. 3'. cORGANIC CHEMISTRY . 31succinic acid into the corresponding cyanide, and decomposing thelatter with potash, thus :-C2H,(CNj.(COC)H)2 + 3KOH = NH3 + HzO + CzH3(COOK),.As secondary products of the action of bromine on succinic acid, inthe preparation of the monobrominated acid, a compound of theformula, C2H4Rr5, melting a t 51", and the bromides, C2H2Brz andC2H,Br4, are obtained.The author hopes to obtain this acid from thebromide C2H3Br3, through the corresponding cyanide ; and further,by replacing the bromine-atoms in the same compound by hydroxpl, toobtain a new triatomic alcohol, the next lower homologue of glycerin.He has found, in effect, that by the action of silver cyaiiide upon thisbromide, a compound of the formula, C21T3. ( CN)3.3Ag( CN), is formed,crystallising in pearly scales. These dissolve easily in bcth alcoholand ether, with separation of silver cyanide, to a dense liquid, fromwhich a crystalline body is deposited, which fuses a t 42", and is c. F. c. probably the tricyanide CZ€&.( CN),.Pyruvic Acid. By CARL BOTTINGER (Liebig's P-n,izalen, clxxxviii,293-352) .-The author gives a historical sketch of the results obtainedhy Berzelius, Volckel, Moldenhauer, Pinckh, Kolbe, Kekulk, Wisliccnus,Debus, Wichelhaus, Baeyer, Pittig, Klirnenko, Beckurts and Otto,Grimaux, and others, as to the formation and constitution of pyruvic acid,from which it results that either of the two formule, CH,.CO.CO.OH,or o\ 1 , will express the relationships of this body, whilstthe formula, COH.CH,.CO.@H, is not well applicable, the ketonicformula first mentioned being the more probable.I n order to see whether pyruvic acid behaves like other ketonicacids on oxidation with chromic acid, forming carbonic and acetic acids,the experiment was tried with the result of obtaining these products,and nothing elsea(oxidation with nitric acid forms oxalic acid, as pre-viously stated by Volckel).According to Wichelhaus, ketonic acidsshould first split up into two acids, e.g.,,OH2CH.CO.OHCH,.CO,CO.OH + H.OH = CH3.C0.0H + H.CO.@H.No formic acid, however, was found by the author.Condensation of Pyruvic Acid.-On standing for some time, py-rnvic acid thickens, and becomes viscid, and then furnishes bydistillation more decomposition-products of higher carbon pcr-centage, and less acetic acid than the same quantity of freshly yre-pared acid ; the author attributes this change io the doubling of tllcmolecule rather t'hail to any splitting up or decomposition. On heat-ing it alone with a reflux condenser to 170", carbon dioxide was evolvetl,and a resinous mass formed, from which water dissolved out smallquantities of acetic, uvic, and pyrotartaric acids. On heating a neutrslsolution of the barium salt to boiling, with a reflux condenser attached,for three days, carbon dioxide is evolved, and uvic, uvitic, acetic, pyro-tartaric, and oxalic acids are formed to an amount jointly equal t32 ABSTRACTS OF CHEMICAL PAPERS.some '7 to 10 per cent., a syrupy mass not further examined constitutingthe great majority of the product.By heating with hydrochloric acidon the water-bath, carbon dioxide is eliminated, and a mixture of crps-tallisable acids formed, one of which is difficultly soluble, melts a t 201-203", and appears to be ?nesnconic acid; the other is more easily soluble,melts at 113", and is apparently pyrotartaric acld. A substanceformerly obtained by the author yielded a barium salt, agreeing withthat of citraconic acid, and as mesaconic acid is derivable from citra-conic acid, he concludes that citraconic acid is obtainable from pyru-vic acid by condensation, $c.In order to compare the pyrotartaric acids formed from citraconic,mesaconic, and itaconic acids, the author prepared them by acting onthe respective acids with zinc and alcohol, to which a few drops ofhydrochloric acid were added from time to time.The three pyrotartaricacids thus obtained melted a t the same temperature, 112*5", end yieldedcalcium salts contzining about 17.4 per cent. of water of crystallisation,and 23.4 of calcium in the dry salt, in each instance ; by tlie action ofphosphorus pentachloride, water was abstracted, and an oil formed,apparently Markownikoff's p yrotartaric anhydride.The body described as wwitonic acid is regarded by the author aspartially decomposed dipyruric acid ; no concordant analytical numberscould be obtained, with specimens of different preparations.Beckurts and Otto have stated that both tartaric acid and glycericacid, when distilled, form pyruvic acid; the author could not obtainglyceric acid by heating tartaric acid with excess of baryta ; but bothtartaric and glyceric acids form pyruvic and also pyrotartaric acid onheating, wherefore the connections indicated by the formulE,and H-CH( OH)-CH(0H)-CO( OH),CO( OH)-CH(0H) -CH(OH)-CO(0H)are probably justifiable, notwithstanding that the latter acid cannot beobtained from the former by loss of C02.Nuscent hydrogen, from zinc-dust, converts pyruvic acid into lacticacid, according to Wislicenns and Debus.The author finds that inaddition a new acid is formed, easily separable from the lactic acid, itszinc salt being insoluble, or nearly so ; by decomposing this with sul-phuretted hydrogen, a syrupy acid is obtained to the amount of some4 to 6 per cent. of the pyruvic acid employed ; this is a bibasic acid,forming two anhydrous potassium salts, CGK9KO6, and C6HHK206, anda barium salt, C6H,Ba0,3Q HZO. This acid he terms dimethylturtaricacid. [ Qy. formed thus :- ?-I C(0H) (CH).CO.OHC(OH)(CH,).CO.OH -2(CH,.CO.CO.OH) + H2 = IIt is not volatile ; the ma'gnesium salt is readily soluble ; the neutralpotassium salt is precipitated by mercuric chloride and by coppersulphate, the precipitate i n the latter case being readily soluble indilute acids and ammonia, sparingly soluble in water.When an aqueoua solution of silver pyruvate is treated with suZ-yhuretted hydrogen, and the liquid concentrated, acetic acid is giveORGANIC CmMISTRT.33off, and a syrupy body formed, which can be crystallised from hotdilute sulphuric acid in needles, melting a t 141", and containingCH,-CH( SH)-CO.OH, whence the author terms it thiolactic acid(Schwefelmilchsaure) ; by oxidation this body forms acetic and sul-phuric acids. When heated with dilute sulphuric acid, it does notsplit up into thioaldehyde and formic acid, as might have been anti-cipated from the behaviour of lactic acid.By. passing salphnrettedbydrogen through freshly prepared pyruvic acid, a white powder isseparated, melting at 8 i 0 , and containing c6H8s05, or the elements ofpyruvic acid t thiopyruvic acid, C,H,O, + C3H,SO2. By heatingthis with hydriodic acid, iodine separates, thiolactic acid is formed,and a nonsulphurised body, apparently pyruvic acid ; continued actionof sulphuretted hydrogen also forms thiolactic acid.A mixture of hydroc!ya.izic acid and pyruvic acid is converted intolactic acid on dropping in hydrochloric acid and warming, no crystal-lisable acid being formed. Ammowin gas passed into pyiuvic acidcauses the evolution of carbon dioxide and formation of an oily body ;aqueous ammonia forms an acid, the calcium salt of which contairis20.45 per cent.of Ca ; alcoholic ammonia forms a chalky, nitrogelloussubstance, containing n( C4&No,), and soluble in acids and alkalis.The anthor regards it as the ammonia-salt of an amido-acid, whichhe terms uviitowic acid, CYH9N04, different from the body formerlydescribed as uvitonic acid (this JoumaZ, 1876, i, 566). This acid ISreadily obtained from the chalky substance by dissolving in ammonia,and adding hydrochloric acid, whereby a crystalline precipitate of tbeacid is thrown down. The barium salt is C8H7BaN04.3H20, of whichonly two-thirds are lost a t 160' ; it crystallises in small needles. Thecalcium salt crystallises in hard, transparent nodules, and in white cohe-rent needles, containing C8H,CaN0,.5H20, and C8HgCaKO5,2H.0, re-spectively, whilst the silver salt is C8H,Ag2NO5 ; whence it appears thatthe body regarded as the acid, C8H9NO4, is really an anhjdride, thebarium salt being properly represented as C8H9BaNO6.2H20.Strongnitric acid has no action on uvitonic acid ; chromic acid oxidises it tocarbonic and acetic acids, and ammonia with a little of a red powder notyet investigated. By fnsion with potash an acid is formed, apparentlyoxyterq7Ltkulic acid, together with pyruvic and acetic acids. Whentreated with an ethereal solution of aniline, pyruvic acid evolves liest,and forms an anilide, C,H40, + C6K5.NH, = H,O + C,W,NO,. Thisdarkens a t 114', and melts a t 122"with decomposition; it forms a bariumsalt, (C,HsNOa)2Ba.On fusion with potash, it seprns t o undergo anisomeric change, forming a strong acid of the same composit,ion, sub-limable in needles, which turn brown a t 220", and decompose at 24(3",and forming a barium salt, (C9H,N02)2Ba, after drying a t 130". Whenadded to melting ant,hranilic acid, an acid is formed, containing appa-rently CloH,N04, the barium salt being CloH7BaNOa ; but this has notbeen obtained pure.From all these results the author concludes that whilst the constitu-tion of pyruvic acid cannot be deduced from its origin, the breaking upof tartaric acid on heating being complex, the behaviour of pyruvic acidto wards hydrogen, sulpharetted hydrogen, and hydrocyanic acid isindicative of its possessing a ketonic character ; he does not, however,YOL.XXXITI. 34 ABSTRACTS OF CHEMICAL PAPERS.decide definitely which of the two formulz, CH,-CO-CO.OH, oris to be preferred.CH-CO-OH, C. R. A. W.Note on Tartronic Acid. By E. DENLOLF: (D&. Ckem. Ges.Ber., x, 1788-1790) .-The conversion of dinitrotartaric acid intotartronic acid, by exposing its aqueous solution to a temperature of30°, is proved by the author to take place directly, without the for-mation of intermediate compourids.The formation of oxalic acid, with evolution of carbonic anhydrideand nitric oxide gases, which occurs when the temperature is allowedto rise to 50", is referred to the secondary decomposition of tartronicby nitric acid, these acids resulting from the following reactions :-(1.) (CH.0N02)2.(C0.0H)2= CO, + N,Os+ CH.OH.(CO.OH),and(2.) H20 + 3N203 = 2HN03 + 4x0.Guided by the above facts, the author has devised a method forconverting dinitrotartaric into tartronic acid a t higher temperatures,and therefore much more rapidly : the essence of which cotisists ineliminating the nitric acid at the instant of its formfition, and thuspreventing the secondary conversion into oxalic acid.60 C.C. alcohol,sp, gr. 0.925, are heated in a porcelain dish on a water-bath, and20 grms. of dini trotnrtaric acid added in successive small portions.The heating is continued until the evolution of gas has ceased, and thesolution is allcwed to crystallise. The acid is purified by recrystal-lisation. The author has determined its melting point to be 150-151". c.F. c.Pyromeconic Acid. By E. IHr, E E (Liebig's A.inalen, clxxxviii,31--42).-When pure dry meconic acid is gradually heated in a tubewhich is bent a t an obtuse angle, and the sublimate is redistilled, almostthe whole comes over a t 227-228", when the mercurial column iscompletely immersed in the vaponr. Neither oily products nor aceticacid are formed, and only at the end of the second distillation doesthe temperature suddenly rise, gases being evolved ; arid if the operationbe not tlxw stopped, a small quantity of feathery crystals, consistingprohbly of Stenhouse's paraconienic acid, sublimes. The yield ofpyromeconic acid was 25 per cent. of the meconic acid employed. Itcrystallises from hot water i n long, brilliant, four-sided prisms, doesnot dissolve freely in ether, which however on shaking it repeatedlywith an aqueous solution, takes it up almost completely.The pure acid begins to sublime a t lOO", and melts a t 121.5" ; it isa strong acid, decomposing alkalis and forming well defined salts.Analcoholic solution of the acid and alcoholic potash form a crystallinemagma, which after washing with alcohol and drying, consists oEC,H,O,K. In the light it gradually turns bluish-green, green, brown,and after some weeks becomes colourless again. It is decomposed byheating it to 130" and by boiling it with alcohol. The barium anORGANIC CHENISTRY, 35calcium salts are obtained by heating an aqueous solution of the acidwith the carbonates only until the acid reaction ceases, or by addingthe corresponding chlorides to a warm, ammoniacal solution of theacid. They crystallise in glistening needles and are acid salts(C,H,O,),M .‘LC,H,O,. The copper salt, (C6H303)2Cu, is. sparinglysoluble in cold water, and crystallises from hot water in green needles.An ether of pyromeconic acid could not be obtained.All pyromeconates are decomposed by boiling them with water, andmore quickly if a free alkali be present, different products beingformed, the principal being formic acid and an acid forming arnorphoussalts. According to Stenhouse (L‘%‘eZlig’s Amcr,Zen, xlix, 18) and Brown(ibid., lxxxiv, 32), from a solution of the acid in an excess of potash,the free acid separates; in this case probahly decomposition hadtaken place and sufficient formic acid was formed to neutralise lzotonly the potash, but, also to precipitate some of the unclecornposed acid.Comenic acid is also decomposed by boiling it with baryta-water, butmore slowly, with apparently the formation of the same products.c. s.Action of Ferricyanides on Metall€c Silver. By J. $1. En E n( J . pr. Chew,. [ 2 ] , xvi, 211--218).-The author has shown that silveracts on potassium ferricyanide, producing the ferrocyanides of silverand potassium (Cheni. Cents.., 1876, 569) ; and it was supposed that theaction of silver on lead ferricyanide would be analogous. Warthn(Photopwph. Correspondenz, xiv, 154) has found that this reaction isattended with the formation of yellow silver ferricyanide, according tothe equation-4Pb3Fe2Cy,, + 6Ag = 6PbnFeCy6 + AgsFe2Cyla.The author finds that the yellow precipitate formed by the action ofsilver on lead ferricyanide becomes whiter the more thoroughly i t iswashed, assuming finally a green colour owing to decomposition ofsilver ferrocyanide.The weight of the thorcughly washed productagrees with the formation of ferrocyanide of silver: also, as silverferrocyanide is decomposed by hydrochloric acid and not by dilutosnlphuric acid, and the lead salt by both, the ferrocyanic acid existingas silver and lead salt may be separated, and its amount determined bytitration with permanganate. The results obtained and the absence ofsilver ferricyanide, together with the estimation of silver and lend,agree with the author’s equation, which is as follows :-2Pb3Fe,Cy12 + 4Ag = 3PbzFeCy6 3- &FeCy6.Wartha’s results depend chiefly on the presence of lead ferricynnidc.P.P. B.Potassium Superferricyanide. By Z. H. S K R A U P (Liebiy’sAnna Zen, clxxxix, 368-379) .-Potassium superferricyanide-K-Cy31Fe-Cy3 -Kd 36 ABSTRACTS OF CHEMICAL PAPERS.is best prepared by adding 18 grams of hydrochloric acid, sp. gr. 1.196,diluted with three times its volume of water, to 50 grams of potassiumferricyanide and four grams of potassium chlorate dissolved in 100C.C. of hot water. The mixture, after standing for twenty-four hoursin a cool p'lace, is filtered. The addition of alcohol to the filtrate throwsdown a black precipitate, from which the supernatant liquid must berapidly decanted.The crude product is purified by dissolving in waterand reprecipitating with alcohol ; the pure aqueouR solution evaporatedto dryness in a vacuum a t the ordinary temperature, leaves a brittle,amorphous, black, glassy mass, which decomposes slowly at the ordinarytemperature, and rapidly a t 53". Potassium superferricyanide is ahFgroscopic body insoluble in absolute alcohol ; it dissolves in wster,forming a neutral solution, which smells of cyanogen. This solutiondecomposes on boiling into ferric hydrate and ferricyanide of potassium.Caustic potash decomposes it into ferric hydrate, potassium ferro- orferri-cyanide, and potassium cyanate. The action of sodium amalgamsplits it up into ferric hydrate and potassium ferricyanide.The solution of superferricyanide gives characteristic reactions withmany of the metallic salts, e .g . , with basic lead acetate a dark greenprecipitate ; with silver nitrate a dirty green precipitate changing toyellow and finally to white ; with ferric salts an olive-green coloration,Behaviour of the Thiocyanates of Potassium and Ammoniumin presence of Oxygen-acids and of some Metallic Oxides. BySCHLAGDENHAUFFEN and F. WURTZ (J. Pharm. Chim. [4], xxqi,235-230 and 312--319).-The substitution of sulphur for oxygen inthe cyanates can be effected by means of carbm bisulphide, as in thefollowing equation: 2NCOM + CS, = 2NCSM + CO,; but the con-trary substitution cannot be so easily effected; this probably arisesfrom the fact that the oxidising agents used could act only eitherwhen fused, or in presence of water.When they were fused, thesulphur was always oxidised to snlphuric acid, thus preventing, inmost cases, the formation of cyanate; small quantities of cyanatewere, however, occasioually obtained. I n the second case, where theoxidising agent acts in presence of water, the cyanate, if formed, wouldinstantly be decomposed by the water.Potassium. perm!anganate, in presence of free hydrochloric acid, givesrise t o a more or less abundant formation of perthiocyanogen.Chromic acid with potassium or ammonium thiocyanate, forms thecorrespondirig chromo-thiocyanate. When a small quantity of freeacid is present, chromo-thiocyanic acid is formed, together with per-t liiocyanogen. With much free acid, perthiocyanogen and greenchromic chloride are formed.Potassium bichromate has no effect byitself ; the ammonium salt produces chromium thiocyanate.lodic acid and potassiwn i o d d e (the latter incompletely) precipitateperthiocyanogen. In this reaction no free iodine is formed, as it pro-bably acts further on the thiocyanate. Ammonium thiocyanate isacted on more readily than the potassium salt.Potassium and ammonium thiocyanates mixed with iodine and ex-posed to direct sunlight, form perthiocyanogen.and with ferrous salts a bluish-green precipitate. w . c. wOROANlC CHEMISTRY. 