Organic Chemistry.285A Method for Determining the Constitution of Saturatedand Unsaturated Halogen Derivatives and Hydrocarbons.By M. W~LDERXANN (J. pr. Chern. [2], 44, 470-496).-11his is amethod for the determination of the coristitution of the higherVOL. LXII. 286 ABSTRAOTB OF OHEMICAL PAPERS.members (above n = 4) OF the aliphatic series, founded on Pllternntchxlogenisation and removal of the elements of halogen hydro-acids,with determination of the heats of combustion of the various hydrn-c;wbons produced. The paper is not suitable for abstraction, as themethod could not be made intelligible without a full reproductionof the details both of the argument employed and of the variousexamples given. A. G. B.Platinum Thiocyanate and Platinothiocyanates. By T.GUARESCHI (Chem.Centr., 1831, ii, 620-622; from Giorn. R. Amd.Med., 1891) .-The author has prepared potassium phtinothiocyanatcaccording to the methods of nuckton. Wyrouboff and Norton. Hefinds that the salt crystallised from alcohol is anhydrous, whilstthat crystallised from water contains 2 mols H20. This i t loses ifdried over calcium chloride, but he does not find that it is so readilylost on exposure to the air at ordinary temperatures as Wyrouboflstated.Potassium pZatinothbcyanate, &Pt( cNS)6, gives characteristicprecipitates with many organic: bases, and may be used as a test forcertain alkalo'ids. The platinothiocyanates of tJhe tertiary amines areless soluble than the corresponding salts of. the secondary andprimary amines.In many cases, the double salts of the secondarybiises melt a t a lower temperature than those of the primary.Monomethy Zarnine platinofhiocyancrte, (NH,Me),,H,Pt (CNS),, isprepared by allowing the mixed solutions of potassium platinothio-cyaiiate and of methylamine hydrochloride to remain for severiildays, when the double thiocyanate crystallises out in long, red,rliombic prisms. The dimethylamine salt, (NHMe,),,H2Pt(CNS),. i nprecipitated as red prisms o r needles on mixing the not very concen-trated solutions of the respective salts. It, melts a t 160-170" withdecomposition, arid is soluble in cold water, more readily in hot watei.,readily soluble i n alcohol, insoluhle in ether. The trimethyZamine salt,(NMe,),,HzPt(CNS),, forms red prisms, sparingly soluble in coldwater, soluble in alcohol, but insoluble in ether; it melts at 175" withdecomposition.The ethylamine salt is similar to the methylamine salt.Thediethylamine: salt, (EHEt,)2H2Pt(CNS)6 + 2Hz0, is prepared bymixing 1 part of the hydrochloride in 6 parts of water wittipotassium platinothiocyanate. A liquid precipitate at, first sepa-riltes which rapidly solidifies to a mass of sliort prisms, or rect-angular, lemon-yellow plates, which, after drying in the air, meltat 58-58.5", and in the anhydrous condition, melt a t 79-80'.It is sparingly soluble in cold water, more readily in hot water,w r y soluble in adcohol, insoluble in ether. The triethylamine salt,(NEt,),,H,Pt(CNS),, is precipitated, when the solution of the hydro-chloride, acidified with hydrochloric acid, is added to potassiumplatinothiocyanate, a s a thick, red liquid, which solidifies graduallywhen agitated. When recrystallised from water, it separates intl!e same way.It consists of golden-Fellow plates, melts at165-167", and decomposes at 180". It is sparingly soluble in coldwater, more readily in hot water and in alcohol, insoluble in etherORGANIC CHEMISTRY, 28 7Propylamine, butylamine, and amylamine react in the same manner asmet hylamine and ethy lamine.The ethyienediamine sal t, C2H4N,H4,H,Pt(CNS),, is a yellow pre-cipitate, sparingly soluble in water, and blackens a t 140-150".The pentnmethyl~nediarnine salt, C5H14N1,H,Pt;( CNS),, is obtained I yprecipitatinv the solution of the hydrochloride with platinum thio-cyanate.The precipitate soon becomes crystalline, and forms red-dish needles which commence to turn brown a t 160", and becomequite black a t 176", but do not melt. It is soluble in alcohol andwater, hut insoliible in ether.The dincetonenmine salt, ( CO~e.CHz*CMe2*NH,)~,H2Pt (CNS),, isobtained by precipitating the solution of dincetoneamine oxalate withthe platinothiocyanate. It is thus obtained as a crystalline pre-cipitate, which, when recrystallised from hot water, forms red prisms,soluble in alcohol, insoluble in ether It melts at 165" with decom-position. The g.z~nnidine salt, (C,H,N,),,H,Pt(CNS),, is obtainedin beautiful red crystals on mixing solutions of guanidine hydro-chloride with the platinothiocganate.It is also obtained when theso1 ution of guariidine thiocyannte is mixed with platinum chloride.It blackens a t 1'70-175" without melting.The aniline salt, (NH,PIi),,H,Pt(CNS),, forms dark-red crystalswhich melt a t 100-105", soluble in alcohol and water, insnluble inether. The a-?iaphthyZarnine salt forms a dark-yellow precipitate, thep-salt a light-yellow precipitate, from solutions of the hydrochlorides ;they are both somewhat difficult to obtain crystalline ; they decomposereadily on exposure to moist, air, especially the a-salt,. They bobhmelt to brown liquids, the a-salt a t 140", the P-salt a t 180"Paratoluidine, allylamine, and furfurine are precipitated i n likemanner.PhenyZhydmeine reduces the solution of the platinothioopanate.Tetrahydro-a-napb t h y lamine forms a yellow, crystalline precipitate.The py&line salt, (C5H,N),,H,Pt(CNS),, crystnllises in red prisms,and is precipitated from the solution of the hydrochloride.It is notchanged by exposure to the air, but commences to decompose a t100-105" and melts at 170-172' to a black liquid ; it is sduble in hotwater, but only sparingly in cold water. Protracted boiling wit,h watercauses decomposition. The piperidine salt, ( C5H,,N)2,H2Pt(CNS),,is precipitated a t first as a liquid, which later solidifies in lemon-yellow prisms, sparinglg soluble in cold water, readily so in hotwater and in alcohol. Coniiciie as hydrochloride o r as hydrobromideis precipitated, if the solution be not too dilute, as a i-ed oil, whichcould not be obtained crystalline.A solution of coniine hydro-bromide 1 : 1000 is not precipitated, hut nicotine is precipitated asyellow crystals at a dilution of 1: 3000. This salt is almost in-soluble in cold water, and may serve to distinguish coniine fromnicotine. The spartrzne salt forms a sulphur-yellow, powdery pre-cipitate. The a- and /3-guinoline salts are precipitated as yellow,microscopical crystals; the a-salt is the darker; even a solution of1 : 6000 is precipitated.Fphedrine, apomorphine, apocodeine, cocIxi'ne, tind ecgonine are like-wise precipitated. Glycosamine is not precipitated.x 288 ABSTRACTS OF CHEMICAL PAPERS.The reaction was examined in the case of the following alkdoi'dswith the view of determining the delicacy in each case.Strychminebolution, 1 : 40,000, gave a cryst,alline precipitate after some time ;brurine, 1 : 18,000 ; atropine, 1 : 20,000 ; nzorphine, 1 : 1000 ; reratrine,1 : 10,000 ; nicotine, 1 : 3000 ; codeane, 1 : 2000, all precipitate im-mediately. Quinine, cinchonine, quinidine, cinchmidine, I : 100,000,also give precipitates immediately ; aspidospermine, 1 : 40,000 is alsoprecipitated immediately. J. W. L.Decomposition of Hydrocarbons with Steam. By COQUILL~ONand HEKRIVAUX ( C h ~ m . Centr., 1891, ii, S77 ; from J. UsineR ti, Guz,1890, 355).--The authors haye determined the composition of thegaseous mixture obtained by heatirg methane and steam together.When the gases were Rubjected t o the action of an incandescentplatinum wire fixed at the lower end of the eudiometer, the RRSproduced had the composition : 2.45-2-50 per cent.COz. 13.68-16.50per cent. CO, 17.84-14.60 per cent. CH,; 66.03-66.40 percent. H. When the methane and steam were passed through threeiron tubes heated to redness, the resulting gas had the cornposition:l - U U per cent. CO,, 19-86 per cent. CO, 8-24 per cent. CHI, 70-90 percent H. After passing through tubes heatcd to L white heat, theresulting gas has the composit,ion: 12.01 per cent, GO,, 7.35 percent. CO, 50.64 per cent. H, no methane remaining. J. W. L.Hydrocarbons from a- and p-Amyrin. By A. VESTERBERG(Ber., 24, 3834-3836).-As already stated (Abstr., 1887, 733 ; 1891,165), a- and p-amgrin are converted by phosphorus pentachlorideinto dextro-a- and P-amyrilene, Ca0Hd8, and a-amyrin by phosphoruspentoxide into laevo- a-amyrilene, C,,H4,.Dextro-a-amyrilene issparirigly soluble in acetic acid, readily in light petroleurn and ben-zene, and commences to decompose at its boiling point. Laevo-a-amyrilene is prepared by adding a benzene solution of a-amyrin tophosphoxus pentoxide, allowing the cherry-red jelly to remain forsome drlys, and adding water t o remove phosphoric acid. The ben-zene solution, on spontaneous evaporation, deposits prismatic crystalsmrrounded by a glutinous mass ; the latter is removed by ether, andthe residue reci-ystallised from hot bepzene. It fornis rhombic c r p -tala (a : b : c = 0.789 : 1 : 0.505;, melts at 193-194", is Rparinglysoluble in ether, more readily in light petroleum and benzene, and hasthe sp.rotatory power [ol]D = -1lu4.9.p-Amyrilent: is almost insoluble in alcohol and acetic acid, and lessreadily soluble in ether, light petroleum, and benzene t h a n dextro-a-am yrilene. H. G. C.Derivatives of Glycerol. By E. SEELIG (Ber., 24, 3466-3471).-Diacet ylgljcerol (diacetin) is obtained in quantitative yield byboiling 95 per cent. glycerol (4CO grams) with glacial acetic ncid(1000 grams) in a reflux apparatus for t3+ hours, dist.illing up to 116",replacing the distillate (about 270 grams) by an equal weight ofiresh glacial acetic acid, boiling for a further 1 7 honrR, and, after dis-tilling off the acetic acid, rectifying the product under a, pressure oOBGXNIC CHEMISTRY.28940 mm. It boils a t 172-174" (40 mm.), stndnt 259-261" (760 mm.)has a sp. gr. 1.178, is miscible with water, ether, chloroform, andbenzene, but almost insoluble in light petroleum and carbon hisulphideOn one occasion the author treated a sample of ordinary glycerol inthe above manner, and obtained a product which was only misciblewith water to a limited extent, and did not become acid on boilingwith it. Diacetylglycerol can only be converted into the triacetylderivative (triacetin) aw follows :-Coarsely pulverised, anhydmilseodium acetate (60 grams) is well mixed with acetic anhydride (150grams), diacetylglycerol (200 grams) added, and the m'xture boiledin a, reflux apparatus for 16 hours; the product is shaken withl$ times its volume of ether and an equal quantity of water.when thetriecetrl derivative is dissolved by the ether, and is isolated by distil-lation. It boih a t 171" (40 mm.), and a t 258-259" (760 mm.), hasa sp. gr. 1.155, is sparingly soluble in water, and, unlike the diacutylcompound, in not decomposed when boiled with i t ; it is miscible with~lcohol, ether, chloroform, and benzene, but almost insoluble in lightpetroleum and carbon bisulphide. It would thuR appear that thetriacetylglycerol described by Schmidt (Xbstr., 1880. 312) was i nreality the diacetyl derivative, and Rince a mixture of the two cannotbe separated from one another, Rottinger's method (Abstr., 1891,1183) is invalid.When diacetylglycerol is dissolved in glacial acetic acid, saturatedwith hydrogen chloride.and, after heating at 100" for two hourR, dis-tilled under a pressure of 40 mm., two fractions, consisting of im-pure dichloracetpl derivatives, pass over at 101-107" and a t10 7- 115" respectively, whilst chlorodiace tylgly cerol, contami nrttedapparently with chloracetylglycerol, passes over at 137-144" (seebelow), and, lastly, unaltered diacetylglycerol distils ; lower boilingcompounds are also formed. The same result is obtained by leading astream of hydrogen chloride through Soiling diacetylglycerol. Whencooled acetic anhydride (130 grams) is saturated with dry hydrogenchloride, mixed with diacetjlglycurol (190 grams), again Raturatedwith hydrogen chloride, 70 grams of the gas being absorbed iu all,and the mixture heated a t 110" for 30-40 hours, a chlorodiacetyl-glycerol boiling a t 142-149" (40 mm.), or a t 250-240" (760 mm.),a dichloracetylglycerol boiling at 108-112" (40 mm.), or at189-199" (760 mm.), together with much triacetylglycerol andlower boiling compounds, are obtained ; whilst if hydrogen chlorideis passed through boiling triacetylglycerol for 70 hours, a chloro-diacetylglycero t boiling a t the same temperature as the last-men-tioned one, and haviiig a sp.gr. 1.204, is produced. When thefraction boiling a t 137-144" (40 mm.) from diacetylglycerol andhvdrogen chloride is heated with an excess of acetic. anhydride at18U-190°, a chlorodiacetylglgcerol boiling at 141-148" (40 mm.) isobtained, whilst a similar compound is prodnced by heating a-chlor-hydrin with an excess of acetic anhydride.When dirhlorhydrin (pre-pared from a-chlorhydrin) is heated with acetic anhydride, it yields twodichlorticetylglycerols boiling at 108-112" and at 11%116" (4-0 mm.)respectively. The dichlorecetylglycerol boiling at the lower tempera-ture is probably the symmetrical derivative, and, since only ou230 ABSTRACTS OF CHEMICAL PAPERF.monochloro-derivative is formed from the diacetplglycerol, the twoacetoxy-groups in this compound probably occupy consecutive posi-tions, and support is afforded to this view by the fact that thediacetylglycerol yields an aldehyde on oxidation with nitric acid ; thehydrazone from the latter melts a t 161". A. R. L.Reactions of Xyloae and Arabinose.By TOLLENS (BUZZ. SOC.Chim. [3], 6, 161--16~).-This is a note containing extracts frommemoirs by Wheeler and Tollens (Annulen, 254, 314), and by Allenand Tollens (Annulen, 260, 304), which show that the coloured reac-tions of xylose with orcinol and phloroglucinol, given by Bertrand inthe BUZZ. Cs'oc. Chinz. [3], 5, 932, were already known.W. T.Oxidation Products of a- and p-Amyrin. By A. VESTERHERG(Rer., 24, 3836-3843).-Both a- and P-amyrin, when oxidised withchromic acid in acetic acid solution, yield as chief products the corre-sponding ketones (or, possibly, aldehydes), a- aud ,8-amyrone.a-Amyrone, C30H480 + H,O, crystallises from a mixture of alcoholand acetic acid in large tablets, melts a t 125-130", dissolves readilyin ether, hot benzene, and acetic acid, sparingly in light petroleum:mi alcohol.The substance thus obtained is, however, not quite pure,but, on treatment with hydroxylamine, it readily yieldR pure a-umyi*on-oxinae, C30H48:NOH, which crystallises from benzene in needlr s, andmelts with evolution of gas at 233-234". ,%Arnyrone, C30H480, formsnodular aggregates of small prisms, melts a t 178-180", is readilysoluble in chloroform, ether, and benzene, sparingly in light petroleumand alcohol ; its oxime, CBUH4&NOH, crystdlises from benzene in long,pointed plates which melt wit,h evolution of gas a t 862-263".When a-amyrin acetate is subjected to the action of chromic acidi n acetic acid solution, two atoms of hydrogen are replaced by one ofoxygen with formation of oxy-a-uniyrin acelate, CwH4,0.0Ac, whichc.rystallises from benzene in PIX-sided, rhombic plates (a : b : c =Oti845 : 1 : 1.2538), melts a t 278", and is insoluble in alcohol andether, sparingly soluble in acetic acid, readily in benzene.By theaction of alcoholic potash, it is converted into ozy-a-aniyrin,C,H4,0mOH + 2Hz0, which melts a t 207-2808", and forms acicularcrystals readily soluble in alcohol, ether, and benzene, insoluble inlight petroleum; the 2 mols. H?O are slowly evolved a t 100". ItsHolutions in alcohol and benzene, like those of bromo-@-amyrin,solidify to jellies on cooling.P-Amyrin acetate, on oxidation, appears to behave i n a mannersimilar to the a-compound, but the. 0x3 -p-amyrin acetate could not beobtained free from unaltered p-amjrin acetate.The oxygen atom in these compounds is not present in the form ofa hydroxyl or carbonyl group, for oxy-a-nmyrin acetate is not actedon by acetic anhydride or hj-droxylamine ; i t is therefore probablypresent in the same form a s in the alkylene oxides.A similar corn-pound was obtained by Schrot.ter (dbstr., lW2, 6ti) by the oxidationof borneol acetate.The alcohol8 related to amyrin appear to be widely distributed inthe vegetable kingdom Liebermann's cholesterin reagent (acetiORQANIO CHEblISTRY. 