3 7Hydriodic acid, brornic acid and potassium bromate, and chloricacid all produce the same effect ; the latter also produces some sul-phuric acid.Nitric acid: either concentrated or dilute, oxidises all the sulphur tosulphuric acid; the liquid at the same time acquires a rose or greencolour. Nitrite of potassium does not act on thiocyanates until anacid is added, when a precipitate of perthiocyanogen is formed.Nitric oxide produces no effect, but if nitrous fumes are passed intoa solution of a thiocyanate, a blood-red colour is produced, whichdiffers from that produced by ferric chloride i n that, on evaporationon the water-bath, no coloured residue is obtained.SeZenious acid added to potassium or ammonium thiocyanate, gives aprecipitate of selenium, which is mixed with perthiocyanogen if hydro-chloric acid be added to the solution.A r s e n i o u s acid in presence of hydrochloric acid gives an orange pre-eipitat e, consist,ing of perthiocyanogen mixed with a dark-brownarsenical compound.A r s e n i c acid gives a similar precipitate, beingitself reduced to arsenious acid.i'iolybdic: acid in presence of free acid produces a yellow colour,which gradually changes, through orange and red, to amaranth.Tungstic acid with hydrochloric acid, is reduced, with production ofa yellow, and then a red, colour. I f a large excess of hydrochloricacid is present, a fine blue colour is produced, probably due to tungstenthiocyanate.The oxides of mercury, siZver, and copper, when heated with potassiumfhiocyanate, are converted into sulphides ; with the ammonium saltammonia is liberated, and double thiocyanates are formed.Ferric oxide heated with ammonium thiocyanate, forms ferric thio-eyanate; no reaction takes place with the potassium salt with thisand the following oxides.Oranic oxide produces a double salt of a yellow colour.Ch,rornic oxide, when freshly prepared, produces ammonium chroino-Action of Potassic Thiocyanate on Compounds of Mono-chloracetic Acid.By PETER C L A E s s o N (Deut. Chm. Gcs. Rer.,x, 1346-1354) .-By the action of potassic thiocyanacetate on chlor-acetic ether, Heinte (Ann. UlLern. Phnrrn., cxxxvi, 22) obtained a bodywhich he named sulphocyanacetic ether, but which was incapable ofyielding salts on treatment with alkalis. Acids, however, especiallyhydrochloric, dissolved it readily, forming (besides other bodies) ailacid which he regarded as sulphocyanacetic acid.He also found that,on distilling his sulphocyanacetic ether, there remained in the retort abody of the same composition, named by him pseudosulphocyanaceticether. By the following experiments the author has now shown thatHzintz's sulphocyanacetic (thiocyanacetic) acid is identical withVolhard's (J. pr. Chem., 1874, 6) thiocarbimidacetic acid, and hispseudothiocyanacetic ether a polymeric form of thiocyanacetic ether.Such an effect of hydrochloric acid as that above mentioned ap-peared to the author very improbable, and on repeating Heintz's ex-periment, he observed that the presence of water is a conditioiithiocyanate. c. w. w38 ABSTRACTS OF CHEMICAL PAPERS.necessary for the reaction ; from which he concludes that the nssimi-lation of water is the primary change which takes place, and thatthiocarbimidacetic acid is only a secondary product.True tkiocyanacetlc acid and its salts are prepared by dissolvingcrystallised monochloracetic acid in an equal weight of water, nentra-lising with sodic carbonate, and adding the proper pantiby of potassicthiocyanate.The reaction begins immediately, and after the lapse ofsome time the mass becomes solid, from the seprtration of alkalinethiocyauacetate and chloride. From the mixture of salts, freed frommother-liquor, the former is extracted by boiling alcohol, from whichi t separates almost completely on cooling. The mother-liquor con-tains, besides thiocyanncetate, salts of thioglycollic and carbnminthio-glycollic acid (vide ir~ru), the two latter being secondary products dueto the action of the acid on the first.Similarly, when chloracetic ether is added to a boiling alcoholicsolution of potassic thiocyanate, potassic chloride separates immediately,thiocyanacetic ether being formed.Since free thiocyana#cetic acid combines very readily with water toform carbaminthioglycollic acid, it is best extracted from soltition ofits sodium salt by adding sulphuric acid, and at once shaking withether.The ethereal solution, dehydrated by calcium chloride, andevaporatad over sulphuric acid, gives the acid, which is separatedfrom the accompanying small quantity of carbaminthioglycollic acidby repeated solution in absolute ether. It is thus obtained as acolourless, odourless and uncrystallisable oil, which, on gently heating,becomes polymerised into a porcellanous mass) very difljcultly solublein boiling water.'I'hiocyanacetic ether, when heated to 120" with ethyl iodide o rbromide, forms ethyl thiocyanate and iodacetic or bromacetic ether.The reaction, which is quamtitative, affords an advantageous methodfor preparing bromacetic and iodacetic acids.If thiocyauacetates in solution are brought i n contact with salts ofsilver, mercury or copper, thioglycollic acid is formed : for example,Na.O.COCH,.S.CN + Z(Ag.O.NO,) + 2H20 = Ag.O.COCH,.S.Ag +NH, + Na.0.N02 + H.0.N02 + CO,.The reaction with copper saltsis characteristic, an amorphous black precipitate of cuprous thiogly-collate being formed on gently heating.Alkalis also decompose saltsor ethers of this acid : bromine and nitric acid oxidise its salts, pro-ducing snlphacetic acid.Cnrbamintltioglycollic acid, H. 0. COCH,. S. C ONH2, is easily formedby adding hydrochloric acid to solution of a thiocyariacetate, andleaving the mixture to spontaneous evaporation. It crystallises inlarge rectangular tables or rhombic prisms, and melts a t 132-134'.Boiled in aqueous solution it is quickly converted into thioglycollicacid, but when heated with concentrated hydrochloric acid it4 yields,in addition, thiocarbimidacetic acid. Alkalis convert it slowly intothioglycollic acid and ammonia : bromine oxidises it energetically tosulphacetic acid. Salts of metals which easily combine with sulphureffect its decomposition very readily into t~hioglycollic acid, carbonicanhydride, and ammonia.Heated to 110" with methyl alcohol and methyl iodide, carbamin-A few of its salts and ethers are describedORGANIC CHEMISTRF.39thiogly collic yields trim ethyZ-szcZfin,iodide, which cry stallises on cooling.The reaction occura in two stages-(1) H.O.COCH,.S.CONH, + CH,I = H.O.COCH2.S + CH,.S.CONH,.(2) CH,.S.CONH, + CHJ + CH,OH = (CH,),SL + CO, + NH,.Methyl and ethyl ethers of this acid have also been obtained byordinary processes. The methyl ether is also obtaiiied when methylthiocysnacetste is heated with an equal volume, of modcrately dilutehydrochloric acid.Under the inflnence ofhydrochloric acid, thiocyanacetic ether first assimilates water to formcarb~~inthioglyeollic ether, which is then partially decomposed intoalcohol and the free acid.The latter is further acted upon, YJaTt of i tabsorbing water to form CO, and thioglycollic acid, anot)lier imrtionpartiiig with water to form thio-carbimidacetic acid. Strong hydro-chloric acid favours the development of the latter.Thio-curbimidacetic ucicl, which tlie author shows t o be ideriticalwith Heintz’s thiocganacetic acid, was obtained by Volhard ( h ~ . cit.)by acting with chloracetic acid upon t,hiocarbamide ; thiohydarito’inhydrochloride is thus formed, and on boiling with water splits up asfo~lows :-CS/ I .HC1 + H,O = NHiC1 + H.O.COCH,NCS. Volhard’sreaction yields the acid in theoretical quantity when chloracetic etherand thiocarbamide are boiled together for a short, time in alcoholicsolution.The thiohydantoln hydrochloride crystallises out. h muchbetter process consists in boiling together for a long time amyl thio-cyariacetate and fuming hydrochloric acid, the greater part of theliberated thiocyanacetic acid passing into thiocsrlnimidacetic acid.The latter is colourless, easily soluble in hot, spariiigly in cold water ;it may be sublimed without decomposition, and melts a t 125-126’.I t is a feeble acid, its soluble salts being more or less decomposed bywater into free acid and base.Several reactions andsalts of it are described. The conipounds of the heavy metals decom-pose it, less easily than carbaminthioglycollic acid, into tliioglycollicacid, CO,, and ammonia.I t s solution treated with silver nitrate in excess gives a crystallinecompound of argentothioglycollate of ammonium.Without doubt all these transformations have their origin in a“ tendency towards neutrality ” (Neutralitiitsstreben), since they occurunder the influcnce of acids or bases, or of salts of metals which havea powerful aenity f o r sulphur.Heintz’s results may now be explained.NHCO\NHCH,The mercury aiid silver salts are insoluble.Ch.13.Two New Modes of Formation of Cyanamide. By DRECH-S E L ( J , pr. Claem [%I, xvi, 2Ol-210).-1. Having observed that thecarbarnates of the alkaline earths are decomposed by heat, witli forma-tion of cyamides, and that there is strong evidence for regardingthis as the result of the secondary decomposition of the cyantttes, th40 ABSTRACTS OF CHEMICAL PAPERS.author applies these facts to explain the observation of Geuther andBilstein, who found that by the action of carbonic anhydride uponsodamide, sotLum cyanamide, and riot sodium cyanate, was formed.His deductions may be represent’ed by the three equations :-(i.) NaNH, + CO, = NH,.CO.ONa;(ii.) NH2.C0.0Na = NCONn + H,O; and(iii.) NCONa + NaNH, = Na,CN, + H,O.To prove the truth of (iii), sodamide was allowed to act upon potas-sium cyanate ; from the product of tbe reaction, cyanamide in largequantity was obtained. This, taken in conjunction with the factexpressed by (ii), is undeniable evidence of the superior exactness of(i) to the equation proposed by Geuther, viz.:C,O, f 2NaNH2 = C,N,H, + 2Na0 + 2HO{C = 6; 0 = 8 ; €3 = 1).It is neeclless t o add that the water formed in the above reactionsdecomposes a portion of the sodium amide into ammonia and sodiumhydrate.11.The decomposition of calcium carbamate by heat, with formationof cyamide, appears to occur in two steps, represented by the equations(i.) (NH,.CO.O),Ca = (N.CO),Ca + 2H,O, arid(ii.) (NCO),Ca = CaCN, + CO,.To verify independently the truth of (ii), calcium cyanate (in effect amixture of anhydrous CaC1, with 2KNCO was heated for some timein a platinum crucible to a low red-heat :-cyanamide was identified inlarge quantity in the resulting mass. Similar observations on thecy yates of barium and thallium entirely confirmed this result.iSilver cyanate exposed to a high temperature is decomposed withconsiderable evolution of gas, which latter, towards the end, is com-posed of N and GO, in the ratio of 10 t o 22 vols.This, togetherwith the fact that silver cyamide is entirely decomposed by heat,points to a precisely similar interprctation of the reaction w1iiclLoccurs, viz., 2AgCNO = Ag2CN, t CO,. Generally, therefore, bytJhe action df beat upon the cyanates, metallic cyaniides of thc formB”CN2 are produced. These when treated with a small yuaiitity ofwater are decomposed into monocyamides of the form HHCN, ; thus,e.y., .tCaCN, + 2H,O = CaH2(CN2), + Ca(OH),, than which, how-ever, they are much more stable in relation to heat; thus T12CN2, BaCN,and CaCN, withstand a red heat without decomposition, whereasNaHCN, is at once decomposed on heating.I n conclusion the authorrecommends the action of heat upon a mixture of anhydrous CaCl,with KNCO as an effective mode of preparation of cyanamide.c . F. c.On Amido-acids. By FRANZ HOFM E r s T E R (fiebig’s AnnnZen,clxxxix, 6--43.)-In a recent paper, Engel (Compt. rend., 80, 1168)has described two new reactions of glycine, namely, the production ofa red colour with ferric chloride, and of blue on addit,ioii of phenoland a hypochlorite ; these, together with its power of reducing merORGANIC CHEMISTRY. 41curous nitrate and of preventing the precipitation of cupric sulphateby caustic soda, he considers to be characteristic of the acid. Engelhimself, however, having shown (Joum.Yharm. Chim. [ 5 ] , xxi, 194;Clzenz. Centr., 1875, 246) that the hypochlorite reaction is exhibited bymost amides, the author has systematically examined the behaviourwith certain other reagents of the ipportant group of amido-acidswhich are frequently met with as decomposition-products of albumin-ous bodies. The results may be summarised a3 follows:-G'Zycine andsarcmsiwe give with ferric chloride red, with cupric chloride or sulphateblue, with cupric sulphate and caustic soda deep-blue solutions. Theyreduce mercurous nitrate, and are not precipitated by mercuric chloride,nitrate, or sulphate, or by the chloride after the addition of sodiccarbonate : with the nitrate and sulphate, after such addition, theygive white precipitates which are insoluble in excess of the carhonate.Asparugine, aspartic acid and glutamic acid giTe similar reactions,except that the first is precipitated by excess of mercuric chloride, andthe two latter (in the cold) precipitate, as well as reduce, mercurousnitrate. These two also give with mercuric nitrate or sulphate whiteprecipitates soluble in excess, but, after addition of sodic carbonate,precipitates which dissolve in large excess of the carbonate.Leucinebehaves in general like glycine, but the precipitates with sodic carbon-ate and mercuric nitrate or sidphate are soluble in excess of the car-bonate, Taarine does not react with the above-mentioned ferric,cupric, or mercuric salts alone, and does not prevent the precipitationof copper sulphate by alkalis ; it reduces mercurous nitrate, and giveswith sodic carbonate and mercuric nitrate or sulphate white precipi-tates which do not dissolve in excess of the carbonate. Aceturnidein its reactions resembles.taurine ; but the precipitate with sodic car-bonate and mercuric sulyhate dissolves in cxcess of the carbonate.Urea also behaves in general like taurine, but gives precipitates withmercuric nitrate or sulphate, the former insolublo, the latter dificultlpsoluble in excess. It also precipitates mercuric chloride after additionof sodic carbonate. Creatine gives a red colonr with ferric chloride,and blue with copper salts, and does not prevent the precipitation ofcopper by alkalis. It does not precipi-tate mercuric salts alone, but after addition of sodic carbonate it giveswith them precipit'ates which dissolve in excess of the carbonate, butreappear on standing.C1-entiw;ne differs from creatine in givinga precipitate with ferric chloride, a deep blue solution with cupricsulphate and caustic soda, and a white precipitate with mercuricchloride.The copper salts of leucine, aspartic acid, glutamic acid and tyro-sine, in consequence of their slight solubility in water, are well adaptedfor the detection and estimation ot'these acids. They may be readilyprepared by gradually adding hydrated cupric oxide to boiling solu-tions of the acids, and filtering hot. The salts separate from thefiltrate on cooling ; those portions which remain with the excess ofcopper hydrate on the filter may be extracted with boiling water.Their exact formula?, solubilities, and properties are given by theauthor. Tyrosine-copper is soluble in 1,230 parts c.f cold water ; theother copper salts in (about) 3,000 parts.It reduces mercurous nitrate42 ABSTRACTS OF CHEMICAL PAPERS.The separation of the amido-acids is rendered difficult by the pro-perty which they possess of uniting with each other to form salinecompounds. A series of these compounds prepared by the author willbe described in a future paper.They are all decomposed by boilinqwith cupric hydrate, but even so their constituents cannot be separated,since the more soluble copper salts, those of glycine and glutamic acid,for example, prevent the precipitation of the less solnhle ones.Con-sequently the non-appearance of a crystalline precipitate on a,ddingcupric hydrate to a boiling liquid does not prove the abseiice of one ofthe latter.It is well known that the oxyacids and multivalent alcohols have thepower of retaining in alkaline solution half an equivalent of copper for.each hydroxyl-group in their molecules. Coray and Wislicenus ex-plain this by supposing that compounds are formed in which coppertakes the place of the alcoholic hydrogen. Amongst aromatic oxy-acids, according t o Wekh (Deut. Chern. Ges. Be?.., ix, 342), this pro-perty is confined to those which belong to the ortho series, and is not;shared by their isomerides ; and Dossios (Liebiy’s AnnuZen, cxlvi, 174)has observed a similar difference between the isomeric lactic acids.With the exception of taurine, the above amido-acids can retain inalkaline solution a definite quantity of copper.This amount theaut,hor, by a process of titration which is fully described, has foundto be, for each molecule of glycine, sarcosine, leucine, glutamic acidand tyrosine, one-Anlf ntom of copper, and f o r each molecule of aspar-tic acid and asparagine, one atam of the metal. I f the compounds hereformcd are ordinary copper salts, it is difficult t o see why they are notdecomposed by alkalis. The author rather inclines to the belief thatthey are saline compounds in which the soda salts of the acids playthe part of base, and the cupric hydrate that of acid. Evidently thesolvent action on copper must be due to the presence in the amido-acid of the group CHNH2, since this power is totally want,ing in thefundamental acids, and their amides which contain the groupingCONH,.Now cupric oxide is known to form saline cornyounds withammonia and (less easily) with potash and soda ; and the fact tlist theamido-acids are substituted ammonias, and can really play the part ofbases, makes i t not improbable that they can combine in a siuiilarmanner with cupric oxide, especially when their acid properties areiieutralised by the presence of a grmt excess of alkali. Thus the com-pound of glycino would be (COONa.C13.NHG2.HO)2Cu ; that of aspar-tic acid COONa. CH (NH,.HO.C uOH) . CH,. C OONa.This theory does not explain why aspartic acid and its amide, aspara-gine, hold in alkaline solution twice as much copper as the other acids ;it cannot he due to their basicity, since t’his increased solvent powerdoes not appear in the bibasic glutamic acid.Ch. B.Arnido-acids. By %. H o F 31 E I s T F: R ( Wiev,. Aknd. Bei-., lxxv, 469-498) .-Leucine, tyrosine, aspartic, and glutnrnic acids may be isolatedand detected by the insolubility of their copper salts. Copper-Zeucirie( C6H12N02)2C~ forms pnle-blue, shining, crystalline scales, soluble in3,045 parts of cold, and in 1,460 parts of boiling water. The othercopper-salts described by Goessmann (Gmelin-Kyaut, Supplement, l246)ORGANIC, CHEMISTRY. 