291anhydride and concentmted sulphuric acid) gives strongly colouredsolutions witlh almost all amyrin derivatives, the bromine compoundsgiving a blue, and the others a violet or purple-red, coloration.Laevo-a-amyrileae gives only a yellowish, or, at most, pink, coloration.Pectin Substances.By A. HERZFELD (Ckem. Centr., 1891, ii,618-619 ; from Z e i t . Verein Riibenziick. Ind., 1891, 667-678).-Para-pectic a-cid was obtained by the author by heating 500 grams of slicedbeetroot with 1000 grams of water and 50 C.C. of concentrated hydro-chloric acid at 70” for one hour. The liquid was separated fimom thesolid portion, neutralised with sodium carbonate, and precipitatedwith alcohol. The substance thus obtained was not quite free frommineral matter, and contained 29.6 per cent. of mucic acid and 4 percent. of furfuraldehyde. Parapectic acid appears to consist of amixture of substances which yield arabinose and galactose.hetapectic acid was obtained both from the sliced roots and fromparapectin by treatment with calcium carbonate.The specimens thusobtained diil’ered in their optical properties, the one being dextro-rotatory, whilst the other was 1Eevo-rotatory, and the amounts of mucicacid and furfuraldehyde obtained from each were not the same.H. G. C.J. W. L.First Product of the Reduction of Nitro-compounds withTin and Hydrochloric Acid, or with Stannous Chloride. By E.HOFFMANN and V. MEYER (Ber., 24, 3528-3535).--Tt was obfiervedlong ago that, in preparing normal butylamine by the reduction ofnitrobutane with tin and hydrochloric acid, there is formed a con-siderable quantity of a substance which reduces Fehling’s solution.The authors’ recent experiments have shown that other fatty nitro-compounds, such as nitromethane, nitroethane, and secondary nitro-propane, show a like behaviour, but that nitrobenzene and nitrophenoldo not yield any substances which have a reducing action on Fehling’Asolution.It was also found that when nitromethane (I mol.) istreated with piire stannous chloride (1 mol.) in concentrated hydro-chloric acid solution, methylamine hydrochloride, ammonium chloride,and /3-methylhydroxylamine hydrochloride, NHMe-OH, HC1, areiormed ; the three compounds are best separated by fractionally pre-cipitating the alcoholic solution of the mixed products with dryother.These experiments show that the conversion of nitromethane intomethylamine takes place in the follow in^ two phases :--CHyNO, +2H, = H20 + NHMe*OH and NHMeBOH + H2 = H,O + NHrJMe,and that the reduction of the Fehling’s solution is due to the forrna-tion of a, hydroxylaniine derivative.By G.Mrwmr (Gazzetta, 21, ii, 192-205).--The author replies to Hantzsch’s criticisms (Abstr., 1891,823) on his explanation I€ the isomerism of oximes (Abstr., 1891,1354). The conversion of the p-oximes into nitriles is readily ex-plained by snpposing the formation of a nitrouo-derivative as an iiiter-mediate product. The intramolecular change uoted by Beckmann canF. S. K.Isomerism of Oxirnes292 ARSTRAOTS OF OHEMICAL PAPERS.also he explained in a somewhat Rimilar manner. To the argument thatthree, and not two, isomeric oximes are accounted for by the author'shypothesis, i t is replied that the stereochemical hypothesis is, in manyoases, open to the same objection.Finally, the author's hypothesisis in no way dependent on the presence of the benzene nucleus, butonly requires the compound to contain the group X=C-C=X; at3this group is contained in the oximes of succinic acid, the isomerismexisting among them is satisfactorily explained. W. J. P.Action of Oxidising Agents on Aliphatic Thiocarbamides.Ry D. E. HECTOR (J. pr. Chem. [2], 44, 492-506 ; compare Abstr.,1889, 872 ; l890,526).-When thiocarbamide is heated with hydrogenperoxide in hydrochloric acid solution, it is decomposed with theformation of ammonium chloride, sulphur, sulphuric acid, and carb-onic anhydride.Pseudothiocyanogen, HC3N3S3, was the ultimate product of theaction of hydrngen peroxide on ammonium tbiocyanate in hydro-chloric acid solution; it did not dissolve in alcohol, but dissolvedreadily in potassium hydroxide solution, from which it waH precipitatedby hydrochloric acid ; the alkaline solution p v e a yellowish-brownprecipi t8a te with silver nitrate.Allylthiocarbamide is decomposed when heated with hydrogenperoxide in neutral solution, and subsequently with barium hydroxide,*with formation of sulphnric acid, formic acid, allylamine, and am-monia.Allylforma~midine bisulphide, S,[ C (NH*C,H,) INHI,, is prepared byheating ally1 thiocarbamide with hydrogen peroxide (Q mol.proportion)in an acid solution. After filtering off the sulphur, separating sulph-uric acid by barium hydroxide, and the excess of the latter by carb-onic anhydride, the liquid is evaporated, until a viscid oil separatesou cooling.The oil is dried on the water-bath, and cooled in a deRic-cator, when it sets to a vitreous mass, the analysis of which points tothe above formula. The new base is bivalent ; i t dissolves readily in hotwater. but sparingly in cold, and these solutions turn red litmus blue ;it also dissolves i n alcohol, but not in ether, benzene, or chloyoform.It decomposes when heated. Its salts do not crysiallise, but are verysoluble in water. An aqueous solution of the bisulphide gives a whiteprecipitate with silver nitrate, which rapidly becomes black ; it isalso precipitated by platinic chloride, mercuric chloride, picric acid,potassium ferrocyanide, and potassium ferricyanide. When i t isheated with barium hydroxide, ammonia and allylamine are evolved.The suzpphate, C8HI4N4S2,H2SO4 + HzO, forms a viscous, white mass,but does not cr.ystallise ; the picrate, C8Hl4N4SZ,2CeH3N3O7, formsyellow granules, which melt at 178-180" ; the plntinochZorides,C,H14N4S2,H,PtC16 + 2H20 and (CJI,,Nd3,,2HCl),(PtC14)2, wereboth obtained ; the mercurodloride, C8H1i"S2,4HgC12, is a white,crystalline powder, and melts a t 171-172".-This compound isobtained by dropping a solution of potassium nitrite (4 grams) intoC S-y.C,H,C S.N-CqH5' DiaZly ldifhiotetrahydrotriazole, NEORQANIC CHEMISTRY. 293R d u t i o n of allylthiocarhamide ( 5 grams) acidified with sulphuricItcid ; the fiolution is afterwards shaken with ether, and the etherealsolution washed with dilute sodium hydroxide solution, dried, andevaporated. It is a yellow oil, insoluble in water and dilute acids, butsoluble i n alcohol and ether; it is a feeble base, giving precipitateswith platinic chloride, si h e r nitrate, mercuric chloride, and coppersulphate.pimet h.y Zdit hiote trah y dro triazol e, NH<CS.NMe is prepared in likemanner, and is a yellow oil, giving similar reactions.Constitution of Caprylaldehyde. By A. BEHAL (BuEI. SOC. Chim.131, 6, 131-137).-Substances having the formula C,HIsO havebeen prepared by the author in four different ways : (1) by the dis-tillation of castor-oil soap ; (2) by oxidation of capryl alcohol obtainedby the distillation of castor-oil soap in presence of an alkali ; (3) bythe action of zinc methyl on oenanthylic chloride ; (4) by the addi-tion of the elements of water to true acetylenic caprylidene.All these substances have the same odour, and boil at 171-172" ;their densities at 0" me respectively: (1) 0.8331 ; (2) 0.8337; (3)0.8399, 0.8387 ; (4) 0.8399.The smaller values.obtained i n the first two cases are probably dueto the presence of a little capryl alcohol.None of these compoundsreduce ammoniacal silver nitrate in alcoholic solution. The productAare identical, and by the third met,hod of preparation the substance mustbe a methyl ketone. This is substantiated by the preparation of theoxime, which boils at 218", and, on treatment with acetic chloride,yields an acetyl-derivative, which gives barium acetate and theoriginal ketone when distilled with baryta.The products of oxida.+ion of the compound prepared in each ofthe four ways are caproic and acetic acids.The caproic acid obtainedhas been prepared in large quantity and purified. The fractionpassing over at 204-206" readily crystallises from methyl chloride :it fuses at -10.5", a point much lower than that indicated by Fittigfor the normal acid (Annnlen., 200, 49), but this difference is,perhaps, due to a trace of impurity." Its density at 0" is 0-9456.The calcium salt crystallises in plates containing 1 mol. H,O. Thesolubility of this salt is such that at +lo the solution contains2.084 grams of the anhydrous sa.lt per 1OOc.c., and at 23.5" the corre-sponding amount is 2.852 grams.These numbers correspond withthe determinations of the solubility of the calcium salt of normalcaproic acid made by Lieben and Rossi.The so-called caprylaldehyde is therefore normal methyl hexylketone. W. T.Dry Distillation of Orgsnic Silver Salts. By W. KOENIGS(Ber., 24, 3589-3590).-The author points out that the decom-position of organic silver salts when heated frequently takea a course* The difference between the temperature of fusion found, -10 5", and thatgiven for the normal acid, -2', would require as much 8 s 2 per cent. of an im-imrity of low molecular weight, such as water, for its production, according toItaoult's law.-Note by Abstractor.The pZatinochZoride, (C,H,,N,S,),,H,PtC'l,, was obtained.CS-Y MeA.G. B294 ABSTRAOTS OF OHEMXCAL PAFERS.quite different from that rJtdndied by Knchlor (this vol., p. 37). Hequotes a number of well-known cases in which the Rilver salt is de-composed, with evolution of carbonic anhydride, yielding considerablequantities of a substance of which the acid in question is n carboxyl-derivative. 1'. S. R.Glycocine and its Derivatives. By B. GOLDBERG, P. KUXZ,and K. KRAUT (Annalen, 266, 292-310; compare Mauthner andSuida, Abstr., 1891, 38 j.-Amidoacetic acid (glycocine) is best pre-pared by gradually adding a concentrated aqueous snlutim oEchloracetic acid to a large excess of Concentrated ammonia withconstant stirring, and, after keeping for 24 hours, expelling theexcess of ammonia, first with a stream of air, and then bywarming on the water-bath; the acid is isolated by means of itacopper salt.The mother liquors from the copper salt contain di-atid tri-glycolamidic acid (compare Heintz, Annalen, 122, 257 ; 124,297), but 20-30 per cent. of the chloracetic acid is converted intoproducts other than those already named, the nature of which couldnot be determined. The barium salt, (NH,~CH,C'OO),Bn + 4Hz0,is obtained in small, lustrous crystals when the acid (1 part) andcrystalline barium hydroxide (2 parts) are dissolved in a little water,the filtered solution poured info alcohol, and the precipitated oil leftf o r some days in contact with the supernatant liquid; it melts R tFtbont 42", arid cannot be obtained in an anhydrous condition. Thestrontium salt, w i t h l$H,O, calcium d t , with H,O, and the magne&masalt, with 2HI,0, were prepared in like manner, and are all crystalline ;the calcium salt loses the whole of its water a t 105-llO", and itsaqueous solution has a strongly alkaline reaction.These experimentsprove the inaccuracy of Curtius' statements regarding the nou-existence of such salts. A double salt of the compositionNH,GHz-COO Ho'CHzCoo>Zn + 2H20is formed by the union of molecular proportions of, zinc amidoacetateand zinc glycollate ; i t is a crystalline compound, sparingly soluble incold, and decomposed by hot water with separation of zinc oxide.When methyl amidoacetate hydrochloride is boiled with excess ofcopper oxide, it is completely dricomposed, yielding methyl alcohol,copper amidoacetate, a.nd cupric chloride ; ethyl amidoacetate hydro-chloride, under the same conditionp, is decomposed in a similai.manner. There is, therefore, 110 reason for supposing that in thesecompounds copper can be suhst'ituted for the hydrogen of the amido-group (compare Curtius and Goebel, Abstr., 1888, 576), and it, ismobable that all the metallic derivatives of amidoncetic acid are formed I .by the substitution of the hydrogen of the carboxyl group.F. S. R.Diethylamidocaproic Acid. By E. DUVILLIER (BUZZ. SOC. Clrim.[3], 6, 90--92).-Normal a-bromocaproic acid (1 mol.) is heated insealed tubes at 100" with excess of diethylamine (3 mols ) in concen-trated aqueous solution, The base is recovered by boiling withbaryta, the baryta precipitated exactly with sulphuric acid, aud thQRQANIC CHEMISTRY. 295product treated with silver oxide.A little dissolred silver is removedby hydrogen sulphide, and the solution evaporated to a Hyrup, fromwhich the pure amido-acid is obtained by conversion into the coppersalt, which is deposited on evaporation a t a low temperature a s a violetsalt, accompanied by a small quantity of a p e e n salt, and is purified bycrystallisation from aqueous solution over sulphuric acid ; the copperdiethylamidocaproate is then decompofled by hydrogen sulphide.The acicular crystals of the copper salt are of a dark-violet colour,resembling that of chrome alum ; they give fine, violet solutions inwater and alcohol, their solubility in the latter being much the greater.The free acid, CH3.CH&HzCH,-CH(NEtz).COOH, is very solublein water and alcohol, but insoluble in ether.I t s solutions, whenstrongly concentrated, give a crystalline mass which decomposes ondistillation. The hydrochloride is a syrupy substance, soluble in allproportions in water and alcohol.The pZatinochZoride is deposited from very concentrated aqueoussolutions in oTange-red, monoclinic prisms ; it is very soluble in water,and soluble in alcohol, but insoluble in pure, dry ether. Ether precipi-tates it from its alcoholic solution aR an orange-coloured oil. T t con-t sins 1 mol. H20, which it loses at 110". The corresponding aurochlorideis almost insoluble in water; i t is deposited as a yellow oil fromhot solutions, forming small, crystalline plates on cooling, Thecrystals are anhydrous, very soluble in alcohol, also soluble in pure,dry ether.The green copper compound accompanying the copper diethyl-amidocaproate is copper hydroxycaproate ; it yields barium hydroxy-caproate on treatment with barium sulphide.The barium salt crjs-tsllises with 4 mol. H,O in brilliant needles, forming radiating groups,W. T.Derivatives of Tsocrotonic Acid. By P. MELLKOFF and P.PETRENKO-KRITSCHENKO (dnnazen, 266, 358-378).-W hen a slightexcess of hypochlorous acid is gradually added to an aqueous solu-tion of isocrotonic acid, and the solution then extracted with ether, athick, acid syrup is obtained, which consists of /3-chlor-a-hydroxy-hutyric acid (m.p. 8S-8SD), small quautities of a-chloro-p-hydroxy -butgric acid (m. p. 62-63"),. the formatioil of which is probablyduo to the presence of crotonic acid, and a-chloro-p-hydroxp butyricacid (m. p. 80.5").The /3-chlor-a-hydroxybutyric acid (m. p. 85-86") is easily iso-lated by means of its sparingly fioluble zinc salt (compare Abstr.,1884, 1301); the other two acids form readily soluble zinc saltsand are separated from one another by means of their potassium salts,t,hat of the a-chloro-/3-hydroxy-acid (m. p. 62-63") being much themore readily soluble in alcoholic ethcr.a-ChZoro-8-hydl.oxybutyr~c acid (m. p. 80m5"), prepared from ihpotassium salt, crystlallises from ether in .well-defined, rhombic prisms,and is readily soluble i n water, alcahol, and ether.The potassiumd t , CAH,C103K + 14K-0, crystallises from hot 96 per cent. alcohoiin long, silky, efflorescent prisnis, and is readily soluble in water, butonly sparingly in cold 96 per. cent. alcohol. The sodium salt296 ABSTRAOTS Olr OHEMIOAL PAPERS.CdH6CIO,Na, separates from hot alcohol in small, ~ r a n u l a r crystals,and seems to decompose at 70". The cnlciiim salt, zznc Aalt, and silversalt are amorphous. When the acid is distilled witah concentratedsulphuric acid, it is converted into a-chlorocrotonic acid (m. p. 99").l9-Methyhoglycidic acid, isomeric with the P-methylglycidic acidobtained from a-chloro-/?-hydroxybutyric acid (ru. p. 62-63'), isformed when a-chloro-/?