43Ritthausen, and Kreussler (Chem. Centr., 1871, 394) were not obtaiiied.Coppel. aspartate, C,H,CuNO, + 44H20, dissolves in 2,870 parts ofcold, and in 234 of boiling water.It is very soluble in dilute aceticacid, and can easily be obtained in the pure state by recrystallisationfrom this solvent. The crystals lose their 44 molecules of water a t120" ; the anhydrous salt is hygroscopic. Copper gZutamatc,C5H,CuN04 + 2+H,O, soluble in 3,400 parts of cold water and in 400parts of boiling water, bears a strong resemblance to the aspartate.The two other copper glutamates described by Ritthausen (Cherr~..Celztr., 1867, 276) could not be obtained.Copper t y ~ o s i n e ( C,H,,N03)2Cu, forms small glistening dark-blueneedles soluble in 1,230 parts of cold, and in 240 parts of boiling water,but insoluble in alcohol and ether. It is decomposed by acids, and byboiling with water.The precipitation of the four copper salts just described is hinderedby the presence of free acids and by the soluble copper salts of glycineand other organic bodies.One molecule of glycine, tyrosine, sarco-sine, leucine, or of glutamic acid can dissolve lialf an atom of copperin an alkaline solution. One molecule of aspartic acid or asparaginecan hold one atom of' copper in solution. The constitution of thesebodies may be represeiited thus :-Copper glycine.COONaCopper aspartate.COONaI CHNH2H0.CuOHII CH2COONa ICHNH,HOCHNH2H0 >cu ICOONa.The author also gives a tabular statement of the reactions of theamido-acids with ferric chloride, copper sulphate, mercurous and mer-curic salts. w. C. w.The Action of Bromine on Succinimide, and a New Modeof forming Fumaric Acid.By E. KIS I E L I N s ~i ( Wlen. Alcad.Rer., lxxiv, 561- 570).-A mixture of dibromsuccinimide, monobrom-fumarirnide and fumaric acid is obtained by heating succinimide withbromine to 130" in sealed tubes for four hours. The dibromsuccini-mide is separated from the other bodies by its insolubility in water.It crystallises in slightly yellow rhombic prisms melting at 225", solublein warm alcohol, and slightly soluble in ether and glacial acetic acid.On evaporating the liquid from which the dibromsuccinimide has beenremoved, impure monobromofumarimide separates out, and fumaric acidis deposited from the mother liquor.Monobromofumarimide dissolves readily in alcohol and in hot water ;it is only slightly soluble in ether, chloroform, carbon disulphide, andglacial acetic acid.It forms faintly yellow tabular crystals, whichmelt a t 150-152'.The action of dry ammonia gas on a well cooled mixture of alcoho44 ABSTRACTS O F CHEMICAL PAPERS.and monobromofumarimide yields transparent prismatic crystals ofzuonobromofnmaramide, melting between 168" and 175". This body isinsoluble in ether, slightly soluble in water and absolute alcohol, butdissolves easily in spirits of wine of 75 per cent. The aqueous solu-tion is decomposed by heat.The fumaric acid is probably formed by the action of water onmonobromosuccinimide. This may show why no monobromosuccinimidecould be obtained-CHBr.CH,(CO),NH + 2HOH = (CH.COOH), + NH4Br.w.C.W.On some New Carbamates. By DRECHSEL ( J . pr. Chenz. [23,xvi, 180--200).-1. Ammoni.1~?7z Carbawmte.-By passing carbonic acidgas into milk of lime previously diluted with 3-4 times its volumeof strong aqueous ammonia, a clear. liquid is obtained, which is decorn-posed OIL heating, with separation of calcium carbonate, and by sodiumcarbonate with immediate precipitation of the same. Carbamic acidis thus formed by the union of carbonic anhydride and ammonia p s e sin presence of water. We have here proof that the affinity existingbetweell these gascs is greater than that between lime and carbonicanhydride, and strong grounds for regarding aqueous ammonia assimply a, solntion of the gas in water. Ammonium carbarnate in solu-tion is ~ l o ~ l y converted into the carbonate.The conversion is, how-ever, incomplete, and is much impeded by the prcsence of free ammonia.Even on long boiling of its solution, the carbarnate is not completelydecomposed, and in presence of ammonia it is comparatively stable.While this compound thus passss more or less readily into ammoriiumcarbonate so inversely the latter salt in aqueous solution parts withthe elements of water and is converted into the carbarnate.2. Calcium Cicrbnmate, 2(NH,.C0,)2Ca + H,O.-Intcresting detailsof the preparation of this salt are given. It forms a fine powder, re-vealing under the microscope the presence of small flat prisms. Fromits saturated solution in warm aqueous ammonia, in which form itexhibits considerable stability, it crystallises, when cooled to 0", inbeautiful four-sided prisms.I n aqueous solution this salt is extremelyunstable. When newly prepared, it is entirely without smell ; but anamrnoniacal odour soon becomes perceptible, the salt entering into de-composition with its own water of crystallisation. Heated to 95-100"in an air-bath it is partially decomposed ; after some time the weightbecomes constant, the residue amounting to 76.56 per cent. of theweight of carbarnate taken, and consisting of a mixture of calciumcarbonate and carbarnate. This result entirely conforms t o the equa-tion-2(NH2.C0.0),Ca + HzO = NH,.CO,.NH, + (NH,.CO.O),Ca + CaCO,.The anhydrous salt exhibits decomposition on being heated to thesoftening point of ordinary glass.This occurs accordiiig to the equa-tion (NU12.C0.0)2Ca = CaCN, + 2H2O + GO*, calcium cyanide beingformed.-ORGANIC CHEMISTRY. 453. Strontium Carbamnte, (NH2.C0.0),Sr, occurs i n the form ofminute shining plates. The dry salt, being anhydrous, is much morestable than the calcium salt, which in other respects it entirely re-sembles.4. Ba&m Cccrbainnte was obtained only in the form of the doublcsalt which it forms with barium chloride, viz., (NH,.CO.O \,Ba.BnCl,.5. Lithium C'urbamate.-The author's attempts to prepare this com-pound were unsuccessful.6. Sodium Carbawmte crystnllises with water in beautiful prismswhich effloresce rapidly in the air, and quickly lose their water ofcrystallisation over sulphuric acid. I n the anhydrous state they arepermanent.The crystalline and anhydrous salts are decomposed onheating according to the following equations :-1. Crystalline salt.. . . . . 2(NH2.C0.0Na) + xH,O = Na,CO, +2. Anhydrous salt.. . . . . NH2.C0.0Na = NCO.Na + H20.NHz.CO.ONH, + (3 -1) HZO.7. Potassium Cadamate, NH2.C0.0K, has been prepared by theauthor according to several methods. It occurs in small needles andprisms, which %re deliquescent. The decomposition of the anhydroussalt by heat i R entirely analogous to that of the sodium salt. In neithercase is the formation of cyanamide observed. That this should occurin the case of the carbamates of the alkaline earths, is explained by asecondary decomposition of the cynnates of the latter, which are firstformed.Similarly ammonium carbamate yields urea as a product ofits decomposition by heat, mediately through the cyanate. All thecarbamates, therefore, hitherto investigated exhibit uniformly thisdecomposition into a cyanate and water. This dehydration isregarded by the author as identical in kind with that which dcter-mines t8he conqersion of amides into nitrils, and the constitution of theresulting cyanates as therefore identical with that of cyanetholin,thus :-CO{Egf = C { g i , + H20.c. P. c .Furfuramide and Furfurine. By R. S CH I FF (Deut. Chenz. Ges.Bey., x, 1186-11'33) .-The ammonia derivatives of a certain class ofaldehydes bave long been known t o be capable of being converted byheat or by boiling alkaline solutions into similarly constituted bodies,which, however, differ from them in stability and other properties.Similar reactions are seen in the conversion of hydrazobenzene intobenzidine, and of methyl-aniline into toluicline.The relation of theszreactions to the above-mentioned molecular changes must be gainedfrom a study of the hydrnmides, and the bodies which are isomericwith them.The hydramides - are formed according to the general equation46 ABSTRACTS OF CHEMICAL PAPERS.and they have hitherto been represented by the constitutional for-mula-R-CHR-CHydracetamide, wliich is formed in a similar manner, is also repre-sented by a similar formula (RICH,).But the aromatic liydramides (such as hydrobenzamide) and finfar-amide, &c., are unstable in presence of acids, while hydracetnmideyields two series of salts with strong mincral acids, so that the suppo-sition of an analogous constitution between hydrobenzamide a dhydracetamide may well be questioned.The author has investigated furfuramide and furfurine with theview of throwing light on the constitution of the hydramicles andtheir isomerides.Prepration of E'zLrfwanzide.-The best method is that of Fownes, byacting on aqueous furfurol with ammonia.Furfurine is obtained bybringing pure dry furfuramide (m. p. 117") into contact with boilingdilute caustic potash. Pure furfurine melts at IlCi", instead of looo,as stated by Fownes.A c t i o n of Acetic Anhydride o n ~u1.fUrine.-Monacetyl-furfurine,C1,H,,( C2H,0)N,0a, is produced in the form of small, white, flocculeyrtcrystals, insoluble in water, and moderately soluble in alcohol andether.It is decomposed byfusion with caustic potash, Heated So 240" it becomes charred, and a t250" melts and decomposes.The basic properties of the furfurine areperfectly lost in this derivative ; it is not altered by dilute acids, but isdecomposed by concent,rnted nitric acid.The acetyl group is undoubtedly united to the nitrogen-atom, but asecond hydrogen-atom does not seem to be present in this position,since ethyl and methyl iodides have no further action on acetyl-furfu-rine. It is n o t altered by being brought in contact with sodium inboiling xylene, and nitrous acid has no effect upon it.When furfurine is warmed with carbon bisulphide, and left in con-tact with it for a long time, it turns red, but snffers no further nltera-tion.Chloroform and alcoholic solution of caustic potash yield notrace of a body resembling the carbylamines.IrurfuTiwe and ATitrous Acid.-A yellowish crystalline body is formed,which is insoluble in water and ether, but easilysoluble in alcohol. Itmelts at 94-95" to a red liquid, which consists of C30H27N5015. Thisbody, treated with hydrochloric acid and platinic eldoride, yields a fineplatinochloride, (C30H2,N,0,,HC1),PtC1,. With ammoniacal solutionof silver nitrate it forms a double salt which is not altered by light).When an absolute ethereal solution of furfnrine is saturated withNz03, in the absence of every trace of moisture, a small quantity of avery unstable body is obtained, which becomes dark-coloured a t 82",and slowly chars.AcetyZ-$hTfu&ne is an exceedingly stable bodyORGANIC CHEMISTRY. 47FuTfzwnmide and Nitrous Acid.-Furfurol and ammoninm salts a1 t:separated, but the reaction goes further.The ethereal solution of fuy-fur01 saturated with N,03 deposits nothing on standing, but if theether is allowed to evaporate spontaneously, a violent reaction beginswhen it has nearly disappeared. The red syrupy residue grows warm,streams of nitric oxide escape, and a red oil is left, which tinally solidi-fies, yielding a body with strongly acid properties. This phenomenonOccurs only when small quantlities of furfurol ( 3 to 4 grams) areoperated upon. If a larger quantity (e.g., 10 gmms) is used, as socmas the ether has evaporated, a flame is suddenly observed, about ametare in height, accompanied by steam or smoke, and a porous massof carbon is left behind.Furfurine is not attacked by nascent hydro-gen or by the thiocarbimides (mustard oils).Act;on of Thiocarbimides o n Fwfuramide.-(l.) With a l l y l i c thio-c a r bimide. Fine silky-white needles are obtained, insoluble inwater, but soluble in alcohol and partly so in ether. They melt at118", and are decomposed a t 135". The composition of these crystalsis C1,H12N20,.CSNC,H5. (2.) With phenylic thiocarbimide awell crystallised snow-white compound is formed, consisting ofC,,H,,N,0,.CSNC6H, 4- H,O. This body is insoluble in water. It,may be heated t o 100" without loss of weight.Aldehydes do not seem to form any compounds with furfuramideand f urf urin e .Action of Bromin,e on AcetyZ~urfiL~-iiie.-The product is hexbrom-acetpl-furf urine, a yellowish-white powder, which is dissolved byacetic acid, and reprecipitated of a lighter colour on addition of water.It dissolves in alcohol, hnt suffers decomposition, the alcohol takingup hydrobromic acid.The formula of this body is C15H,1N203 $;,C2K30 + CBr. The formula assigned by the author to the '' furfurgroup is-0HC '=' CHI n pyrrol the carbon-atom connected with group X is replaced by>NH, the presence of which, and the absence of an KH2 group, re-main to be proved. Experiments on this point, have been begun, andit has been found that aldehydes, thiocarbimides, and bisulphide of car-bon do not act upon pyrrol.G. T. A.Distillation of Benzene, Toluene, and Xylene by Steam. 1-3~A. NAUMANN (Druf. Chem. Ges. Be?.., x, 1421). When the above-mentioiled hydrocarbons are distilled by means of stcam, the proportionof water and hydrocarbon which pass over, and also the boiling point,remain constant so long as the mouth of the tube which conducts thesteam into the boiling liquid remains wholly in the hydrocarbon,They are also independent of the rate of distillation, of the height ofthe liquid akove the point at which the steam enters, and of thespace above the liquid occupied by vapour ; when, however, the levelof the condensed water reaches the mouth of the tube, the tem48 ABSTRACTS OF CHEMICAL PAPERS.perature and proportion of the liquids in the distillate is no longerconstant.The results with regard to the boiling points are as follows :-Temperature atboiling pgjnt."Of mixed Of mixed,.>liquid. vapours. Diff. B.P.Benzene and water = 68.5 69.1 -6 Benzene only 79.5Toluene ,, ,, = 82.4 84.1 1% Toluene ,, 108.5Xylene 9 , 2, = 89.0 91.5 2.5 Xylene ,, 135.5The boiling point is in all caqes below that of the lower-boiling liqnid,owing to the attraction of uiililce molecules being less than those oflike molecules, as is also shown by the fact that the liquids are notmiscible. The difference between the temperatures of the liquid andof the vapour increases as the boiling point approaches that of water.Proportion of liquids in the distillate :-H,O.c6ir6. C7H8 C9ILbVolume.. . . 100 8.5 21.2 442.4 *79 5611 Nolecules . . -- -1 { "i-s:, - -The relation 0-41 : 1.24 : 1.78 = 1 : 3 : 4, the author considers to beHe hopes from these and further results to be able merely accidental.to draw conclusions as to the molecular constitution of the vapours.T. C.Reduction of the Aromatic Hydrocarbons. By B E R T H E r, o T(Conzpt. rend., lxxxv, 831-836).-The final product of the reductionof benzene by hydriodic acid is hexane, C6Hll, boiling a t 69", whilstC6H8, C6HlD, and C6LIIz, are formed as intermediate products.To explain this, the author supposes benzene to consist of one mole-cule of acetylene saturated with two others. Thus, C,H,(C,H,) (C,H,),these two latter molecules being capable in their turn of unitingseparately into hydrogen, to form the above bodies.L. T. 0's.Preparation of Pentabromotoluene. By 31. G u s T A v s o N (Bu7Z.Hoe. C h h . [2], xxviii, 347).-l'he author gives certain details of thepreparation of pentabromotoluene by the action of bromine on toluenein presence of aluminium bromide. The proportion in which thereagents should be employed are expressed by the ratio C7H8 : 5Br,,care being taken to have the bromine in slight excess. Resultsapproaching the theoretical are obtained. The reaction may even berecommended for the preparation of gaseous hydrobromic acid ; inthis case benzene may, of course, be substituted for toluene. Thepentabromide is easily soluble in benzene, from which it crystallises inlong needles, melting at 282-283".c. F. cORGANIC CHEMISTRY. 49Action of Bromine on Cymene. By M. GUSTAVSON (Bull.SOC. Chirn. [2], xxvi, 346-7). By the action of excess of bromine, inpresence of aluminium bromide, upon cymene (b. p. 174-1 75") toluenepentabromide and isopropyl bromide are formed. The reaction, whichtakes place a t 0", is represented by the equation, CloH14 + 5Br, =4HBr -+ C3H7Br + C7H3Br5, and is a striking instance of the decom-position, at a comparatively low temperature, of an aromatic hydro-carbon, with formation of a body belonging to the methyl series.The products of the decomposition are obtained in quant'itiescorresponding almost exactly with those required by the aboveequation. The toluene pentabromide obtained.melts a t 282-283" ;the isopropyl bromide boils a t 60-63".The formation of isopropyl bromide in this reaction may be explainedon two hypotheses. FIimt, that the cymene employed has the con-stitution of isopropyltoluene, and is resolved by the action of bromineinto its constituent radicles. Secondly, that the bromide in question isformed by the addition of HBr to propylene, this body being pro-duced according to the equation, CloH,, + 5Br2 = C7H3Br6 + 5HBr +C,H,. The author inclines to the latter view. c. I?. c.Cymene-Derivatives. By E. v. GERT c HTE N (Deut. Chsm. Ges.Ber., x, 1249-1252). Chlorine acts readily upon cymene (fromcamphor) in presence of iodine to form a nearly colourless chlorocymeite,of sp.gr. 1.014 at 1 4 O , boiling a t 208-211". This product yields, byoxidation with dilute nitric acid, a chZorotoZuic acid, crystallising inlarge lamin=, m.p. 194-195". The acid dissolves sparingly in hotwater, easily in alcohol. Its barium. salt, [C,H,Cl(CH3)C00]zBa +3H,O, crystallises in fine needles.The calcium salt, [ C6H,C1( CH,) C001,Ca + 3H20, forms crystallinenodules. By fusion with potash the acid yields an oaytoluic acid,which gives an intense violet coloration with ferric chloride.Cymene yields, by Fittica's process, a nitro-compound which crys-tallises in snow-white needles, melting at 124.5". The nitro-compound dissolves rapidly in warm strong sulphuric acid, and onpouring the solution into cold water, there is deposited a large quantityof white flocks, consisting, not of cymenesulphonic acid, as might beexpected, but of p-toluic acid, melting at 177-178".The formationof this last substance is not due simply t o oxidation of the propyl-radicle a t the expense of the nitro-group, but to a much morecomplicated reaction, which is being further investigated.A dichlorocymene, boiling a t 240-244", is also formed by the actionof chlorine upon cymene. J. R.On the Action of Sodium upon Halogen-substitution Pro-ducts of Aniline. By R. A N S C H ~ ~ T Z and G. SCHULTZ (Deut.Chem. Ges. Ber., x, 1802-1804). The authors find that by the actionof sodium upon ortho- and meta-cbloraniline, as they have previouslyfound in the case of the para-compound, azobenzene is formed.TheyVOL. XXXIII. 