-hydroxybutyric acid (m. p. 80.5") is treatedwith hot alcoholic potash, and the crystalline potassium salt decom-posed with dilute sulphuric acid ; it is a thick liquid, having a strongodour of butyric acid.Thepotassium salt, C,H,O,K + H20, separatesfrom alcoholic ether in prismatic crystals, melts a t 82", and is readilysoluble in water and cold alcohol. The silver salt, C4H,03Ag, crys-tallises from hot water in small, colourle.qfi needles.A B-chlor-a-hydi.oxllbutyric acid, melting at 125", and isomeric withthe lJ-chlor-a-hydroxy-acid (m. p. 85-86") referred to above, is ob-tained when the potassium salt of /I-rnethylisoglycidic acid is treatedwith very concentrated hydrochloric acid ; it crystallises in prismsand is readily Holuble in water, ether, and alcohol. The C ~ Z C ~ U ~ I L salt, (c4&clo3)2ca + 4H20, is crystalline ; the zinc salt, (C4H6C1O3)&,crystxlhes in well-dt!fined, transparent plates, and is readily solublein water.When the acid is treated with alcoholic potash, it is recon-verted into /3-methylisoglycidic acid; on boiling a solution of itssodium salt, carbonic anhydride, propaldehyde, and sodium chlorideare formed.When a-chloro-p-hydroxgbutyric acid (m. p. 80.5') is heated withconcentrated hydrochloric acid at 1W0, it yields a dichlorobutyric acid(m. p. 72-73"), identical with the compound obtained from a-chloro-p-hydroxybutyric acid (m. p. 62-63") in like manner.p- Het hy lisqqly ceric acid, C,H,O,, is formed when P-methylisogly cidicacid i R heated with water a t 100" for 5-6 hours in sealed tubes ; i tcrystallises in short, seemingly rhombic prisms, melts at 45', and iureadily soluble in alcohol and water, but only sparinglyin ether.Thepotassium salt, C4B,04K + H,O. crystallises from alcohol in pris-matic plates, and is readily soluble in water. The barium salt,(C,H,04)2Ba + 2H20, is a granular, crystalline compound. Thesilver salt, C4H704Ag, crystallises from water, in which it is onlyRparingly soluble, in large prisms. When the acid is repeatedly melted,its mclting point rises, poksibly because it is partially converted intop-methylglyceric acid (m. p. 80").The authors are of the cpinion that the chlorhydroxy-acids obtainedfrom isocrotonic acid are the geometrical isomerides of the correspond-ing crotonic acid derivatives, and that their experiments afford addi-tional proof of the stru-tural identity of crotonic and isocrotonic acids.Preparation of Dehydracetic Acid.By H. v. PECHMANN (Ber.,24, 3600) .-Dehydracstic acid can be very conreniently prepared bytreating acetonedicarboxylic acid with acetic anhydride, dissolvingthe crystalline substance (m. p. 254") obtained in this way in diluteRoda (1 mol.), evaporating to drgnesn, and then precipitating theaqueous solution of the residue with acetic acid ; the yield i R about3UO grams from 1 kilo. of citric acid.F. S. I(.F. S. KORGANIC OHEMISTRT. 297Resolution of Inactive Lactic Acid by Penicillium Glaucum.By G. LINOSSIER (Bull. SOC. Chim. [S], 6, l0--12).-After threemonths, solutions of ammonium lactate (corresponding with 5 percent.lactic acid) in which pure cultivations oE Penicillium glaucumhave been growing become alkaline and lsvogyrate. From bhe pro-ducts the author has isolated a dextrogjratle lactic acid, which yieldsa lsevogyrate zinc salt. Mixtures of hot solutions of this salt and ofdextrogyrate zinc paralactate deposit, on cooling, ciystals of inactivezinc lactate.During the first two months, when the mould is vigorouRly growing,no active acid appears ; it is only in its later stnges of development,,when fat appears in its hyphse, that the nutrient solution manifestsoptical activity. Hence it appears that the healthy f u g u s attacks bothvarieties of lactic acid equally, but, when weakened, the lsevorotatoryvariety is more easily assimilated.Decomposition of Glutaric Acid at a High Temperature.By W.LOSSEN (AnnaEen, 266, 264-266).--8 reply to Clam (thisvol., p. 40).-The author does not deny that carbonic anhydride isevolved when glutaric acid is heated under certain conditions ; his andWisbar's experiments (Absir., 1891, 101 1) were undertaken simplpin order to ascertain whether, and if so which, butyric acid is formedOIL heating glutaric acid ; they found that butyric acid is not produced,and, consequently, CIaus' original statement is untrue.T. G. N.F. S. K.Conversion of Unsaturated Acids into their StereocherhicalIsomerides by Soda. By A. DELISLE (Her., 24, 3620-3622).-Maleic acid undergoes no change when it is heated with aqueous oralcoholic potash for a short time at loo", as has lately been shown bySkraup (Abstr., 1891, 1338).The author finds that 30 per cent.soda is also without action at loo", but that when the temperatureis raised to 106", the male'ic acid is slowly transformed into fumaricacid ; malic acid is converted into fumaric acid under the same con-ditions.When a solution of citraconic acid (6.5 grams) in 28 per cent. soda(100 c.c.) is heated for six hours on the water-bath, it yields mesa-conic acid (3.7 grams) and itaconic acid (1.2 grams), but a consider-able .quantity of citraconic acid remains unchanged ; when mesaconicacid (6.5 grams) is treated in like manner, it gives citraconic acid(1% grams) and itaconic acid (1 gram), a large quantity (3.7 grams)remaining unchanged.Pyrocinchonic acid is not acted on by concentrated soda at loo",but diphenylmale'ic acid is converted into a substance which meltsconsiderably above 25U", and which seems to have the same percentagecomposition as diphenylmaleic anhydride.ap-Dimethylglyceric Acid from Angelic Acid.By P. MEL~KOFFand P. PETRENKO-KR~TSCEENKO (Annulen., 226, 378--38U).-When theliquid dimethplglyceric acid obtained from angelic acid (Abstr., 1891 j,862) is kept for a long time, it gradually solidifies to a mass ofF. S. K298 ABSTRACTS OF CHEMICAL PAPENS.crystals ; this crystalline acid is identical with the alp-dimethyl-glyceric acid obtained from tiglic acid.Derivatives of Glutamic Acid. By A. MENOZZI and G. APPIAxr(Rend. Acrid. Linc., 7, i, 33-40).-Glutamic acid, prepared by themethod of Hlasiwetz and Habermann, melts at 200", and in aqueonss Blution (2-4 per cent.) has a specific rotatory power [ a ] n = +1;1.5"a t 22". For the hydrochloride in aqueous eolutions (4 per cent.)[ a ] D = +27*5"at 15", and for the calcium salt [a],, = -3.6" a t 16".'J'hese results agree fairly with those.of Scheibler (Abstr., 1884, 1308).The authors were unable to prepwe the diammonium salt describedby Habermann (Annalen, 179, 248).Glutimide is best prepared by passing dry hydrogen chloride into asolution of glutamic acid (20 grams) in absolute alcohol (100 grams) ;the ethyl glutamate hydrochloride t h u s obtained is decomposed hymoist silver oxide, and the dissolved silver precipitated by hydro-gen sulphide ; on concentration, ethyl glutamate separates, and,nft,er heirig recrystallised from dilute alcohol, is conveyted intoglutimide by heating in a closed tube with alcoholic ammonia for7-8 hours a t 140".Or an alcoholic solubion of glutamic acid may besaturated with hydrogen chloride, alcoholic ammonia added, t8hesolution filtered from aitimoninm chloride, saturated with ammonia,and then heated in a closed tube for conversion into glutimide. Theglutimide thus obtained is optically inactive, and crystallises with-out water of crystallisation i n the oblique system, a : b : c =Active glutinaide, CSH8N,0,, is prepared by saturating the solutionof ethyl glutamate obtained as above with ammonia in the cold ; aftersome time glutimide separates, and, on recrystnllisation from water,is obtained in large, orthorhombic pyisms or tables (a : b : c =0.661 : 1 : 1.016) containing 1 mol.HzO, which is lost on drying oversulphuric acid or on heating at 1UO". It melts at about 165", and itsspecific rotatory power [a]D =: -140" in aqneous solutiou (8.5 percent.) at 15". The aqueous solution is not changed by boiling withmagnesia, but readily yields ammonia when boiled with hydroxides ofthe alkalis or alkaline earths. The anhydrous compound dissolves in13 parts of water a t 9", and in 125 parts of absolute alcohol at 13".When heated with alcoholic ammonia in a closed tube for 8-9 hoursat 140-1.50", i t is completely converted into inactive glutimide.On treating inactive glutimide with conceutrated hydrochloric acid,ammonium chloride and inactive glutamic acid hydrochloride areobtained.The latter substance forms orthorhombic crystals ( a : b : c= 0.8852 : 1 : 0*3866), part of which show right-handed and part left-handed hemihedrism ; it is therefore a mixture of the hydrochloridesof dextro- and lsvo-glutamic acid.On boiling the aqueous solution of inactive glutimide with bariumhydroxide, precipitating with sulphiiric acid, and concentrating thefiltrate, inactive glutamic acid is obtained in orthorhombic crystals.These crystals are completely holohedral, but, on repeated crystullisa-tion from water, crystals showing right- and left-handed hemihedrismare obtained. W. J. P,F. S. K.1.403 : 1 : 1.421 ; /3 = 86" 58'.ORGANIC OHEMZSTHY.299A New Isomeride of Galactonic Acid andof Mucic Acid. B yE, F~SCHER (Bey., 24, 3622--3629).-When galactonic acid is heatedwith quinoline or, better, with pyridine, it is partially converted into astereochemical isomeride, which bears the same relationship to g&c-tonic acid as gluconic does to marinonic acid ; this new componn(],which the author names talonic acid, yields, on reduction, a, syrupysugar (talose), which is converted into talomucic acid, the stereo-chemical isomeride of mucic acid, on oxidation with nitric acid.Tnlonic acid is prepared by heating a 50 per cent. aqueous solutionof pure galactonic acid (125 grams) with pyridine (125 grams) andwater (1 litre) for two hours atl 150" in a closed vessel; the filteredsolution is boiled with crystalline barium hydroxide (125 grams) untilfree from pyridine, mixed with a quantity of sulphuric acid exactlysufficient to precipitate the barium, treated with animal charcoal, neu-tyalised with cadmium carbonate and cadmium hydroxide, and filtered.On cooling, the sparingly soluble cadmium salt of gslactonic acid isdeposited in crystals ; after separating this compound as completely aspossible, the diluted mother liquors are treated with hydrogen sulph-ide, and the tnlonic acid in the hot, filtered solution precipitated withhasic lead acetate.The colourless basic salt obtained in this way isdecomposed with hydrogen sulphide, the filtered solution, which stillcontains galactonic acid, boiled with brucine and evaporated to asyrup ; the brucirie salt of talonic acid, which is deposited in crystalson cooling, is washed with a little alcohol and t'hen dissolved in hotmethyl alcohol, from which it separates in slender crystals melting a,t1:30-133", and readily soluble in water.The yield of the pure saltis 23 per cent. of the galactonic acid employed, which is equivalent to7 per cent. of talonic acid. The free acid is obtained by boiling anaqueous solution of the brucine salt with barium hydroxide, evaporat-i n g the cold filtered solution to dryness, and extracting the residualb;irium'salt with boiling alcohol to free i t from brucine ; if now thebarium salt is decomposed with sulphuric acid in the usual way, andthe filtrate evaporated, there remains a syrup which consists of amixture of tnlonic acid and its lactone ; this syrup is strongly dextro-rot,atory, and is readily soluble in hot alcohol.The caZcium, strontium,barium, and zinc salts of the acid are very readily soluble in water,and do not crystallise. The cadmium salt, (C&,,O,)&d + HzO, is acolourless, crystalline compound, very readily soluble in cold water.The hydrazide, C6H,106*NzH2Ph, crystabes from hot alcohol in small,colouriess prisms, melts a t about 155" with slight decomposition, andis much more readily soluble in water than the corresponding deriva-tive of galactonic-acid.Talose, prepared from the mixture of the acid and its lactone in theusual manner, is a colourless syrup ; its hydrazone differs from that ofgalactose in being very readily soluble in water, but its osnzone cannotbe distinguished from the corresponding galactose derivative.When talonic acid is heated with pyridine under the conditionsdescribed above, it is parhially converted into galactonic acid.TaZomucic.acid, G6H,oOR, is obtained when talonic acid is evaporatedwith dilute nitric acid, and is purified by means of its calcium salt.It crystallises from acetone in colourless, microscopic, quadratic plates300 ABSTRACTS OF OHEMLCAL PAPERS.melts at about 158" with decomposition, and is very readily Roluble incold water and warm alcohol, but only sparingly in warm acetone, andalmost insoluble in ether, chloroform, and benzene ; its specific rota-tory power is [a]D"' = + 29.4' (approximately), but this value rapidlydecreases on boiling the solution, owing to the formation of thelactone; it does not reduce Fehling's solution even on boiling.Aqueoiis solutions of the acid give colourless precipitates with leadacetate and with barium hydroxide, and in neutral solutions, cadmiumsulphate produces a colourless precipitate.The s?:Zver salt is insoluble,and is decomposed by boiling water. The potassium hydrogen salt is acolourless syrup, very readily soluble in water. The calcium sa,lt,CsH,O,Ca, separates from hot water in the form of a colourlesd, crys-talline powder; when boiled with water, it changes to a paRty mass,and only dissolves to a slight extent, but it is =ore readily so!uble inhot, very dilute acetic acid. The phenyZhydrazide crystallises inalmost colourless plates, melts at 185-190" with decomposition, andis much more readily soluble in water than the dihydrezide of mucicacid. When talomucic acid is heated with concentrated hydrochloricand hydrobromic acids a t 150", i t is converted into dehydromucicacid j on treatment with pyridine and water at 140", it gives, mucicacid.F. S. K,Constitution of the Hydroxamic Acide. By F. TIENANN (Ber.,24, 3447--3453).-The reactions by which the hydroxamic acids areformed suggest at once that they are hydroxamido-derivatives of thegeneral formula R*CO*NH(OH) ; the hydrogen of the hydroxyl groupbeing displaceable by alkyl and alkoyl radicles. Lossen at first putforward this viow, but he has since expressed the belief that they areoxinlido-derivatives of the general formula R.C (N0H)nOH on theground that they are convertible into compounds containing either anoximido-group or an alkylated or alkoylated oximido-group.' Thus,when treated with silver nitrate in alkaline solution, silver derivativesare formed which, on subsequent treatment with alkyl iodides, yieldthe compounds R*C(NOR')-OR', but Tafel and Enoch have shown(Abscr., 2890, 491) that certain aromatic amides, under similar con-ditions, yield compounds analogous to the last mentioncd, thus,RC(NH).OR', from which it might with equal force be urged t h a tthese amides had the constitution R-C(NH).OH.The author isinclined to ascribe these phenomena to tautomerism, and he holds tbeopinion that t,he hydroxamic acids have the constitution R-CO.NH-OH.A.R. L.Alkyl and Acidyl Sulphides. By S. H. DAVIE~ (Ber., 24, 3548-35521.-A compound of the composition MeJS is obtained whenmethyl bisulphide or methyl tersulphide is heated at 100" for 3-4hours with methyl iodide ; it crystallises in colourless needles, and,after having been converted into the corresponding chloride, giveR aplatinochloride of the composition (Me3SC1),, PtCld.Acetic sulphide (thiacetic anhydride). SAC,, prepared by heatingacetic acid with phosphorus pentasulphide, boils at 66-67' under apressure of 20 mm., and ut 156-158" under a pressure of 747.5 mm.ORGANIC: OHEXISTRY. 301with park1 decomposition ; when heated with water, i t is decompo3edinto acetic acid and thiacetic acid.F. S. KThio-derivatives of Furfuraldehyde. By E. BAUKWN and E.FROMM (Bet-., 24, 3591-3599 ; compare Abstr., 189 I, 1008).