50 ABSTRACTS OF CHEMICfAL PAPERS.regard the reaction as occurring in three stages, expressed by theequations-(1.) 2(C6R4Br.NH2) + Na, = 2(C,H4.Br.NH.Na) + H,(2.) C6H4.Br.NH.Na + H, = C6H.,NHNa + HBr and(3.) 2(C6H,.NH.Na) + O2 = CI2HION2 + 2NaOH.The substitution by Na of the I3 of the NB2 group of bromanilineis probably determined by the presence of the Br atom in the benzenemolecule. The authprs have independently corroborated equation (33by a,n observation upon C6H5.NHK, which they have succeeded in con-verting into azobenzene, by subjecting it to the action of a stream ofair in presence of ether.The authors are engaged in extending this reaction to the productionof azo-compounds generally. c. F. c.Decomposition of Parabromaniline by Heat.By R. F ~ T T I Gand E. B ~ C H N E R (Liebig's Anm-den, clxxxviii, 23-30). Pure para-bromaniline melts at 63" to a colourless liquid, which when morestrongly heated, suddenly assumes a deep purple colour; at 190" acolourless liquid begins to distil, the boiling pojnt rising steadily to270", when it dark solid is left behind. The volatile product behaves onredistillation in a similar way, but the dark residue becomes less andless until at last only pure aniline distils. The residue consists of a smallquantity of a colouring matter, dissolving in alcohol with a splendidblue colour, and a mixture of dibrom- and tribom-aniline, which weredistilled off with steam, and separated by means of hydrochloric acid,in which the tribromo-compound is insoluble. The dibromaniline meltsat 89-90', and the tribromaniline at 119-120".When parabromaniline is heated for some hours with hydrochloricacid to 160", if is also partly resolved into aniline, dibromaniline, andtribromaniline. This singular reaction is explained by the equations :2C6H4BrNH2 = C6H5NH2 + C6H,Br2NH,, and C6H4BrNH2 +C6H3Br2NH2 = C6H5NH2 + CsH2Br3NH,.It is quite analogous tothe decomposition of certain metallic chloridss by heat as : 2MoC1, =MoC1, + MoCl,, and 3WC14 = WC12 + 2WC1,. c. s.Chlorobrornaniline. By R. F I T T I a and E. B ii c H N E R (Liebig'sAnn., clvxxviii, 14-23). When parabromoiiitrobenzene is reduced by tinand hydrochloric acid, a certain quantity of chlorobrornaniline is alwaysformed, which is most conveniently separated by crystallising the mixtureof the free bases from alcohol.To the mother-liquor, which containsall the chlorobromaniline and some pasabromaniline, hydrochloric acidand water are added. On distillation only the chlorinated base goes overas its hydrochloride is decomposed by water. The new base crysta,l-lises in colourless, glistening prisms, which are often an inch long ; itis almost insoluble in cold wat'er, sparingly soluble in boiling water,and freely in alcohol. It melts at 69--695", and readily sublimes.This compound has previously been observed by Hubner and Alsberg,who believed it to be nitrobromaniline. Several chemists have alreadORGANIC CHEMISTRY. 51found that by the reduction of nitro-compounds with tin and hydro-chloric acid chlorinated amido-compounds are formed.Beilstein andKuhlberg think that this is due to the action of stannic chloride, whileJager believes that a nitro-compound may be formed, which is thendecomposed by hydrochloric acid, and Hubner regards the nitrG-com-pounds as oxidising agents, which liberate chlorine from the hydro-chloric acid.I n order to test these differentl views, the authors made a series ofexperiments, in which they found that the quantity of chlorobromani-line iiicreases when the reaction goes on very violently, whereas when thenitrobrcimobenzene is gradually added to a boiling solution of stannouschloride and hydrochloric acid, only parabromaniline is produced.When bromonitrobenzene is heated with concentrated iiitric acid to100" for 16 hours, no reaction takes place, and bromaniline is also notchanged under the same conditions ; but a t 160" it is partially con-verted into dibromaniline (see last abstract).Chlorobromani line is,however, readily obtained by passing chlorine into a hot solution ofparabromaniline in concentrated hydrochloric acid. At the same timea dichlorbromaniline is formed, which does not combine with hydro-chloric acid, dissolves readily in alcohol, and separates from it in large,probably monoclinic crystals melting a t 93.5" to a, deep red liquid,which on solidifying again becomes colonrless. From these results i tappears that, during the reduction of the nitro-compound, some of thenascent oxygen liberates chlorine, which then exerts a substitutingaction. c.s.Dichloracetanilide. By C. 0. C E C H (Deut. C7~enz. Ges. Ber., X,1265--1267).-1n a former paper (Deut. Chem. Ges. Ber., ix, 337;abstract, Journ. Chem. Xoc., 1876, i, 710) the author described a sub-stance formed by the action of aniline on chloral cyanide-cyanate,which he then represented as an anilide of chloral, COH-CCC12.NHC,H,.Pinner and Fuchs (Deut. Ohem. Ges. Ber., x, 1063; abstract, Jourrz.C'henz. Soc., 1877, ii, 584) afterwards obtained the same substance bythe action of aniline acetate on chloral acetyl-cyanide, and came to theconclusion that it is the anilide of dichloracetic acid. The author hasnow succeedAd in preparing dichlora.cetanilide directly by the action ofphosphoric anhydride on aniline dichloracetate, and finds that it isidentical with the body first obtained by him as above.He has,therefore, established the correctness of the conclusion arrived at byPinner and Fuchs as to the constitution of the body.Dichloracetanilide may also be obtained by the action of aniline ondichlorace t amide. J. R.Condensation-products of Tertiary Aromatic Bases. By0 TT 0 F I S C H E R (Deut. Chem. Ges, Ber., x, 1623-1626).-1. Phthahhof ~~oo.izobromodiinethylaniline. - Bromodimethylaniline heated wihhphthalic chloride, yields a base, the hydrochloride of which crystallisesfrom alcohol in feathery steel-blue needles having the formulaC,4H,,Br,N202.HCI. This salt dissolves easily in alcohol, wood-spirit,chloroform, and glacial acetic acid, and sparingly in water.Strongacids dissolve it, with yellow coloration. The solution in stror;g bydro-e 52 ABSTRACTS OF CHEMICAL PAPERS.chloric acid deposits, on addition of water, a dirty green precipitatehaving the formula C2rH22N20,Br2.2HC1. The base separated fromthe hydrochloride is of a bluish-violet colour, and easily soluble inalcohol and ether. Its etheread solution gives with picric acid a greenprecipitate of picrate. ThepZatinum salt, 2( C2aH22N2Br202.HCl). + PtCl,,is an indigo-blue crystalline powder.2. Bemaldehyde and Di7n,ethylaniZine.-These substances act uponeach other in presence of zinc chloride in the manner shown by theequation-The base thus formed crystallises from alcohol in white needles melt-ing at 92-93', and dissolving easily in ether.It forms a picrate,C,3H26N2.2C,H2(N02)30H, which crystallises in yellow needles, anda platinum saZt, C23H26N2.2HC1.PtC14, which is white at first butturns green in the air. The other salts, especially when dissolved inalcohol, speedily undergo oxidation to bluish-green colouring mattersof complex constitution.3. Furfkrol and Dimethylaniline react similarly, under the influenceof zinc chloride, to form a white, crystalline, basic substance, whichmelts a t about 70". The composition of this body has not yet beendetermined with certainty. Its salts have the tendency to becomeoxidised to red colouring matters.Derivatives of Diphenylamine. By R. GNEHM and G. WYSS(Deut. Chem. Qes. Rer., x, 131 8-1324) .- T e t r u n ~ t r ~ ~ ~ l ~ e n y l a ~ ~ ~ a e . -1 part of diphenylamine dissolved in 40 parts of glacial acetic acid isheated in a capacious flask with 3 to 5 times its weight of nitric acid.Red fumes are evolved, and the solution turns green. When the re-action i s complete, excess of water is added, when a yellowish flocculentprecipitate separates. On drying it forms a dirty greenish-yellowpowder, forming a sticky mass when heated, and on cooling solidifiest o a brown resinous body. It is purified by boiling with dilute sodiumcarbonate solution, from which it separates on cooling in brownish-yellow flocculent masses which melt a t 150-1 70". Methyldiphenjl-amine yields the same body when thus treated, and not a methylnitro-diphenylamine. The largest and purest yield is obtained by actingwith 3 to 5 parts of nitric acid on 1 part of diphenylnitrosamine dis-solved in 10 parts of hot glacial acetic acid.When pure the new body crystallises from glacial acetic acid in fineyellow needles or prisms which melt a t 192", and on being morestrongly heated in the air burns with ease, but does not explode.Onanalysis it was found to have the composition NC12H7(N0,)4. It is,therefore, tetranitrodiphenylamine, NH. { C6H3(N02)2)2, and conse-quently is isomeric with Austen's pampicrylmetanitraniline melting at205" (Chern. 8oc. J., 18i5, 165) and parapicrylparttnitraniline meltincr 9 at. 216".Tetranitrodiphenylamine is soluble in alcohol, ether, and benzeue,and crystallises from its solution in fine yellow needles or prisms.Like its isomerides it is easily dissolved by a hot solution of sodiumor potassium hydrate, forming it magnificent scarlet solution, whichJ.RORCIANIO OHEMISTRY. 53on cooling deposits the body unaltered in red-brown minute needles.The authors were unable to obtain an acetyl-derivative, even by theaction of hot acetyl chloride in pressure tubes.Tetramidodiphenylaw&ne.-When tetranitrodiphenylamine is reducedby means of zinc and dilute hydrochloric acid, it forms an easilysoluble colourless salt, from whose aqueous solution sodium hydrateprecipitates a colourless, flocculent, basic body. This the authors con-sider to be tetramidodiphenylamine, NH. { C6H3(NH2), rz, but they wereunable to obtain it in a state fit for analysis.The solution in hydro-chloric acid of the new base turns red-violet in the air ; gives a violetcolour with platinum chloride, gradually resolving into a dark preci-pitate ; a dark violet with ferric chloride ; a dark brown-red with zincchloride, and with sodium nitrite a blue colour quickly turning red,and then resolving itself intlo a brown precipitate. By the addition ofammonia a colourless precipitate is formed, but on exposure to air theprecipitate redissolves, and a splendid deep blue solution is formed, ofvery unstable character.By the action of air the new base is readily cxidised, with probableformation of tetrimidodiphenylamine, the reaction being similar tothe formation of diimidonaphthol from diamidonaphthol (Ann.Chem.Pharm., cliv, 303).Din.itrotribro~~~zocli~lzenylnmine.-When a solution of 1 part of tetra-bromodiphenylamine in 1 to 2 parts of nitric acid is heated, muchnitrogen tetroxide and bromine is evolved, and on cooling a browncrystalline mass separatles. By treatment with alcohol, glacial aceticacid, and sodium hydrate solution, different bodies are separated. Theportion soluble in alcohol yields after repeated recrystall'isations a newbody which melts a t 209-210", and gives on analysis numbers agree-ing with the formula Cl2H6H3Br3O,. It is diiiitrotribromodiphen yl-amine, N.C12HI,(N0,),Br3. When pure it forms thin, glittering, yellowplates, soluble in ether to a reddish-yellow solution, arid in benzeneand chloroform with a yellow colour.It melts to a yellow liquid, andburns easily when strongly heated in the air. E. N.Action of Primary Amines on Diphenylnitrosamine. By0 rr T o N. W I T T (Dezct. Chem. Ges. Bey., x, 1309). -Diphenylnitros-amine and aniline react vigorously on one another at 70°, the tem-perature rising to upwards of 100". Hydrogen is evolved, of veryevilodour, a dark tarry mass being formed. If excess of aniline is em-ployed, it is possible to isolate amidazobcnzene, diphenylamine, anddiazoamidobenzene from the products, but only with difficulty, onaccount of the tarry bye-products. If, however, paratoluidine beemployed (4 parts to 1 of nitrosamine) paradiazoarnidotoZluelze, meltingat 115.3" to 116" is readily obtainable from the product by washingwith dilute acetic acid and crystallisation from ligroin.The bodycorresponded in all respects with pure paradiazoxmidotoluene ; itformed an amido-aaoderivative on heating with hydrochloride ofaniline, and when it was heated with alcoholic phenylenediamine, nocoloration was developed (difference from diazo-bodies). On furtheradding acetic acid, an orange-red chrysoidin was produced. From th54 ABSTRACTS OF CHEMICAL PAPERS.mother-liquors diphenylamine, melting at 55", was obtained.action of the paratoluidine hence appears to be-The re-N(CsH5)zNO + NHz.C,H, = HZO + N(C6H,)zN=N.C,H,N(CJ&),N = N.C7H7 + NHZ.CTH7 = N(CtjH,),H +C~H~.NIZN.NH.C~H~.When a mixture of diphenylnitrosamine and aniline hydrochloridein equal numbers of molecules with double the weight of aniline, isleft to itself for some hours and then gently heated, an almost quan-titatlive yield of amidoazobenzene is obtained by a parallel reactlion,the diazoamidobenzene first formed being further acted upon by theaniline hydrochloride.At a higher temperature and with a larger excessof aniline, a different body is produced, crystallising in lustrous rubyneedles, soluble in concentrated sulphuric acid, with an intensecharacteristic violet tint. The forniation of this body was traced tothe reaction of the diphenylamine sct free in the earlier stage on theamidoazobenzene, the equation being-SO tlhat the new product is the saffranin of tbhe series. The author re-gards it as the type of a new class of compounds containing 3 N-atomslinked together, to which he proposes to apply the term triazo-deiiun-iiv es .C. R. A. W.Derivatives of Orthotoluidine. By A. L A D E K B u R G (Deut.Chem. Ges. Ber., x, 1260--1262).-1n a former paper the author statedthat he had obtained, by heating formotoluide, a substance agreeingin composition with the formula CsH,N. Further examination hasshown that the substance is identical with methen;yldiorthotolyldiami~~e,CI6HIRNZ, obtained by the action of phosphorus trichloride on formo-toluide containing toluidine. The identity of the two products isshown by their crystallising in prisms which melt at the same tern-perature (150") ; by their dissolving in dilute hydrochloric acid onlyon heating ; by their platinum double salts having the same crystal-line form ; and by their behaving in the same manner with bromine,with which they combine to form a substance crystallising in yellowprisms, a,nd having the formula C 15H16N2Br2.The author has also obtained ethenyldiorthotolyldiamine, Cl6HlRN2, bythe action of phosphorus trichloride on orthotoluidine and glacialacetic acid.This substance crystallises in colourless needles, whichdissolve easily in dilute hydrochloric acid and melt at 140.5".J. R.A New Xylidine. By E. WROBLEVSKT (Deut. Chern. Ges. BcT.,x, 1248).-This substance was obtained by the following steps :-Purified isoxylene was converted first into nitro-compound, and then,by reduction, into xylidine. The xylidine was converted, by heatingwith acetic acid, into acetoxylidine (melting point 127"), and this proORGANIC CHEMISTRY.55duct was heated with nitric and sulphuric acids, to form acetonitro-xylidine, which crystallised from alcohol in colourless needles meltingat 180". The acetonibroxylidine, when heated with sulphuric acid,yielded solid nitroxylidine, which crystallised in red needles meltingat 76". This nitroxylidirie gave by Griess's reaction a solid nitro-xylene, which crystallised from alcohol in large flat needles (meltingpoint 2 5 5 O ) , and yielded by reduction a liquid xylidine of sp. gr. 0.9935at O", boiling a t 220-2'21".The following salts have been prepared :-C,H,NH,.HCl. Long colourless brilliant needles.CBH,NH2.HN0,.( C8H,NH2),H2SOa + H,O.The acetyl-compound, C,H,NH( C,H,U), crystallises from .alcohol inThe constitution of thisLong white nacreous needles, soluble in 21 partsof water at 13".Long white needles.large flat needles, which melt at 144.5".xylidine is not yet made out. J.R.On the Bases C,H,,-,ClN,. By 0. WALLACE and F. OPPEN-PIE I M (D&. Chem. Ges. Ber., x, 1193--1199).-The authors obtainedfrom diethyloxamide a basic body of the composition C,H,C1N2, t owhich the name of cklorozalethyliiie was given (this Journal, 1877, ii,184). I n order to determine whether it is possible to remove thechlorine from this body by simple reactions, it was dissolved in petro-leum-naphtha, aiid finely divided sodium was added to the solution.The following equation represents the results of the reactioll:-2C6H,C1K2 + Naz = C,,H,,N, + 2NaCl.When bromine isadded to a solution of chloroxslethyline in carbon disulphide or chlo-roform, i t is eagerly absorbed, and a reddish crystalline mass is formed,which can be separated into two parts by crystallisation.The largerof these consists of red needles, melting at 112~5--113*5" : tlie otherpart forms fine red crystals, melting at 132-133", the crystallographicmeasurements of wliich are given in the paper. Both these bodies aresoluble in chloroform, carbon disulphide, and alcohol, but not in coldwater. Hot water dissolves them, with decomposition. The follow-ing formule show their composition :-The base Gl2Hl,N4 may be called cliomdethyline.Tetrabromide . . . . . .Tribromicle . . . . .. . . CsH9C1N2Br4 = C,H8C1BrN,.Br2.BrHC6H9C1N,Br3 = C6H,C1BrN,.Br2Both compounds yield the same base when boiled with water. Thisbase, C,H,ClBrN,, may be called bromochloro~alethyline. It is spa-ringly soluble in water, but dissolves in alcohol, and possesses a pecii-liar aromatic: d o u r . I n addition tothe hydrobromic acid salt (which is very hygroscopic) the followingsalts were obtained : the hydrochloric acid salt in hydrated prisms,the nitric acid salt in small curved needles, the platinum salt,(C,H8Cl13rN2.HC1)2PtCl~, in fine plates.It forms fine crystalline salts.The silver salt56 ABSTRACTS OF CHEMICAL PAPERS.is very characteristic. It may be obtained by mixing an aqueoussolution of the base with silver nitrate. It crystallises from dilutealcohol in remarkably well formed, transparent, glassy prisms.Saltsof the base may also be formed from other metallic salts.The bromine of the free base seems to be as intimately united as thechlorine. It is scarcely acted on by aqueous and alcoholic solutions ofpotash, but is perfectly decomposed by distillation. There is a strikinganalogy between the halogen-derivatives of chloroxalethyline and ofnicotine, as the following table shows :-Derivatives of oxalethyline. Derivatives of nicotine.CsH,oK ClOH,,N,CsH,BrzN2.Br.HBr ClOHl2BrN2.Br2.HBrCsHsBr2N,.Br2 C,oH12Br2N,.Br2C6HsBr2N2.HBr C,oHE2Br,N,.HUr.Iodine unites with chloroxalethyline in the same way as brominedoes. G. T. A.Xylene Sulphamides. By IRA REMS E N (Dewt. Chem.Ges. Bey.,x, 1199--1200).-The author has described the preparation of thesulphoxylenes in a previous paper. I t has since been found that theperfect separation of the xylenesulphamides is not so easy as at firstappeared to be the case. Three bodies have been isolated from thecrude product. The first of these melts at 132" ; the second at 110".These two are both derived from isoxylene. The third body has notbeen obtained in a state of purity, and it is not known whether it is aderivative of para- or of isoxylene. The amide, which melts at 132",yields, when distilled alone or with lime, a body which is insoluble inwater, but crystallises from alcohol. It has not yet been examined.Oxidation of a mixture of the amide melting at 110" with the thirdamide yielded parasulphaminetoluic acid, together with a second acidwith similar properties.Most of the tri-derivatives of benzene are found to split up on oxida-tion into the simplest products.Bromoparaxylene yields on oxidation a monobasic acid, bromopara-toluic acid, which shows that the bromine-atom prevents the oxidationof one of the methyl groups.The bromine protects the group towhich it holds the ortho position. Bromethyltoluene may be either-From the first formula oxidation should produce an acid-C,H,.C2H,.Br.COOH :from the second, C6H3.CHI,.Br.COOH. G. T. ORGANIC CHEMISTRY. 57Compounds of Elements of the Nitrogen Series with Aro-matic Organic Radicles. By A. MICHAELIS and E. BENZINGER(fiebig's Annalen, clxxxviii, 275-292) .-This section of the author'sresearches treats of the derivatives of benzenephosphonic acid, whichbears to phosphoric acid the same relationship that benzenesulphonicacid does to sulphuric acid :The authors apply to it the term phosphenylic acid.Benzenephosphonic acid dissolves in nitric acid without alterationeven when heated; but on heating it with 7 parts of fuming acid insealed tubes to 100-110" for 5 or 6 hours, nitration takes place, littlebut nitrobenzenephosphortic acid (nitrophosphenylic acid) being formed,C6H4(NOZ).PO3Hz.A white solid mass is left when the contents ofthe tubes are evaporated to dryness; this is best purified by con-verting it into barium salt by means of barium carbonate, and treatingthe product with cold water till nothing more is dissolved ; benzene-phosphonate of barium is then left undissolved.On concentratingthe €ltrate on the water-bath, brilliant yellow plates of nitrobenzene-phosphonate of barium separate, containing CGH4(NOz) .P03Ba,2Hz0,three-fourths of the water of crystallisation being lost at 180", whilethe remainder is expelled only at a higher temperature at whichdecomposition commences. From this salt the free acid is obtainedby decomposition with sulphuric acid and treatment of the productwith ether ; it crystallises from water in cauliflower-like masses, fromether in white symmetrically arranged needles, very soluble in water,and highly deliquescent. When dry it is quite white, but the aqueoussolution is strongly coloured yellow, leaving a white residue on evapo-ration to dryness ; 100 parts of water at 22" dissolve 98 of acid ; at98", only 92 parts are taken up : the barium salt also is more solublein cold than in hot water. Alcohol and ether readily dissolve nitro-benzenephosphonic acid, but it is insoluble in benzene; it melts at132", the fused mass solidifying at 105"; at upwards of 200" itexplodes, the odour of nitrobenzene being evolved and much carbonbeing left; hence in making a combustion of it, it is necessary to mixit thoroughly with finely divided copper oxide.When it is fused withsoda-lime, aniline is evolved, the acid first splitting up into nitroben-zene and phosphoric acid (just as benzenephosphonic acid formsbenzene and phosphoric acid), and the nitrobenzene being subse-quently altered by the soda-lime ; fusion with caustic potash forms a,dark-red product soluble in water w i t h the same colour ; the colour-ing material is not taken up by ether or by alcohol after passing incarbon dioxide and evaporation to dryness.The alkali-salts of nitrobenzenephosphonic acid are readily obtainedby neutralising the acid with the appropriate alkali ; they are readilysolnble and do not crystallise ; those of the alkaline earths are diffi-cultly soluble and are crystallisable.Besides the neuiral salt, an acidburiuna salt exists (C6H4(N02).P03H)zBa,2H20 j this is obtainabl58 ABSTRACTS OF CHEMICAL PAPERS.from the neutral salt by treatment with enough sulphnric acid to with-draw half the barinm present; it is more soluble in water and lessreadily crystallisable than the neutral salt ; alcohol t,akes up tracesof it.The calcimz salt, C6H~(N02).P03Ca.~H,0, when dried oversulphuric acid, may be obtained as an amorphous powder by neutra-lising the free acid with marble-powder, collecting the insoluble mass,dissolving it in water, evaporating the filtered liquid t o a smallbulk on the water-bath, and finally leaving it over sulphuric acidin a vacuum. The & h e r saZt, C6H4(No2).PO3Agl, is amorphous, asis also the lead salt, C6H4(N0,).P03Pb; these are obtainable fromthe neutral alkaline salts by double decomposition as precipitates ;from a neutral solution of sodium nitrobenzenephoaphonate, bariumchloride throws down a white crystalline precipitate on boiling ; leadacetate, a white precipitate soluble in nitric or hot acetic acid ; ferricchloride, a red precipitate, soluble in hydrochloric acid ; copper sul-phate, a slight precipitate in the cold, becoming much more copiouson boiling, and soluble in much acetic acid.Cobalt nitrate onslightly warming gives a violet precipitate soluble in hydrochloric acid ;bismuth nitrate, a white flocculent precipitate soluble in hydrochloricacid, insoluble in acetic acid ; mercuric chloride, ZE white flocculentprecipitate ; and zinc chloride, a white precipitate, soluble in hydro-chloric acid on warming, and re-precipitated by addition of ammonia.By the action of nascent hydrogen (tin and hydrochloric acid)nitrobenzenephosphonic acid is readily converted into amidobenxene-phosphonic acid (amidophosphenylic acid), C6H4(NH2) .PO,H,, crystal-lisable in white shining needles, soluble in hydrochloric acid, sparinglysoluble in water (0.43 part in 100 a t go", 0.52 at loo"), and insoluble inalcohol and ether.When heated i t does not fuse, but turns bluislz-green a t 280" wit>h decomposition ; heating with soda-lime splits it upinto phosphoric acid and aniline, thus :-CsH,(NH,).PO(OH)Z + HZO = CsH5.NH2 + PO(OH),.With hydrochloric acid it does not form any stable isolable com-pound ; although it readily dissolves in that acid, the solution fur-nishes nothing but unaltered amidobenzenephosphonic acid on spon-taneous evaporation over lime. Amidobenzenephosphonatcs of thealkaline earths and alkalis are readily soluble in water ; the lead, silver,and copper salts, respectively, C6H4( NH,) .P03Pb, CaH4( NH,) .P03A g,,and C,H,(NH,) .P03Cu, are obtained as precipitates by double decom-position.Sodium amalgam and nitrobenzenephosphonic acid do not formazo- or hydrazo-benzenephosphonic acid, the main product being thesodium salt of amidohenzenephosphonic acid, C8H4( NHz).PO3Na23HzO.From this the acid is obtained by addition of lead acetate, and de-composition of the precipitated lead-salt by sulphuretted hydrogen.Diaxobenzenepl~osphonic nitrate or DiasophospherLylic nitrate,C6H,Ns03.POJL = CJb<po,H, O r C6H3(N0,)<p03H2 This N=N03 N=NO.His an acid compound produced by the action of nitrous acid on a soln-tion of amidobenzenephosphonic acid in nitric acid.It forms wellORQANIC CHEMISTRY. 59defined prisms containing 3H20, melting at 18V, and exploding atslightly higher temperatures ; 100 parts of water dissolve 57.82 partsat 18", 59.03 at 80", the solutions being yellow ; in alcohol it is readily,in. ether sparingly, soluble. On boiling it with watei* alone, no forma-tion of nitric acid is noticeable, nor is any produced by the furtheraddition of sulphuric acid ; but on boiling with caustic soda, a dark-red colonr is developed which almost disappears on addition of sul-phuric acid; nitric acid can then be readily distinguished in theliquid. The salts which it forms with the alkalis and alkalineearths are soluble and crystallisable ; those of the heavy metals forthe most part insoluble and red or yellow; they are all explosive.The sodium saZt, C6H,N303.P03Na, + 2H20, is precipitated as a yellowcrystalline substance on adding alcoholic caustic soda to a concen-trated solution of the acid in absolute alcohol ; it is almost insolublein alcohol, but readily soluble in water, and crystallisable therefrom.The potassium salt, C6H,N303.P03K2 + 2H20, is similarly obtained, andpossesses the same properties.The barium saZt, CsH4N303. P03Ba + 3H,O,is obtaiiied by neutralising t,he acid with barium carbonate, dissolvingthe sparingly soluble salt in water, and conccntrating first over thewater-bath, then in a vacuum over sulphuric acid ; it forms reddish-yellow shining needles. The sdver and Zeud saZts, CIH4N,03.P0,Ag,and CsH4N3O3.Po3Pb, may be obtained as amorphous precipitates byadding the corresponding metallic salts to an alkaline salt of the acid.It is noticeable that of the 3 mols.of water of crystallisation in thefree acid, only 2 are lost at 130°, the third not being expelled until atemperature is reached at which the acid begins to decompose : hencethe monohydrated acid may be regarded as C6H,(NO2) { ;z;:( 0 H>zif the acid be viewed as containing the nitro-phenyl group C,H,(NO,).In general properties this diazo-derivative is different from mostmembers of the diazo-group hitherto described, especially in notevolving hydrogen and forming an oxy-acid on boiling with wateror alkalis. Experiments on the action of reducing agents are con-templated with a view to determine which of the above two formulacorrectly represents the substance.C. R. A. W.Azophenetol. By E. HEPP (Deut, Chenz. Ges. Ber., x, 1652).-This substance is prodnccd by the action of reducing agents on nitro-phenetol. It is best obtained by heating an alcoholic solution ofnitrophenetol (1 : 4) with potash and zinc-dust, and filtering the liquidwhile hot. The azophenetol (1 : 4) is depositled, as the solut'ion cools,in small orange-yellow lamin=, which melt at 175" and afterwardsdistil without deconiposition. It is insoluble in water, but dissolveseasily in ether, benzene, and hot alcohol. The numbers obtained byanalysis agree with the formula-C2H50.C6H,.N3!?. C,&.OC2H,.Similarly, nibrophenetol (1 : 2) yields aeophenetol (1 : 2)60 ABSTRACTS OF CHEMICAL PAPERS.Azophenetol is also formed on treating the silver salt of azophenolwith ethyl iodide.Conversely, azophenetol, when heated to 180" withhydrochloric acid in sealed tubes, yields azophenol, together with ethylchloride. J. R.Derivatives of Thymol. By A. LADENBURG and TH. ENGEL-B RECHT (Dezd. Chern. Ges. Rer., x, 1218--1225).-The ethyl-ether ofdiirh-othymol is obtained by heating the sodium salt to 140-150" insealed tubes with ethyl iodide and alcohol. It crystallises in colour-less tables, which melt a t 52-53", dissolve easily in alcohol and ether,and decompose when distilled.The ether yields, by reduction with tin and hydrochloric acid, a bodywhich is converted by distillation with dilute aqueous ferric chlorideinto oxythymoquinone and clioxythymoquinone.Dinitrothymol reacts with phosphorus pentachloride, when heatedtherewith, to form chZorodinitrocy~)zene, C,,H,,Cl(NO2),. This sub-stance melts a t 1OO-l0lo, and is moderately soluble in alcohol andether, less freely in carbon bisulphide and chloroform.Chlorodinitrocymene is converted by reduction with tin and hydro-chloric acid into an amido-compound, which, by oxidation with potas-sium bichromate and sulphuric acid, yields oxythymoquinone and chlo-roxy thymoquhn e, C,CH3CsH7 0,O H.The latter substance crys tallisesin lemon-yellow prisms, which melt a t 122", sublime very readily, anddissolve easily in alcohol and toluene. It dissolves in solution ofpotassium hydrate or carbonate, with fine violet colour, and is pre-cipitated unaltered by hydrochloric acid.But on boiling the alkalinesolution it is converted into d ioxythymoquiizone or thymozarin.Dioxythymoquinone, CloH120a, crystadlises from hot alcohol in prismsof a beautiful red colour, which melt a t 220" and sublime without de-composition. It is only sparingly soluble in alcohol and water, butdissolves easily in ammonia and potash with violet colour. The sameproduct had been previously obtained by the authors by boiling a con-centrated solution of oxythymoquinone in potash.According t o Ladenburg, the foregoing facts afford a new and, hethinks, incontestable proof of his proposition, that benzene containstwo pairs of symmetrically-combined hydrogen-atoms.If the formula of thymol be written thus :a. 6 .C. d. e. f-GI3 CH, C,H, OH H H Hthat of chlorodinitroxycymene must be-a. b. c. d. e. f.CS CH, C,H, C1 NO, NO, HIn whatever way the oxidation of the corresponding amido-compoundis effected, the chlorine in the resulting chloroxythymoquinone willundoubtedly occupy the position c ; consequently the dioxythymoqui-none obtained from the last-named body will have the group (OH) iORGANIC CHEBDSTRT. 61the same position, and its formula must be one of the three follow-ing :-a. 7). C. a. e. f .CS CH3 C3H7 OH 0 0 OHCS CH3 C3H7 OH 0 OH 0CS CH3 CsH, OH OH 0 0On the other hand, since dioxythymoquinone may also be obtainedfrom thymoquinone, by previous conversion into oxythymoquinone,and since thymoquinone from thymol must have one of its oxygen-atoms in the position c, it follows that dioxythymoquinone thus pre-pared must have one of the three following formulze :-a.6 . C. a. e. f.C6 CH3 C3H7 0 0 OH OIICS CH3 C3H7 0 OH 0 OHc6 CH3 C3H7 0 O H OH 0Now, in whatever way these six formulze may be arranged, theylead direct to the above proposition, or (what the author, in his Theorieder aromatischen V e d k h c n g e n , has shown to be the same thing) to thenecessary condition, that two of the hydrogen-atoms in benzene aresymmetrical in regard to the other four. J. R.Diatomic Phenol of Xylene. By CH. GUNDELACH (BUZZ. SOC.Chinz. [ 21, xxviii, 342-346).-The author prepares the potassium saltof isochloroxylenesulphonic acid, C6H,C1.SOsK + H20, which he de-composes by fusion with potash ; he thus obtains a body crystallisingin small prisms, and exhibiting reactions similar to those of beta-orcin. This circumstance, together with the analogous formation ofthe latter compound from chloro-sulphocresylic acid, are regarded bythe author as warranting the formula C6&( OH)2, C. F. C.Action of Hydrochloric Acid upon Resorcin. By L. B A BT Hand H. WE J D E L ( D e u t . Ohem. Ges. Bey., x, 1464--1472).-By heatingresorcin (20 grams) with fuming hydrochloric acid (25 c.c.) for somehours in sealed tubes to 180", a resinous mass is obtained whichexhibits a green metallic lustre iu reflected light. From this theauthors have isolated two bodies, A and B, its chief constituents :(A.) A bright brownish-red amorphous powder, insoluble in watcrand in ether ; slightly soluble in cold alcohol, easily solnble in hotalcohol and in glacial acetic acid.It is further dissolved by concen-trated sulphuric acid, and is precipitated from this solution unchangedon dilution. Aqueous alkalis also dissolve it, forming a deep redsolution, which exhibits a beautiful green fluorescence. The authorsassign to this body the formula C12H1003.By heat,ing it with acetyl chloride to 100" in sealed tubes, r2 diacetylsubstitution-product, C,H30),03, is obtained as a dark-brownpowder. By fusion with potassium hydrate i t is converted into re-sorcin. By heating it, according to the usual method, with zinc-dust,a distillat'e is obtained in small quantity, in which traces of benzene anddiphenyl may be detected62 ABSTRACTS OF CKEMICAL PA4?ERS.As the simplest representation of the reaction by which this dichroicresinous body is formed, the authors suggest the equation 2C6H,O, =H,O + CI2H,,O,, and infer the following constitutional formula(C,&),O(OH),. Deducing from this an obvious analogy to fluoresce'in,they have prepared a tetrabrominated derivative by the action ofbromine upon the cold solution of the original substance in glacialacetic acid-in anticipation of its possessing colouring propertiessimilar to t h p e of Baeyer's eosin-which is essentially a brominatedanhydride of resorcin.The compound was found, in effect, to possesstinctorial properties, but the colours communicated by it to fabricswere a brownish- and greyish-red, and decidedly lacked purity. Hencethey conclude that while fluorescence is characteristic of bodies formedupon the type of anhydride, beauty and purity of colour follow onlyfrom the introduction of the phthalic acid residue.(B.) A bright red amorphous powder, easily soluble in ether,alcohol, and glacial acetic acid, and to a certain extent in both cold andhot water.The aqueous alkalis dissolve this body to a brownish-yellowsolution, which exhibits a blue flixorescence. Its empirical constitutionis reprnsented by the formula C,4H,805. By heating it with acetylchloride to 100" in sealed tubes, the diacetyl-product, C,,H,,( C,H,O j205,is obtained as a brown powder. By fusion mith potassium hydrate,resorcin is regenerated.By the action of broniine upon the cold solu-tion of this body in glacial acetic acid, a hex-substitution compound,C,,H,,Br,O,, is formed.The authors express the reaction by which this second const'ituentof the original resin is formed, by the equation 4C6H,O2 = 3H20 +C24H1805, from which, in conjunction with the above reactions, theyinfer the constitutional formula (C,H4),.03.