-z- Trithiofurfi~raEdeIL~dd, (C,H,S and the /$compound desc1.i bedbelow, are produced when an alcoholic solution of furfuraldehyde isc:Lrefully mixed with alcoholic hydrochloric acid a t -so, and thensaturated with hydrogen fiulphide in the cold ; after keeping for 24hours, excess of sodium carbouate is added, the precipitate separatedby filtration, dried in a desiccator, and dissolved in benzene or chloro-form ; on adding alcohol to the solution, the /?-compound is for themost part precipitated, the a-compound remainin: in solution.a-Tr.ithiofurfur;tldehydt: is obtained in colourless crystals when thebrown alcoholic benzene mother liquors are shaken with animalcharcoal.the so111 tion evaporated, arid the residue repeatedly recrys-tallised from dilate alcohol; it melts a t 1B0, turns yellowish-brownon exposure t o the air, arid is very readily soluble i n benzene andchloroform, but rather more sparingly i n alcohnl, and insoluble inwater. Molecular weight dettmninations by Baoult's method iiinaphthalene solution gave results agree ng with those required bya cornpound of the mol Acular formula given above.B- T,-itlril,fiLrfur.nldehyd~, (C,H,SO),, is obtained i n co'onrless needleswhen the precipitate referred to above is repeatedly re jrystallisedfrom benzene, using animal charcoal; it is formed when the a-corn-pound, in benzcne solution, is treated with ethyl iodide cqntaininga trace of free iodine. It melts at 229' with decomposition, turnsyellow on exposure t o the air, and is readily soluble in chloro-form, but more spiiringly in benzene, axid almost insoluble in alcohol;molecular we'ght determinations showed that the compmnd hAs themolecular formula a3signed to it above.The polymeride of thiofurfnraldehyde described by Cahours(Aiinalen, 69,55) is deposited in colourless crystals when t m alcoholicsolution of furfuraldehyde is treated with alcoholi: ammonium sulph-ide a t the ordinary temperature ; it softens at 80°, melts completelya t 9U-9l0, and has the empirical formula C5H,S0.Its molecularweight was determineJ by Raoult's metohod i l l naphthalene solution,and found t o be about 2200, a result which corresponds approximatelywith th 1 molecular formula (C,H,SO),, ; a<, however, the depressionof the freezing point of the naphthalene increases continuously withthe time during which the solution is heated, it seems likely that theinoleoule is even greater than that given above, probably (C4H5SO)2,.It is readily soluble in benzene, and i f ethyl iodide containing freeiodine is adJeLi to the solution, 13-trithiofurfuraldehjde is depositedin crystals after Some time.When heated a t a temperature justbelow 160 fur 10-12 hours, it yi2lds large quantities of the furfuro-stilbene described by Cahours and Shwnnert ; this cornpound is alsoobtrtined when either of the trithiohrfuraldehydes is heated a t about230" ; it melts a t 101", and hasthe molecular formula Cl0H8O2, a s wasprvved by molecular-weight determinations in glacial acetic acidsolution.F. S. K.Y VOL. LXII302 ABSTRACTS OF CHFFI'VIICATI PAPEhS.Constitution of Tetrole Nuclei. By G. CIAMICIAN and A .ANGELI (Gazzetia, 21, ii, 109--133).-The authors' views of the con-&rution of tetrole nuclei have been lately expoundcd by Ciamician(Abstr., 1891, 1195), and in the case of thioplien are greatly sup-ported by the following experiments, showing that. derivatives of thatsubstance on oxidation yield open chain compounds containing theSynthetical tetrabromothiophen (1 part), on treatment with nitricmid (AP. gr. 1.52, 10 parts), cooled in a mixture of snow and salt,is converted into a brown, semi-solid substance ; o n withdrawing thecooling mixture, this dissolves with development of heat, brominebeing liberated, and on pouring the product into cold water, awliite, ci-ptalline compound separates which, however, soon redis-solves.After being nearly neutralised with caustic alkali, extractedwith et'lier, and the latter evaporated, dibromomaleic anhydride isleft, the Tield being almost theoretical. It melts at 117-118", audnot at 114-115" as previously stated.Tetrabrornothiophen (3 grams), on oxidation in boiling acetic acidsolution (50 c.c.) with chromic anhydride ( 5 grams), gives off bromineand yields a yellowish product which is insoluble in most of the ordin-ary solvents. On boiling with alcohol, and crystallising from boilingxylene, yellow scales are obtained which darken at 240°, and do notmelt a t 310" ; this compound probably has the compoc;ition C9Br,SpOz.It dissolves in boiling caustic potash, yielding a brown soh-tion, and with alcoholic potash gives a solution which is yellowwhile hot, and brown when cold.On heating the cornpound withphenylhydraeine, either directly o r in solution in xylene or acetic acid,aniorphoufi, highly-coloured products are obtained. On concentratingthe xylene mother liquors from the crystallisation of the substance,a yellow, amorphous substance is obtained which is soluble in Iienz-ene, and melts a t 220" ; it is possibly a decomposition product of theless soluble substance.Synthetical a-methyltribromothiophen (1 part) is gradually intro-duced into nitric acid (sp.gr. 1.52, 10 parts) cooled in snow andsalt ; it immediately dissolves t o a reddish-browE liquid, but broniineis not evolved. If the solution is now poured into water (60 Farts),the excess of acid partly neutralised by an dkali hydroxide, andtbe solution extracted with ether, the ether on evaporation leaves anoily residue ; when this is suspended in water, and again extractedwith ether, a yellow oil is obtained which solidifies after a time ; bydlssoiving the product in warm benzene, precipitating by light petr-oleum, and crystallisiiig i t from benzene, colourless, orthorhombicprisms, a : b : c = 0.6381 : 1 : 0.4670, of dibromoacefylacrylic acid areobtained melting a t 78-79". This acid dissolves in solutions of thealkali carbonatleg with effervescence, is very ~oluble in hot water,ether, and alcohol, sparingly in cold water and benzene, and insolublein light petroleum ; on reduction with 2.5 per cent.sodium amalgamin dilute sulphuric acid solution, it yields dibromolevulinic acid.With phenylhydrazine in amtic acid solution, a deposit of yellowneedles is obtained ; this, after crjstallisation from dilute alcohol,melts at 84-10U". and is probably a mixture.I Igroup -co.c: c*co--303 OROANIC CHEMISTRY.p-Methyltrihromothiophen (1 part'), when dissolved in nitric acid(sp. gr. 1-52, 10 parts), and treated in a manner similar to the above,yields a yellow oil which soon solidifies. If t h i s is dissolved inbenzene, decolorised by animal ohrcoal, and precipitated severaltimes by light petroleum, bromoci trnconic anhydride is obtainedmelting a t 100-lOl", a slightly higher temperature than has pre-viously been given.Experiments on the oxidation of 2 : 5-dimethyldibromotl1 iopllenand 2 : 5-methytphenyltribromothioplien led to no positive result, t,heoxidation products being badly characterised.The above experiments show the great analogy existing betweenthe thiophen.pyrroline, and furfurnn nuclei, and also afford a methodof determining the position of the alcohol radicles in substitutedthiophen derivatives.The speed a t which the oxidation proceeds was determined byallowing iiitric acid of knqwn strength t o act on the thiophen deriva-tive for a fixed time, interrupthg the reaction, and estimating thesulphnric acid produced.Nitric acid of sp. gr 1.47, acting for 18minutes, decomposed 2.92 per cent. of tetrahromothiophen, 84.62 percent. of a-methyl tribromothiophen, and $2.00 per cent. of P-methyl-tribromothiophetl ; acid of sp. gr. 1.45, acting for 51 minutes, con-verted 24-14 per cent. of a-methyltribromothiophen and 31.12 percent. of p-methyltribromothiophen. W. J. P.Derivatives of Ethyl 1-cetothienoneoxalate. By S. SALVATORI(Gazaetta, 21, ii, 268-294) .