(0Hj,.Both ethers are vigorously acted upon by nitric acid ; amorphousproducts are obtained as precipitates on the addition of water. Afterlong boiling with nitric acid, until water no longer occasioned a pre-cipitate, a crystalline powder was deposited on evaporation, which,after purification, was identified as isophthalic acid.I n conclusion, the authors recommend the original reaction withhydrochloric acid as an exceedingly delicate test for the presence ofresorcin.This react'ion is unaffected by the presence of pyrocatechin,and of the impurities which often accompany resorcin. C. F. C.A New Mode of Formation of Hydroquinone. By El. HEPP(Deut. Chenz. Ges. Bcr., x, 1654) .-On adding hydroxylamine hydro-chloride to a dilute aqueous solution of nitrosophenol in soda-ley, andgently warming the liquid, nitrogen is evolved and hydroquinone pro-duced. The first product of the reaction is diazophenol, which breaksup into hydroquinone and nitrogen thus :-C6H4(OH)NO + NH,.OH CcH,(OH)N=N.OH + H,O;CBH,(OH)N=N.OH = CsH,(OH), + Np J. R.Actions of Amines upon Chlorinated Quinones.By G. NEU-H ~ F F E G and G. SCHULTZ (Dezd. Chenz. G'es. Ber., x, 1792-1793j.-The objects of this investigation are to ascertain (1) in what respects thORGANIC CHEMISTRY, 63action of amines upon the quinones differs from their action uponketones; and (e), whether this action is confined to monamincs, or iscommon to the diamines, imides, and amides. From the solution ofthese questions the authors hope to be able to draw conclusionsrespecting the constitution of the quinonamines.By the action of trichloroquinone upon aniline, the authors haveobtained a compound crystallising in shining plates having a metalliclustre. The composition of this body is expressed by the formulaC,,Hl,N,C1O2. It appears, therefore, to be dianilidomonochloroqui-none.C. F. C.Formula of Quinhydrone. By C. L I E 13 E R M AN N (De7~t. C h n .GYes. Ber., x, 1614-1618) .-The formula, C12H1004, assigned t o thissiibstance by Wohler and Laurent., was altered by Wichelhaus, inaccordance with the results of his investigations, to CI8H14o6. Now,since quinhydrone is produced directly by mixing aqueous solutions ofquinone and hydroquinone, and is the only product of the reaction,the first of these formultt: represents i t as a compound of 1 mol. ofquinone with 1 mol. of hydroquinone (C,H,O, + C6H602), whilst thesecond represents it as a compound of 2 mols. of quinone with 1 mol.of hydroquinone (2CGHd02 + C6H602).I n order to determine which of these is the true formula, the authormixed together aqueous solutions of quinone and hydroquinone, andweighed the quinhydrone precipitated.He thus found that (1) whenthe two substances were mixed in equivalent proportions, the amountof quinhydrone thrown down was somewhat less than that required bythe formula, C12H1004 (owing to its being soluble t o a slight extent inwater), but greater than that required by the formula, ClsHl,O, ; (2)when the substances were mixed in the proportion of 2 mols. ofquinone to 1 mol. of hy droquinone, the quantity of quinhydrone throwndown was less than corresponded with either formula.Moreover, on testing the filtrate from the quinhydrone, he foundthat, in the first case, neither quinone nor hydroquinone was in excess ;whereas in the second case, quinone was always in excess.* Hence heconcludes that the true formula of quinhydrone is C12€1,004 ; and thatother quinhydrones must, similarly, be composed of quinonc andhydroquinone in equal numbers of molecules.Formula, of Quinhydrone.By H. WICHELHAUS (Deut.Chern. Ges. Ber., 1781--l’i83).--The author defends the empiricalformula, CI8HlpO6, assigned by him to quinhydrone, against the stric-tures of Liebermann, and further shows that his hypothesis of the con-stitution of this body, out of 1 mol. quinone and 2 mols. hydroquinone,is not inconsistent with its formation by the reaction of its constituents inthe proportion of single molecules. For, in the formation of 1 mol. quin-* Quinone, in aqueous solution, may be rcaclily detected by means of an alcoholicsolution of hydroccerulignone, one drop of which added to a quinone solution instantlycolours it yellowish-red, and thm tames a deposit of the steel-blue iridescent ncedlesof ccerulignone.The reaction is exceedingly delicate : it depends upon the conver-sion of hydroccerulignone into ccerulignone on the one hand, and of quinone intohydroquinone on the other. Hydroccltrulignone may likewise be employed for thedetection of many oxidizing agents.-J. R.J. R64 ABSTRACTS OF CHEMICAL PAPERS.hydrone from a mixture of 2 mols. quinone and 2 mols. hydroquinone,1 mol. hydrogen is liberated, and 1 mol. quinone remains. Of these theformer is sufficient to convert the latter into hydroquinone. Since ibisaction occurs gradually, and the resulting formation of hydroquinonedetermines a further production of quinhydrone, it is not unreasonableto suppose that when + of the quinone have been reduced to hydro-quinone, t'he remaining -$ will have disappeared, the whole havingunited to form qninhydrone.c. I?. c.Constitution of the Catechins. By A. GAUTIER (Compt. r e d ,lxxxv, 752-755) .-When the catechins obtained from acacia catechu,(which the author bas shown to have the formula, C21H1808, and notCl,Hl,04, which Hlasiwetz assigned to them), are treated with potash,they yield protocatechuic acid, phloroglucin, and formic acid, which insome cases is decomposed into marsh gas and carbon dioxide. Whenthey are treated with hydriodic acid, iodoform is found amongst theproducts of decomposition. From these reactions it appears that thesecatechins contain either the group, -CH2--CH=C=O2, or the group,The action of sulphuric acid gives rise to protocatechuic acid, aphenol having the formula, CliH16O7, and an anhydride of the latter,C28H2207.Owing to some error in the structural formuh given in thepaper, it is impossible to reproduce them.-CHZ-CO--CHO.L. T. 0's.Parabromobenzyl Compounds. By C . L. JACKSOF and W.Low E R Y (Deut. Chm. Ges. Ber., x, 1209--1212).-PambrornoBe~~zylakohol, C6H4Br. CH2QH, is most easily prepared by boiling parabromo-benzyl bromide with water for some days, in a flask with reversedcondenser. It is also obtained by heating parabromobenzyl acetate to150' with aqueous ammonia. It forms long, colourless, elast'ic, flatneedles, having a fine nacreous lustre and unpleasant odour, meltingat 6Y0, and dissolving easily in boiling water, alcohol, ether, benzene,and carbon bisulphide.The acetate, formed by heating the bromide with sodium acetate inalcohol, decomposes when distilled, and has not yet been obtainedpure.The cyanide, C6H4Br.CH2CN, is obtained by boiling the bromide withalcoholic solution of potassium cyanide.It is a crystalline body ofstrong disagreeable odour, melting at 4 6 O , and dissolving easily inalcohol, ether, benzene, glacial acetic acid, and carbon bisulphide, butnot in water.The thiocyanate, C6H4Br.CH2SCN, formed by boiling the bromidewith potassium thiocyanate, crystallises in needles, melting a t 25",and dissolving very easily in alcohol.Parabro??zaZ~~~a,toZ.uic acid, C6H4Br.CH2.COOH, formed by heating theabove cyanide to loo", with hydrochloric acid in sealed tubes, crystal-lises in long white needles, which melt at 114.5".It decomposes car-bonates very slowly, but dissolves readily in ammonia and soda-ley,.forming salts. By oxidation with chromic acid it is converted intoparabromobenzoic acid. The ammonium, silver, copper, calcium, anORGANIC CHERIISTRY. 65barium salts have been prepared. The ammonium salt forms pre-cipitates with mercuric, mercurous, ferroiis, and lead salts, but notwith salts of aluminium, chromium, zinc, cobalt, nickel, or mag-nesium.Parabromobenzyl bromide reacts with alcoholic ammonia a t the ordi-nary temperature, to form tripal.lxiironzob~nz?/Z(~~?i~~~e, ( C6H4BrCH,),N,and the corresponding I L ? / L ~ T O ~ T O ~ I ~ ~ ~ ~ , ( C6H4J3rCH,),NH13r.The formercrjwhllises from alcohol in needles, which melt a t 78-79" ; the latteris deposited from the alcoholic liquid in which it is formed in white,nacreous scales, melting a t 270°, insoluble in water and alcohol, butA Mitrobenzaldehyde analogous to the Nitrobenzoic Acidmelting at 127".-By F. FITTICA ( D c ~ L ~ . CYhenz. Ges. Be7.., X, 1630-1633) .-This substance is formed, together with a large quan-tity of the ordinary crystalline modification, on dropping a mixtnre ofequal weights of ordinary benzaldehyde and ethyl nitrate into strongsulphuric acid, maintained a t the temperature of 30-35". It is anoily body, having the characteristic properties oC the aldehydes.Byoxidation with chromic acid it yields an acid melting at l27", andhaving the other characters: of the fourth nitrobcnzoic acid.easily solnble in ether. J. Et.J. R.Derivatives of Paraoxybenzaldehyde. By HE RMANN H E RZ-F E r, D (Deut. Chenq. Ges. Be?*., x, 126 7-1272) .-This is a continuationof a previous paper by the author and Tiemann (Deut. C ~ C B L . Ges,B e y . , x, 63).PaI.aoaybenxyZnZcohoZ, C6H,( OH) CH-OH, is formed by the action ofsodium-ama,lgam on paraoxybenza,ldehydc. It is a solid crystallinesubstance, melting a t 197.5", soluble in water, alcohol, and ether, andsparingly in benzene and chloroform. It gives a transient blue color-ation with ferric chloride, and is cofoured brown by strong sulphuriuacid.IIldro~arnoe~benzDi'SL, CI4H14O4, is produced on treating with sodium-amalgam a mixture of paraoxgbenzaldeliyde with more than 10 partsof water.It is thrown down, on neutralisirig the liquid, as a whitecrystalline substance, melting a t 222O, easily soluble in boiling waterless easily in alcohol, benzene, and chloroform.NitTo~urnox?lbenzcxZde~iycle, C6H,0H(N02)COH, is formed by droppinsstlrong nitric acid into a mixture of 3 parts of paraoxybenza1;leliyclewith 20 parts of strong sulphuric acid. On diluting with water it i sdeposited as a golden-yellow mass, which crystallises in yellow needlesfrom its aqueous solution, It melts a t 13!h---14Oo, dissolves easily inalcohol and benzene, sparin& in ether and chloroform, sublimesentirely o n heating, and volatilises with steam.It forms a ~rystslline,sparingly soluble compound with acid sodium sulphite, and producesa, transient reddish coloration with ferric chloride.Paraoxybenzaldehyde absorbs 13.46 per cent. (= 1 mol.) of di*;<ammonia gas, forming with it an oily body, which, on exposure to air,gradually gives off ammonia, and leaves unaltered aldehyde.Salicylic aldehyde likewise absorbs 1 mol. of ammonia, forming GVOL. XXXIII. 66 ABSTRACTS OF CHEMICAL PAPERS.compound which is resolved by heat into water, ammonia, and hydro-salicylarnide.Paraoxybenzaldehyde i n ethereal solution reacts with aniline to forma, pale-yellow crystalline body, which melts a t 190-191", and dissolveseasily in alcohol and ether, sparingly in benzene and chloroform.From the analysis of the body it appears to be formed by the followingreaction :-C,H,O, + CsHTN = C13HnNO + H,O.J. R.Aldehyde Compounds. By E. HEPP (Deut. Chenz. Ges. Eer., x,1649 -1652).-The author showed in a former paper (Ue?it. Chem.Ges. Ber., ix, 1424) that benxonitril reacts with the normal aldehydesof the fatty series to form compounds in which the oxygen of thealdehydes is replaced by two benzamide residues, NH.COC6Hj. Inthe present paper he describes other bodies of analogous constitu-tion.M e t h ? j l e n e - d l p h e n ~ l ~ c ~ t ~ ~ ~ ~ l e is formed by heating a mixture of 1 mol.of metiiylal and 2 mols. of benzyl cyanide with concentrated sulphuricacid, It crystallises in small, white needles, which melt a t 205", anddistil for the most part without decomposition.It is nearly insoluhlein water and ether, but soluble in carbon bisulphide, boiling alcoholand glacial acetic acid. I t s composition and reactions show that itsformula is CH,~NIS.CO.CH,.C,~Ts),. When heated with hydrochloricacid or alcoholic potash in sealed tubes, it yields phcnylacetic acid.By oxidation with manganese dioxide and dilute sulphuric acid, ityields phenylacetamide in theoretical proportion.T ~ i c h l o r e t l ~ ? j ~ i d e n e - ~ ~ ~ l ~ e ~ ~ ~ l ~ c e t a ~ i ~ e is obtained from benzyl cyanideand chloral in the same manner as the precedingcompound. It formssmall white needles, which sublime without melting. I t s compositionagrees with the formula, CCl,.CH( NH.CO. CH,. C,H,),.TrichZoreth?JZiidene-diacetumide, C6H8C1303N2, is obtained by simplyheating to 40-50" a mixture of acetonitril and chloral. It forms,silky needles, which sublime without decomposition before melting.J. R.Phthalic Acid. By JULIUS BESSERT (neut. Chem. Ges. Ber., x,1445).-The author, in continuation of Baeyer's work on this subject,finds that the best method for preparinq the above compound is bythe action of zinc and hydrochloric acid on an ethcrcal solution ofphthalyl chloride. I n this manner 4 to 5 grams of the aldehyde mereobtained from 10 to 12 grams of the chloridc.The melting point of phtlialyl aldehyde is 67" according t o Kolbe andWischin ; the author, however, finds that its melting point is 73".Bythe action of alkalis or their carbonates phthalyl aldehyde is coiivertedinto a new acid thus: C,€€,(CO€I), + H,O = C,H4(COOH)(CH,.COH).This acid is much less soluhle in cold water than the aldehyde, hutdissolves easily in alcohol and ether. It melts a t 11W, giving up onemolecule of water, and being reconverted into the original aldehyde,tlie same reaction takes place on boiling with water. The bariumORGANIC CHEMISTRY. 67silver and lead salts were prepared. The acid is monobasic, and bearsthe same relation to phthalic acid as glycollic does to oxalic.Sodium-amalgam only partly reduces a solution of pllthalic aldehydein dilute alcokiol, the greater part of the aldehyde forming with thealkali the sodium-salt of the above-mentioned acid, which is notfurther attacked by the amalgam; by keeping the liquid acid, how-ever, the reduction is complete, and phthalyl pinacone,is produced, which, when treated with potassium permanganate,.yieldsan acid having the properties aiid composition of the diphthalic aciddescribed by Ador, thus:CH,.OH-C,H-x,-CHOH), + 30, = (COOH-C6H,.CO)2 + 4HZO.Phthalic acid is also simultaneously produced, owing to the furtheraction of the oxidising agent on the diphthalic acid.Phthnlyl pinacone crystallises in needles (m.p. =197"). It issoluble in water and alcohol, difficulty soluble in ether and insoluble inchloroform. By the action of sodium-amalgam on phthalyl aldehydethere is also formed, in addition to the pinacone, the aldehyde-alcoholof phthalic acid, CH,.0H-C6H,-COH, which by oxidation is con-verted into phthnlic acid.Ammonia and ammonium sulphide have no action on the alcoholicor ethereal solution of phthalyl aldehyde even a t 220°, but at 240" acrystalline substance is obtained, which is insoluble in water, alcohol,ether, and carbon disulphide, but soluble in boiling glacial acetic acid,crystallizing therefrom on cooling in stellate groups of needles, whichdo not melt a t 260".The analysis of this body is not yet completed.By heating phthalyl aldehyde with aniline to 200-220°, the anilinecompound, COH-C~HC--CH.NC~H~, is formed, which melts a t lGO",and crystallizes in small plates, which diesolre with difficulty in boilingwater and ether, but easily in benzol and chloroform.The author iscontinuing his investigation. T. C.Paratolylphenyl Ketone. By W. THORNE R (Liebig's Annalan,clxxxix, 83-128). This compound is best prepared by the methodof Collnrits and Merz (Deut. Chem. Ges. Ber., vi, 537), an intimatemixture of three parts of benzoic acid, four of toluene, and the samequantity of phosphorus pentoxide and of sand being heated f o r eightto ten hours to 200-220". By this process 1,000 grams of benzoic acidyielded 330" pure paratolyphenyl ketone, and 402" of the liquid ortho-compound still containing some of the solid. When the para-com-pound is heated with phosphorus pentachloride, it appears to be con-verted into the ketonic dichloride, which, however, could not be iso-lated, as it decomposes on distillation. Dry chlorine acting on theheated ketone replaces the hydrogen in the methyl-group, aiid by re-gulating the temperature and the quantity of chlorine, the threechlorides can easily be obtained pure.Parabenxoylbenzyl chloride, Cd&,.C0.C6H*.CH2cl, is formed at IGQ-f 68 ABSTRACTS OF CHEMICAL PAPERS.llOo, and purified by crystallisation from alcohol and washing withether, which removes some dichloride.It forms long white prismsmelting a t 97-98'. On adding a little water t o its solution inabsolute alcohol it crystallises in long, slender, silky needles. I t isreadily soluble in chloroform, carbon sulphide, benzene, toluene, hotalcohol, and glacial acetic acid, more sparingly in cold alcohol andether. I t can be sublimed, and easily undergoes double decom-positions.Parabenzoylbenzylene dichloride, CsH5.C0.CsHa.CHC1P, is producedby the continued action of chlorine a t 130-140', and crystallises fromalcohol and acetic acid in silky plates, melting at 94-95'.It dis-solves easily in the same solvents as the monochloride, and also inether. It can be sublimed, and boiling alkalis convert it slowly intoparabenzoylbenzoic acid. When it is heated with alcohol and silvernitrate, or with water and silver oxide or lead oxide, the same acid isformed, and not the aldehyde.Parci.benxoyZben~enyZ trichZoilde, c6H5.co.c6~d.cc13, is formed a t 150-160" ; like the preceding compound, it is best purified by the frac-tional precipitation of its boiling solution in glacial acetic acid withwater.It crystallises in small glistening plates or larger thin squareplates, melting a t 111--111.5". It does not dissolve very freely in coldalcohol and acetic acid, but readily in the hot liquids and in the sol-vents mentioned above. It can be sublimed, and on heating it withwater or silver nitrate to 170-180", or boiling it with alkalis, it isconverted into parabenzoylbenzoic acid. On heating it with phos-phorus pentachloride, it is converted into C3H5.CC1,.C6H4.CCI,, whichis readily soluble in acetic acid, carbon sulphide, benzene, &c. It cry-stallises in square striated thin plates, melting a t 78-80" ; it cannot besublimed, and is converted in parabenzoylbenzoic acid by concentratednitric acid, and by boiling it with alkalis.To convert the ketone into the secondary alcohol or the pinacone, itsalcoholic solution was treated with sodium or its amalgam, but withouteffect ; whereas on using zinc and hydrochloric acid, two isomeric pina-coZins, C28H240 were formed.The a-pinacolin, which is the first product, is easily converted intothe @-compound, and therefore obtained pure only by working undercertain conditions.A good yield is obtained by dissolving 10 gramsof the ketone in 500 C.C. of alcohol of 75 per cent., and adding to ita mixture of zinc and so much hydrochloric acid that a brisk evolutionof hydrogen goes on in the cold. * It is then. boiled for two or threehours, and the piriacolin which has separated out is puri6ed by cry-stallising it from alcohol.It forms microscopic glistening needles,melting a t 214-215", and dissolves freely in chloroform, carbon ~ u l -phide, toluene, and boiling acetic acid, less readily in boiling alcoholand ether, very sparingly in cold alcohol.The P-pinacoZirt, is much more easily obtained by using a strongeralcoholic solution of the ketone, and allowing the reaction to go onfor four or five days. It crystallises from hot absolute alcohol invery refractive, small square plates, which become opaque on drying,and turn yellow on exposure to light. It readily dissolves in thesame liquids as the a-compound, and also in boiling alcohol. WheORGANIC CHEMISTRY. 69the a-pinacolin is heated with benzoyl chloride or with concentratedhydrochloric acid to 150-160", or with glacial acetic acid to 170-180",it 1s converted into the &compound.The a-compound is scarcely actedupon by boiling with nitric acid, an aqueous solution of chromicacid, or potassium permanganate, but a boiling snlution of chromictrioxide in acetic acid oxidiaes it again t'o paratolyphenjl ketone.The 6-pinacolin cannot be converted into the a-compound ; onheating it or the latter with concentrated hydriodic acid and amorphousphosphorus to 210-220", the hydrocarbon, (&H26, is fornied, which isreadily soluble in chloroform, cnrbon sulphide, and toluene, but verysparingly in cold alcohol and ether. It separates from boilingalcohol or acetic acid in microscopic, probably tricliiiic crystals, meltingOn boiling the a-pinacoh with glacial acetic acid and chromictrioxide, a large portion is completely burnt to carbon dioxide, and onlya small quantity of an acid is obtained having the formula CzlH1802,or more probably C22H2002, some benzoic acid being formed at thesame tinie.The new acid separates from ether as an amorphoustransparent mass, and is precipitated from an ammoniacal solution byhydrochloric acid, as a bulky amorphous white powder. It dissolvesfreely in ether, benzene, alcohol, glacial acetic acid, &c., nielts at78-83", and cannot be sublimed. I t s alkaline solution is precipitatedby carbon dioxide ; the salts which it forms with the alkali-metals areamorphous and deliquescent, the other salts are gelatinous precipitates.Prom the results of this paper it appears most probable that, by theaction of nascent hydrogen on the ketone, first the corresponding pin&-cone is produced, which, however, at once loses the elements of waterand is converted into the a-pinacolin. As this compound can be easilyreconverted into the ketone, it must have a similar constitution, whilethe P-compound, which by oxidation loses carbon and yields a mono-basic acid, is produced by an intramolecular change, and its consti-tution will therefore be similar to that of the common pinaoolin fromacetom, which by oxidation yields trimethyl-acetic acid.at 213-213.5'.a-pinacolin.C,H51Q II/ C--CsH,.CH,\c-c~H~.CH,c6H5C 6H4. C H,ICsH,--C--CO-C6H5IC6Hi. CH,c. s.Synthesis of Benzoic Acid and Benzophenone.By F R I E D E L,CRAFTS, and ADOR (Cornpt. ~e~zd., Ixxxv, 673-676). When carbonylchloride acts on benzene in presence of aluminium chloride, the fina70 ABSTRACTS OF OHEMICAL PAPERS.product of the reaction is benzophenone, and under certain conditionsbenzoio acid is formed. The reaction is expressed as follows :--first,benzcyl chloride is formed (C,H, + COC1, = C,H,COCl + HCl), whichacts on another molecule of benzene, forming benzophenone-C,€&COCl+ CSH, = C,H,.CO.CsH, + HCl.Toluene and xylene behave in a similar manner. L. T. 0's.Three Isomeric Bromamidophenylacetic Acids. By P. P.REDSON (Deut. Chem. Ges. Ber., x, 1657-1659). This is a continua-tion of a previous paper on derivatives of phenylacetic acid (Deut.Chem. Ges.Ber., x, 530).Parabromo-metanitro-phenylacetic acid yields, by reduction with tinand hydrochloric acid, a crystalline compound of stannous chloridewith the hydrochloride of bromamidophenylacetic acid. On treatingthe compound with hydrogen sulphide, the latter constituent is ob-tained in white needles agreeing in composition with the formula,C7H7BrN.C02H.HC1 + H20 ; and from this salt, by further treatmentwith ammonia and acetic acid, pn,rcxbromoyi.Leta?iLidO-~henyl~cetic acid,C6I&.BrNH2.CH2COOH, is obtained in white silky needles, whichdissclve in hot water, alcohol, and chloroform, and slowly turn red inthe air.Yarabromo-orthonitro-phenylacetic acid yields by the same treatment a bromamidophenylacetic acid isomeric with the foregoingcrystallisiug in white flat needles, which speedily turn red in the airand melt a t 167".A third isomeride, melting at 186", is st.ill under investigation.J. R.Action of Bromine on Ethylphthalimide.By A. MICHAEL(Deut. Ckem. Ges. Eer., x, 1644) .-l3thylphtha1imide7 obtained by dis-tilling a solution of phthalic anhydride in aqueous ethylamine, crystal-tises in long white needles, melting at 78-79". When heated to 130--1.40" with excess of bromine, it yields tribromet7Ly~hthnZr:mide. Thissubstance crystallises in truncated prisms, melts with decompositionat 186-189", and dissolves in hot alcohol but not in water. It isdecomposed by boiling with potash.-.J. R.Thiamides of Monobasic Organic Acids. By AUGUST BE RN-THSEN (Deut. Chem.Ges. Ber., x, 1238--1242).-1t has been shownby the author (Liebig's Annnlen, c1xxxiv, 290) that thiamides whentreated with the hydrochlorides of priniary amines, arc converted intoamidines, with elimination of hydrogen sulphide. Conversely, he nowfinds that amidines, when treated with hydrogen sulphide, yieldthiami de s.When hydrogen sulpliide is passed over fused benzenylriionophenyl-amidine, at 130°, a reaction takes place which results i n the evolutionof ammonia and aniline, and the production of beiiaothiimaide and benzo-thianilide. The formation of these bodies is due to two simultaneousdecompositions, represented thus :ORCANIC CXEMISTRT, 71Benzenyldiphenylamidine, submit,ted to the action of hydrogen sul-phide, a t 166“, yields benzothianilide and aniline-Benzenylisodiphenylamidine, similarly treated, gives off ammoniaand yields diphenylarnine, benzot,liiamide, and a new compound whichcrystallises in small golden-yellow crystals, soluble in hot alcohol,ether, and benzene.This last appears to be b e i . L z ~ d ~ ~ h e n ~ l ~ ~ The reactions are thus expressed :-NH sC6H5-C‘ + H,S = c6H5-cy + NH(C6H5), ;\“C,K), \ N H ~S + HZS = C6H5-c’ C,H,-C\ NNH- N(C,EC,)Z ‘N(c6H5)Z + NH,.Similarly, methenyldiphenylami~i~e, exposed to the action of hydro-gen sulphide a t l49-1.5Oo, yields aniline and $irrnot?~Lia~dide. a bodyidentical with that which Hofmann obtained (Dezct. Chew,. Ges. Ber.,x, 1095) by the action of hydrogen sulphide on phenyl isocyanide-/NC6H5HC’ + H,S = E d S + HzNCsHs-“HC,H5 ‘NHC6H5The analogy of the thiamides of monobasic acids to thiocarbamidesis shown by the fact, that carbon bisulphide acts upon benzenylphenyl-amidine at 100--120” to form thiocyanic acid and benzothianilide-J.R.Contributions to the Knowledge of the Three Isomeric Oxy-benzoic Acids. By H. SMITH ( J . pr. Chern. [el, xvi, 218-233).-Salicylic acid, and pazaoxybenzoic acid, when treated with dryammonia, give first the ammonium salts, which on heating yieldphenol and carbonic acid.Oxybenzoic acid, however, when similarly treated, yields oxybemo-nitril, according to the equation72 ABSTRACTS OF CHEMICAL PAPERS.This oxybenzonitril melting a t 82", corresponds with that preparedby Griess from the sulphate of diazocyanbenzene, C6H,( CN)N,H,SOa(Deut.Chenz. 4es. B e T . , v, 669).The three isomeric acids show a similar behaviour when distilledwith potassium thiocyanate, the oxybenzoic acid alone yielding thenitril. This method of preparing the iiitril is, however, less to be re-commended than the former.The oxybenzonitril yields, by treatment with sulphuric acid andnitric acid, a mononitrated substitution-compound melting a t 182-183", which on boiling with alkalis yields a ni tro-oxybenzoic acid.The sulpho-oxybenzonitril has not been prepared in the pure state.P. P. B.Double salts of Two Organic Acids. By H. S ALK OW s K I (Deut.Chem. Ges. Ber., x, 1257--1259).-The author described in a previouspaper a barium double salt of benzoie and paranitrobenzoic acids(Deut.Chem. Ges. Ber., ix, 24; abstr. Journ. Chem Soc., 1876, i, 710).He has now succeeded in isolating strodiuizz and cuZciun~ double saltsof the same acids. The salts were obtained by neutralising a mixtureof the two acids in molecular proportions with strontium or calciumcarbouate, and allowing saturated aqueous solutions t o evaporatespontaneously in the air. Their composition is expressed by thef ormulm-C6H4(N02) GOz. Sr. CO2.C6H5 + H20 and C6H4(No2) COr.Ca.C02.C6H5 +A calcium double-salt of beizxoic and metanitrobenzoic ucids has alsobeen obtained in the same manner ; but it was not found possible toprepare the corresponding strontium and barium double salts, owing,apparently, to the great difference in solubility of the beneoates andmetanitrobenzoates of these bases.J. R.3HZO.Constitntion of Dinitro-anisic Acid and its Derivatives. ByH. SALKOWSKI and C . RUDOLPH (Deut. Chem. Ges. Ber., x, 1254-l257).-This acid is obtained by the action of a cooled mixture ofconcentrated nitric and eulphur.ic acids on nitro-anisic acid. It crys-tallises in delicate needles, which melt a t 181-182".Dinitro-anisic acid is converted, by heating to 150" with water, intodinitroparaoxybenzoic acid, in accordance with the equation-C6H2(N02),0CH,.CO,H + H,O = C6H2(NOZ)aOH.COaH +CH,OH.On more prolonged heating to 1 70°, however, the dinitroparaoxy-benzoic acid disappears, and 6-dinitrophenol is formed.Now, since anisic acid belongs to the para-series, and since, more-orer, both nitro-groups in /3-dinitrophenol occupy positions coutiguousto the hydroxyl-group, it is obvious that the constitution of the follow-ing compounds must be expressed by the accompanying formuh :ORGANIC? CHEMISTRY. 73Dinitro-anisic acid (C6H,)OCH3 : NO, : GO2€€ : NO, = 1 : 2 4 : 6 ;Dinitroparaoxyben-zoic acid , ... . . . (C6H,)OH : NO, : CO,H : NO, = 1 : 2 : 4 : 6 ;Dinitroparsmido-benzoic acid . . . . (C6H2)NH2 : NOz : C02H : NO2 = 1 : 2 : 4 : 6.Mononitro-anisic acid, when heated to 220" with water, is convertedinto a, carbonaceous mass containing orthonitrophenol, but no nitro-paraoxybenzoic acid, the latter substance being probably decomposeda t tlie high temperature :-C6H3.NO2.OCH3.COzH + HZO = CGH,.NO,.OH + CH3.OH + CO2.J. R.Oxyterephthalic Acid.By G. A. BURKHARDT (Deut. Chem.Ges. Ber., x, 1273).-This acid, when treated with a mixlure of fum-ing nitric and Nordhausen sulphuric acids, yields dinitro-ozyterep h-thuZic acid, which crystalliscs from cold water in fine golden-yellowtransperent, crj-stals, dissolving easily in cold water and melting at 178".No isomeric acid is formed. The dinitro-acid and its salts are explosive.The acid silver mEt, C,H(NO,),OH( COtIH) COOdg, formed onmixing concentrated solutions of the acid and of silver nitrate, is ayellow crystalline powder, moderately soluble in water.The meutruZ silver salt, C,H(NO,),OH( COoAg),, is obtained bytriturating a concentrated solution of t8he acid with moist silver oxide,and evaporating the filtrate over sulphnric acid.I t forms blood-redprismatic crystals, very easily soluble in water. It crystallises fromaqueous solution with 2 mols. of water.The acid Zend salt, C6H(N02),0H(COOH)C00pb (pb = 103.5),formed on adding neutral lead acetate to a solution of the acid, is ayellow crystalline powder, sparingly soluble in water.The mutrul calcium salt, C,H(N O2),0H(C00),Ca, formed by boil-ing a solution of the acid with calcium carbonate, is yellow and crys-talline, and dissolves sparingly in water. J. R.Action of Sodium Amalgam on a-Nitronaphthalenesul-phonic Acid. By CLAUS and GRAEFF (Deut. Chew. Qes. Ber., x,1303) .-Hoping that bodies analogous to the azobenzoic acid andazophenylene producible from nitrobenzenesulphonic acid would beobtained from a-nitronaplithalenesulphonic acid, the author subjectedthis acid to the action of sodium amalgam; but whether the solutionwere acid or alkaline, the same result followed, viz., splitting up intonaphthylamine and sulphuric acid without the formation of any azo-naphthalenesulphonic acid.On the other hand, the nitrobenxene-sulphonic acid obtained by acting with fuming sulphuric acid onnitrobenzene is readily and completely converted into azobenzenesul-phonic acid by sodium amalgam, no aniline or sulphuric acid beingformed. The authors hence conclude that naphthalene has a differentstructure from true aromatic bodies, being prekirnably unsymmetrical.C. B. A. W74 ABSTRACTS OF CHEMICAL PAPERS.Isomeric Sulpho- and Oxynaphthoic Acids. By M. STUNPF(Liebig's AnnaZen, clxxxviii, 1-13).By dissolving napthoic acid inwarm fuming sulphuric acid three isomeric sulphonic acids are formed,which are distinguished as a, p, and 7. The first of these has alreadybeen described by Battershall (Liebig's AnmuZen, clxviii, 114). Toseparate the acids, they are converted into the barium salts ; on con-centrating the solution first a small quantity of the impure salt of theP-acid separates in hard nodular crystals, and then a, large quantityof the a-sulphonate, forming hard, glistening monoclinic crystals, whichby recrystallisation are easily obtained pure. The salts contained inthe mother-liquors are then converted into the acid salts, of whichthat of the ?-acid is but sparingly soluble, while those of the @-acidand a-acid, which remain in the mother-liquor, can be separated onlyby repeated crystallisations.On fusing the acids with potash they yield three isomeric oxy-naphthoic acids, which when heated with lime are easily resolved intocarbon dioxide and naphthols.a-XuZp7~o"iaphthoic acid, C,,H,( SO,H)COzH, is readily soluble butnot deliquescent, and crystallises in prisms, melting without decom-position at 235".The acid salt (C11H7S05)zBa + 2Hz0, which was prepared to com-pare it with its isomerides, is more soluble than the normal salt,and cryst'allises in glistening prisms.a- Oxynnphthoic acid, C,,,H,( OH) SOsH, .has also been obtained byBattershall ; it crystallises from boiling water in thin needles, meltinga t 234-237", and when distilled with lime yields a-naphthol.P-Xulphonapl~thoic acid forms a crystalline mass, and is more freelysoluble than the a-acid; it melts and decomposes at 218-222".C,,H,S05Ba + 3$H,05 crystallises in tufts of thick glistening needles,which are a little more soluble than the normal a-salt.(CllH7S05)211a= 4Hz0 is more freely soluble, and forms soft, voluminous, wartymasses. Cl,H6S05K, is a white, crystalline, deliquescent mass.@- Oxynaphthoic acid crystallises from boiling water in bulky masses,consisting of fine needles and from alcohol in druses, which are linedwith fine hairs. It melts, but not without decomposition, at 245-247".y-8ulphonaphthoic acid is freely soluble in water, and crystallises insmall matted needles, melting a t 182-185", and decomposing a t187".C1,H6SZ0,Ba + l+HzO is tolerably soluble in water, and does notcrystnllise well.(C,,€17Sz05)2Ba + HzO is so sparingly soluble, that asolution of the free acid is precipitated by barium chloride, and one ofthe normal salt by hydrochloric acid. From boiling water, in whichit dissolves also sparingly, it crystallisss in small, hard, warty masses.C,,H6S05Kz is a crystalline, deliquescent mass, and crystallises fromboiling absolute alcohol in tufts of needles.(y- Oxynajihthoic acid is sparingly soluble in cold water, more readilyin hot water, very freely in alcohol, and crystallises in ramifiedneedles melting a t 186-1870 without decomposition. It has some re-semblance to Eller and Schaffer's carbonaphtholic acid, which is formedby the action of sodium and carbon dioxide on a-naphthol.BothOn heating it with lime it yields @-naphtholORGANIC CHEMISTRY. 75acids however differ, not only by their reactions and salts, but also bytheir decomposition with lime, the yacid yielding ,@-naphthol.When isonnphthoic (P-naphthoic) acid is dissolved in fuming sul-puric acid, szdphisonapthoic acid is formed, which has also already beenobtained by Battershall. It is a white crystalline mass, which dis-solves readily in water, and mclts a t 2.29-230". Besides this acid aminute quantity of an isomeride is formed.C,,H,SO,Ba + 6H20 crystallises in tufts of long, silky needles;Battershall obtained it in monoclinic or triclinic crystals, with only onemolecule of water.(CllH7S0,)2Ea + 6&H,O forms long silky needles,or small plates. C11H6S0,K2 is readily soluble, and crystallises fromwater in small needles, and from alcohol in slender, silky prisms.Oxyisonn~hthoic acid crystallises from alcohol in tufts of glisteningneedles, melting at 210-211". On distilling with lime, a-napthol isobtained.The following table explains itself :----a-Oxynaphthoic acid. .fi-Oxynaphthoic acid,. .y-Oxynaphthoic acid..a-Carbonaphtholic acida-Oxyisonaphthoic acidB- Carbon aphtholic acidMelting-point.234-237245-247'186-18'7'--185-186'21O-21lC?Position.-2H.-GI.P.8.a.a.P.-CO2Ha.a.a.2B .3-Crys tdlisationfromWater.--NeedlesNeedlesNeedlesNcecllcsNeedles?Alcohol-Druses-NeedleeYeedlee?Precipitate withferric chloride.---Dirty violet.Rctltlish brown onheating.Chocolate.Deep blue colour,no prccipitate.Dirty crimson.Deep, blackishviolet.c.s.Haloid Derivatives of Anthracene and Phenanthrene. H iV. MERZ and W. WEITH (Deut. Cliem. Ges. Be?.., x, 123;3).-!L'hemost highly chlorinated derivatives of anthrwene, anthraquinone, andalizarin, formed by tbe action of antimony perchloride, are re-spectively octo-, penta-, and tetra-chlorocompouiids. Further actionof the reagent results in the breaking up of these products, with form-ation of perchlorobenzene and perchloromcthane, the anthrsquiiions-derivative yielding also carbon dioxide, and the alizariri-derivsttivs,perchlorethane.Bromine acting on the same substances produces ultimately octo-browmnthrncene, pe?~tcLbromanthraquilLo.lze, and tetrabro~rmlizarin.Of theseproducts, the first two are not further affected by bromine containingiodine, but the last breaks up below 200" into pentabroniobenzene,carbon dioxide, and perbromethene.Tribromanthraquinone, when fused with soda or potash, yieldspurpurin, and at higher temperatures with potash an oxypurpurin76 ABSTRACTS OF CHEhlICAL PAPERS.The ultimate products of the action of chlorine and bromine onphenanthrene are octochloro-, and pentabromo-plLenaictl~re~ae. Theformer is easily resolved on heating into perchlorobenzene and per-chloromethane.Diphenol, carbazol, and benzidine, when treated with chlorine, yieldsimply yercldorodil~lien yl.Chrysene heated with antimony perchloride yields much perchloro-benzene, together with perchlorinated ethane and methane.Perbromophenol, formed by the action of bromine containing iodineon phenol, is converted iuto perbromobenzene by heating with phos-phorus pentabromide.J. R.Brominated Derivatives of Anthracene. By W, HA M M E R -SCHLAG (Deut. Chem Ges. Ber., x, 1212-1214).-Tetrabrornanthra-cene, exposed to the vapour of bromine for some days, is convertedinto tetriLbromu?ith raceize tetrabromide, CI4H6BrH, wFich crystallises froma hot satturnted solution in carbon bisulphide in distinct, colourlessprisms melting, with decomposition, about 212".The tetrabromide, heated to 230" till it ceases to give off bromineand hydrogen bromide, yields paiztnhi,omanthracene. This is a pul-verulent yellow substance, melting about 21 2", and dissolving sparinglyin alcohol and ether, but easily in benzene, toluene, and carbon bisul-phide.By oxidation with chromic acid it is converted into tetru-trol?oaisthraqzL~iao?ze, a body subliming i n broad needles, which meltat 365".The tetrabromide reacts violently with alcoholic soda when warmedtherewith, yielding hezbromcxi.~thracene, a substance which dissolves butsparingly in any solvent, and crystallises from naphtha in yellow silkyneedles, infusible at 370".Hexbronianthrene is completely converted into t e t r a b ~ ' u ~ ~ ~ a ~ s t l ~ ~ ~ ( q u i i i o f i e by oxidation with acetic and chromic acids. This is only slightlysoluble in all liquids, and is deposited from solution in the form ofpowder.By sublimation it may be obtained in thin needles or lamin=,infusible a t 370".Tetrabrornanthraquinone, when fused with sodium hydrate, yieldsalizarin and a small quantity of a colourless product not yet examined.J. R.Phenanthrol. By G. R(E H s (Deut. Chem. Qes. B e y . , x, 12.52-1254).--This name is given by the author to monoxyphenanthrene, C14H100,obtained by treating phenanthrene with the calculated quantity offuming sulphuric acid, converting the resulting monosulphonic acidinto ammonium salt, and fusing the latter with potash. The productcrystallises from a mixture of benzene and petroleum-spirit in finelamin=, which exhibit a bluish fluorescence, and melt a t 112".Phenanthrol dissolves easily in alcohol and ether, less easily inbenzene, and slightly in water.On exposure to air it acquires a redt o brown colour. Alkalis dissolve it easily, forming crystalline coni-pounds, which are readily soluble in water.With acetic and benzoic anhydrides phenanthrol forms ethers whichcrystallise well. The acetyl-compound, C1,H,0(C2H,0), obtained bORGANIC CHENISTRY. 77heating phenanthrol to 150" with acetic anhydride, crystallises fromalcohol in brilliant lamin= which melt a t 117-118". Otller cornpoundsare being examined. J. R.Phenenthrene-carbonic Acid. By F. R. JA P P and G. S c H u J,T z(Deut. Chenz. Ges. Rer., 1661--1663).--Tliis substance is obtained bydistilling the potassium salt of phenanthrene-sulphonic acid withpotassium ferrocyanide, saponifying the resulting riitril with alcoholicpotash, and acidifying the solution with hydrochloric acid, whiclrthrows down the phenathrene-carbonic acid in bulky wliite flocks.Itis nearly insoluble in water, but dissolves easily in alcohol, etlier, andglacial acetic acid, melts a t 260", and sublimes with partial decom-position. The barinm salt,(C,,H,COO),Ba + H,O, dissolves easily in hot water, and crystallisestherefrom i n tufts of needles.It isconverted, by oxidation with chromic and acetic acids, into phenni7,-threne-q.1LiiZo?2e-Carbo/ILic w i d ,I t s alkali-salts are easily soluble in water.The acid yields phenanthrene by distillation with soda-lime.OC-C,H,.COOHAnthraflavone, and a new Dioxyanthraquinone.RJT E.SCHUNK and H. ROEMER (Deid. Ghena. Ges. Ber., x, 122F5-1227).--Anthraflavone, as prepared by Barth and Senhofer (Liebig's rlmtzdei),clxx, loo), and by Rosenstiehl (Coin@ rerid., lxxix, 768 and Ixxxii,1332), contains two substances separable by means of bartya-water,or better, benzene. The substance insoluble in benzene is anthraflavicacid ; that insoluble in benzene is a new dioxyanthraquinone, called bythe authors w? eta benxdioayanthraquin ome.The new body differs from anthraflavic and iso-antlir;ifl:ivic acids inthe following respects :-( 1) It melts a t 291-293" ; ( 2 ) i t dissolves inpotash with tine yellow colour; (3) it dissolves easily i n glacial aceticacid ; (4) it cryst allises from weak spirit in anhydrous needles, (5) itscalcium salt is nearly insoluble.Besides the forcgoing, anthraflavone contains a srnall quantity of athird substance, which dissolves with fine purplc volour in strong sul-phuric acid.J. R.Pseudopurpurin. By C. LIEHERMANN and H. PLArcEr (Deut.Chem. GPS. Ber., x, 1618-16aO) .-The authors' experiments on thissubstance confirm Itosenstiehl's conclusion, that it is a purpuriii-car-bonic acid, C,,H,(OH),.0,.CO2H. They found that the difficultyhitherto experienced in obtaining tlie substance in the pure state maybe overcome by exhausting crude pseudopnrpurin repeatedly withchloroform, and then crystallising the residue from the same liquid.Pure pseudopurpurin forms small red lamin=, which melt at 218-220".When heated in a cnrrent of air it breaks up into purpurin andcarbon dioxide, as previously stated by Roserlstiiehl arid by Plath.The decomposition is quantitive78 * ABSTRACTS OF CHEMICAL PAPERS.Pseudopurpurin, when heated for a short time with potasli-ley, iscompletely converted into purpurin. The reaction affords a rc>a dymeans of obtaining large quantities of purpurin from the crude sub-stance, which contains much pseudopurpurin.When bromine is added to pseudopurpurin or crude purpurin sus-pended in boiling water, carbon dioxide is evolved, and wonobl-onzop MY-p r . i ? z , which crystallises in fine red needles melting at 275", is pro-duced.Cl5HiXO7 + Br2 = CI4H7BrO5 + CO, + HBr.The reaction with pseixdopurpurin is as follows :-J.R.New Colouring Matters derived from Anthracene. By M.PRCD'HOMME (BUZZ. SOC. C'him. [ 2 ] , xxviii, 62--64).-A mixture ofalizarin, glycerin, and sulphuric acid is heated for some time to 200°,when a rapid evolution of gas takes place, and the mixture awumes adark brown colour. The mass is treated with water, and the insolubleresidue exhausted with cold dilute alcohol, in which the colouringmatter is dissolved. It gives coloured soliitions similar to those ofalizarin, which it resembles in its physical properties. Its alkalinesolntions, however, are coloured orange, whilst those of alizarin arepurple. On addition of alcohol to an alkaline solution it becomes di-chromatic, being red in transmitted and green in reflected light.If mononitroalizarin be treated in a similar manner, a residue is ob-tained containing two colouring matters ; one, which is soluble indilute alcohol,.gives with alumina and strong iron mordants, precipi-tates resembling those of alizarin; but n-ith weak iron mordants abluish-grey precipitate resembling indigo.The insoluble portion gives with alumina a brown precipitate, andresembles alizarin in most of its properties. These two colouringmatters are not attacked by soap, feebly by chlorine, but are com-pletely destroyed by acids.The author is inclined to consider these bodies as glycerides, but hehas come to no definite conclusions as to their constitution.L. T. 07s.A New Dye-stuff. By A. W. HOFMANN (Deut. Chenl. Ges Bey.,x, 1378--1381).-There has lately been introduced into the trade anew bright red dye-stuff, which occurs as a, somewhat crystallinepowder, and consists of the sodium salt of an organic acid, generallymixed with a quantity of thy.It dissolves pretty readily in hot w h t x ' r ,and less easily in hot alcohol, to a deep brown solution; it is insolublein ether, and bears a somewhat high temperature without decomposi-tion, but swells up a t a stronger heat, yielding a large quantity ofcharcoal.The author prepared from the sodium salt the pure acid, the ana-lysis of which led to the formula CI,H,,N2S04. It crystallises inbrown-red needles, which .are moderately soluble in water. easilysoluble in alcohol, but insoluble in ether. Alkalis dissolve it t o abrown colour ; the aqueous solution gives a bright red crystalline pre-cipitate with silver salts, and a crystalline precipitate with barium andcalcium salts, the analyses of which prove it to be a monobasic acid.The author discusses the constitution of the substance, and believeORGANIC CHEMISTRY.79it to be nearly allied t o chrysoildin. By acting with one molecule ofsulphonaphthol on one molecule of diazobenzene, thus : CloH8SO4 +CGH,N, = C16H12N2S04, he obtained a body which had the same corn-position and similar properties to the dye-stuff. The two, therefore,appear to be identical.The Terpenes of Swedish Wood-tar from Pinus sylvestris. ByALBERT ATTEBBERC; (Deut. Chern. Ges. Ber., x, 1202-1208).-Crude wood-oil ("holzoel "), the most volatile portion of the tarformed in the dry distillation of pine-wood in Sweden, when treatedwith potsash to free it from creasote and acids, and afterwards sub-mitted to fractional distillation, yields, amongst other products, thetwo following :-1.A terpene boiling a t 156*5-157.5", and having the physical andchemical properties of australene.2. A terpene boiling at 173---175", and differing from all knownterpenes.These two bodies together form about 80 per cent. of the oil.Sylvestrene is a clear liquid of sp. gr. 0.8612 a t 16", and has a pecu-liar odour resembling that of fresh pine. It turns the plane of polari-sation to the right (rotation-coefficient for sodium light = 19.5').With hydrochloric acid gas it forms a mono- and a dichlorhydrate,the former obtained by passing the gas into sylvestrene, the latter bypassing the gas into an ethereal solution.The dichlorhydrate crystal-lises in brilliant needles, which melt a t 72-73", and dissolve easily inalcohol. It is decomposed by potash in a manner not yet clearlymade out. J. R.T. C.This the author calls syZvestreue.Euxanthone. By &I. SALZMANN and H. WICHELHAUS (Deuf.ohern. Ges, Ber., x, 1397--1403).-By the action of sodium amalgamon euxanthone a white flocculent substance was obtained, whichrapidly turned dark violet on exposure to the air. This body dis-solves in alcohol and chloroform, forming a red solution; it is in-soluble in ether, water, benzene, and petroleum etber. A very smallquantity of the substance gives with excess of sulpliuric acid a charac-teristic fuchsine-red coloration. It forms a red amorphous powder withacetyl chloride.This reduction-product resembles a hydroquinone in its properties.No satisfactory formula could be found for it, but analysis shows thatit contains more hydrogen than euxanthone.The reduction of euxanthone by zinc-dust yielded a mixture of ben-zene, phenol, a small quantity of diphenyl, and a new substancehaving the formula C13H80.This body crystallises in white scales,melting a t 99", boiling a t 310-312", soluble in alcohol, ether, chloro-form, benzene, petroleum-ether, and carbon disulphide, and onlyslightly soluble in water. It is oxidised by ordinary nitric acid orpotassium permanganate to C,,H802. This is a white substance, form-ing needle-shaped crystals, soluble in alcohol, ether, chloroform, ben-zene, and hot nitric acid, very slightly soluble in hot water and inpetroleum-ether. It melts at 170-171", and is not attacked by sodiumamalgam or sulphurous acid80 ABSTRACTS OF CHEMICAL PAPERS.A nitro-derivative, C13H802(N02), is formed by the action of filmingnitric acid on C8HI3O or C8H130,. It forms nearly colourless tr:Lnspa-rent leaves, soluble in benzene, melting a t 260".The action of bromine on C,,H,O gives rise to two substitution-prodixds, which can be sepxrated by treatment with chloroform.C13HBr70 is easily soluble in chloroform, benzene, ether, carboil clisul-phide, and petroleum-ether, less soluble in alcol-101, and insoluble inwater. I t crystallises in pale-yellow oblique prisms, which darken a t130" and melt a t 136".C1JI,Br60 is less soluble than the preceding compound in the ordi-nary solvents. It forms lemon-coloured rhombic plates, which blackena t 220-230", and do not melt a t 280".DiacetyZeulcarithone, C13H604( C2H30z)2, is prepared by heating enxan-thone with excess of acetyl chloride tG loo", or with acetic anhydrideto 150", in sealed tubes. It crystallises in pale-yellow prisms, meltingat 185", soluble in benzene, alcohol, and chloroform, less soluble inether, and insoluble in water. The existence of dincetylcuxanthoneshows Baeyer's formula for euxanthone, COc6H,<:>, to he incor-rect, the probable constitution being CO(C6H3),0. (OH),, L c . , a car-bonein of hydroquinone.The product obtained by the action of zinc-dust is ca,rbodipheny-lene, CO ( C6H4),, which was converted by oxidising ageuts into c:trbo-diphenylene oxide, C0(C6Hi,),O. Attempts to prepare enxnntliorieC,Ha. OHsynthetically were unsuccessful. w. c. nr.Quercetagetin. By LATOUR and MAGNIER D E L A SOVRCE ( I 3 ~ 7 7 .Xoc. C h h . [2], xxviii, 337-342) .-The authors have isolated theyellow colouring matter of the flowers of the Tagetes p t z d a . Its reac-tions in alcoholic solution are identical with those of quercetin ; but itdiEers from this body in crystalline form and solubility in alcohol.The crystalline substance loses 4 mol. HzO at loo", and has then thecomposition C,7H,,0,,. The authors call in question the formulaassigned by Hlasiwetz to qucrcetin, viz., C,7H,,Oi,, for which they sub-stitute C27H20013. Quercetagetin is thus quercetin + H,O. Thisdifference in composition confirms Hlasiwetz7s view of the non-identityof the various quercetins. c. F. c.Quassin. By G. GOLDSCHMIDT and H. WEIDEL ( T i e n . A7iar7.Ber., lxxiv, 389-390).-The bark and wood of Qitcnssiu a.marn, IJ.,yield when extmcted with water a yellow resinous body, from whichthe crystalline conipound described by Winkle, and more recently byWiggers, could not be obtained. The resin darkens in colour 011 ex-posure to the air. It is split up into acetic and protocatcchuic acids w. C.W. by fusion with caustic potash.Cubebin. IJy H. WRIDEL (Wien,. Aknd. Rer., lxxiv, 377-3@6).-Cubebin, C10H1003, forms silky white needle-shaped crystals, soluble inalcohol, benzene, and chloroform, m. p. 125". Nitric acid convertORGANIC OHEMISTRT. 81this body into oxalic and picric acids. By the action of nitrous acidon cubebin, minute yellow crystals of CloH,(NO2)O3 are obtained,which dissolve in ether, alcohol, ammonia, and caustic potash. Thepotash solution has a purple-violet colour.C,,H,Br,O, separates out when bromine is added drop by drop to asolution of cubebin in chloroform. It is insoluble in the ordinary sol-vents, but dissolves in boiling xylene, and is deposited on cooling insmall white crystals. The bromine in this body cannot be replacedby hydroxyl. Fusion with caustic potash converts cubebin into car-bonic, acetic, and protocntechuic acids. Although ferulic acid andeugenol yield the same products when decomposed by caustic potash,all attempts to convert cubebin into these bodies have failed. w. C.W.On Crystallised Ergotinine. By C. TANRET (J. Pharrn. Chim.,xxvi, 320--324).-This alkaloid occurs in the proportion of about1 gram per kilogram of ergot of rye. When pure it forms whiteneedles, insoluble in water, soluble in ether, chloroform, and alcohol.Either in the solid state or in alcoholic solution it absorbs oxygenrapidly from the air, and turns brown. The alcoholic solution isfluorescent, and when exposed to the air turns green and then brown ;acid solutions turn red.Ergotinine is a weak base, forming salts which are decomposed byaddition of water or by evaporation ; chloroform removes a part of thebase. The sulphate is crystallisable.When sulphuric acid, diluted with one-seventh of water, is addedto a solution of ergotinine containing a little ether, a reddish-violetcolour, changing to blue, is produced.It iscolourless, crystallisable, of camphor-like odour, and is volatile at theordinary temperature: it is neutral, melts at 165”, boils at 209” (un-corrected), and sublimes in star-like groups of crystals. It is insoluble c. w. w.The author describes also another body contained in ergot.in water, soluble in alcohol and in chloroform.The Albuminoids of Seeds. By H. RITTHAUSEN (P’iiger’sArchiv. f. Physiologie, xv, 269--288).-1n his new work on Physiolo-gical Chemistry, Part I, p. 75, Hoppe-Seyler expresses views contraryto those held by the author with regard to the albuminoids in seeds,and says that “ the statements of Ritthausen relate not to purelyunaltered albuminoids, but to more or less destroyed or insufficientlypurified bodies.”The author combats these statements, and maintains that Liebig’smethod of separating the albuminoids of plant-seeds yields pure andunaltered materials, and that these albuminoids are not similar tothose found in the eggs of animals. F. J. L.Cryptophanic and Paraphanic Acids. By J. L. W. THUDI-CHUM (PJEiiger’s Archiv. f. Physiologie, xv, 455--468).-1n the coiirseof his earlier investigations on the separation of these acids fromhuman urine (Chem. Xoc. J., 1870, p. 116), the author observed thatBOL. XXXILI. 82 ABSTRACTS OF CHEMICAL PAPERS.they were precipitated by ferric chloride. He has now made use ofthis property as a means of separating them, so as further to studytheir reactions. The urine having been made alkaline by addition oflime or baryta, is evaporated t o + its volume, and a solution of ferricchloride is added. This precipitates the cryptophanic and paraphanicacids as iron salts, together with some hippuric and benzoic acids.The iron salt can be decomposed by ammonia, haryta, or lime. Bnrytadoes not completely destroy it, but nevertheless yields the purest pro-duct. Amnionium sulphide decomposes it completely, but the resultingcryptophanic acid contains sulphur. I?. J. L