-Acetothicnoiieoxalic (thenoilpyruvic)acid, obtained hy Angeli (Abstr., 11191, 550) by the action of sulph-uric acid on the ethyl derivative, may conveniently be prepared bytreating a mixture of acetothienone and ethyl oxalate with sodiumethoxide, proceeding according to Rromme and Claisen's method ofpreparing benzoylpyruvic acid (Abstr., 1858, 691).The ethyl de-rivative, C,SH,.CO*CH,.CO.COcl)Et, described by Angeli, gives rise toa series of metallic mlts ; the copper salt, (CloH80J2Cu, forms a veryinsoluble, pale-green mass ; the ammonium salt, C,,H,,S 04,2NH3, isobtained afi a pale salmon-coloured, crystalline powder soluble inalcohol, benzene, and ethyl acetate. It melts at 125" with decomposi-tion, and its solutions evolve ammonia on heating to 60-70". Nonitrofio-derivative could be obtained either from the acid or from tbeethyl derivative by V. Meyer's method, the product consisting ofative of this acid is formed by the- condensation of a molecule o€ ethylacetothienoneoxalate with a molecule of phenylhydrazine with elimina-t,ion of 2 mols.H,O. It crystallises from alcohol i i i colourless, mono-clinic prisms, a : b : c = 1.177 : 1 : 0.716 ; p = 64" 10'' melts at &lo,dissolves in most solvents, Lut not in water. The acid is obtainedfrom the ethereal salt by hydrolysis. It separates from alcohol intriclinic crystals, melts at 195", and decomnoses a t a slightly highertemperature ; the silver salt, C,rH,AgSNzO2, forms a white, curdyy 301 ABSTRACTS OF C IEMICAL PAPERS.mass; salts of copper, mercury, zinc, lead, barium, and iron have;ilsn been prepared. On heating i t above its melting point, it losescarbonic anhpdride, and yields the corresponding thieiay?phen.ylp?ll.az~le,C,,H,,SN,. The latter crystallises from alcohol in white needles,melts at 54", and distils unaltered above 300".It is freely soluble inalcohol, ether, and benzene, and sparingly in water; it is dissolved byconcentrated mineral acids, and reprecipitated on dilution ; it givesKnoi-r's reaction for pyrazoles.The ethindide, ClaHl,SNz,EtI, cr,vstallises from water in colourlesspristris melting a t 175-1 74" ; the platiwoclrloride, ( C,3H,J3N2)z,H2PtCI,,separates in dark orange-yellow flakes. I - ->N.-The ethyl derivative$HC(COOH)Thienylisoxnzolic Acid, C (CASH,) -0of this acid was prepared by Angeli by tlie condensation of ethyl:Lcetot,hienoneoxalate with Ilydrr)xylamirie. The free acid may beobtained in colourless crystals melting a t 177" with decomposition,:)nil readily soluble in alcohol, ether, and water.The silver salt,C8HJAgSN0,, separates in white flakes ; salts of copper, lead, mer-cur-y, barium, and iron were also prepared.A h-jdrated oxime of acetothienoiieoxalic acid, CSHiSN04 + H,Omay be prepared b.y dissclring the acid in a slight excess of sodinacarbonate, and adding the theoretical quantity of hydroxylamine, alsodissolved in sodium carbonate, the solutions being kept so dilute that30-40 C.C. of the liquid only contain 1 grain of acid; the mixtureis then allowed to remain for some time. On acidifying with hydrci-chloric acid, the oxime gradually separates in minute crystals. Itmay be obtained pure by ~llowing a cold ethereal solution to evapor-ate spontaneously, and collecting the first crop <if prismatic crystalsdeposited.It melts with decomposition at 110-112", and dissolresi n most colvents, but is partially converted into thienylisoxazolic acid.The conversion is niore speedily effected by the action of aceticRnhydride, no acetyl derivative being formed. This compound is ofinterest as being the first of the monoximes of the /3 diketouic acidswhich has been isolated.C?ynnacetothienone, C4H3S.CO*CHz.CN, is preparcd by heating smallquantities of thienylisoxaxolic acid in a, narrow tube until the evo-lution of carbonic anliydride ccasm, and treating the residue withsodium carbonate. When pure, i t cr-jstallises from alcohol in colour-less, lustrous plates, and from water in large needles, melts a t 1 3 7 O ,aiid does not decompose at 200".It resembles cyanacetophenonegenerally in its properties.An oxirne of lne~izoylpyruvic acid, ClnH,NO4 + HzO, may be obtainedby the method adopted for the preparation cf acetothienoneoxalicnxime; but if the digestion with hydroxylamine is prolonged f o rmore than three hours, the oxime formed a t first is gradually con-verted into phenylisoxazolic acid. It bears a general resemblanceto the preceding oxime, but is even more unstable; i t melts a t98-100° with decomposition, and crystallises from its cold etherealsolution in prisms.When phenylisoxazolic acid is heated above its melting point iORGANIC CHEMISTRY, 305the manner deqcribed for the preparation of cyanacetothienone, theproduct is identical with the cyanacetophenone described by Haller(Abstr., 1856, 440).The formation of these nitriles sliows that theconstitution of the oximes may be respectivelv represented bv theformu]= C,SH,*CO.CH,*C (NOH).COOH and CH,DzC (NOH)-COO H.The author believes that the behaviour of these oximcs, and especiallythe high temperatures necessary for the formation of the nitriles,indicates that they are =I-monoximes, and hence form a11 exception toHantzsch's hypothesis.Use of Sodium Hypophosphite in Sandmeyer's Reaction.By A. ANGELI (GazzPtta, 21, ii, 258-!261).-Sandrneper's originaliwction has the disadvantage of involving the use of cuprous saltswhich are not very stable and must be fresbly prepared. Gatter-mann's modification (Abstr., 1890, 970) involves the preparation offinely-divided copper perfectly free ft om zinc, and necessitates theconstant agitation of the liquid, especially a t the comniencement ofthe reaction.The following process obviates these difficulties ; i tdepeuds on the circumstance that when a solution of copper sulphateand sodium hypophosphite is acidified with hydrochloric acid andgently warmed, cuprons chloride speedily separates according to theequation 2CuC1, + HJ?O, + H20 = H,PO, + 2HC1 + Cu,CI,(Abstr., 1886, i 7 1 ) . A mixture of copper sulphnte and sodiumhypophosphite may therefore he added to acid solutions instead ofcuprous salts 01- metallic coppei-. Aniline is, for example, conrertediiito chloro-, homo-, iodo-, and nitro-benzene as follows :-Ch1orobenzene.-A solution OF aniline (9.3 grams) in hydrochloricacid (40 grams) and water (60 grams) is slowly mixed with a.solu-tion of sodium nitrite (7 glams), and then with a solution of coppersulphate (12.5 grams) and sodium hypophosphite (7 grams), when ah i s k effervescence ensues, owing to the evolution of nitrogen; assoon as this is over, the product is steani-distilled, and the chloro-benzene separated and rectified. It passes over almost entiiely a t132", and is converted by concentrated nitric acid into parachloro-nitrobenzene melting a t 183".Bromobenzene can be prepared in like manner by treating asolution of aniline (9.3 grams) in sulphuric acid (40 grams) andwater (90 grams) with a solution of sodium nitrite ( 7 grams),allowing the mixture to remain for a while, tlien adding sulphuric acid(20 grams) diluted with water, and solutions of potaseium bromide(36 grams), copper sulphnte (12.5 grams), and sodium hypophos-phite (7 grams).S. B.A. A.Iodobenzene may be prepared in like manner.Kitrobenzene is obtained by mixing a fiolution of dinzohenzenenitrate acidified with nitric acid with solutions of copper sulphateand sodium hypophosphite, and gently warming.The yields are very good, and the operations speediiy performed.The reaction is also available for the preparation ol cuprous bromideand iodide in a state of parity.Displacement of the Nitro-group by Chlorine or Bromine.By C. A. LOHRV DE BRUYN (Ber., 24, 3749--3750).--When theS. B. A. A306 ABSTRACTS OF CHEMICAL PAPERS.dinitrobenzenes are treated with chlorine or bromine in the absenceof any substance that can act as a carrier of t4he halogen, the reactiondoes not begin until the temperature of 'LOO" is rcached.With chlorine, orthodinitrobenzene yields dichlorobenzene ; exceed-ingly little, if any, orthochloronitrobenzene is formed.Metadinitro-benzene yields metachloronitrobenzene and dichlorobenzene. Para-dinitrobenzene yields parachlororiitrobenzene only.With bromine, the three dinitrobenzenes yield the correspondinghromonitrobenzenes ; the further action of bromine leads to the substi-tution of bromine for hydrogen. An oxychloride or oxybromide ofnitrogen is always formed in the reactions described.By G. DACCOMO (Chem. Centr., 1891, ii,532-533 ; from Ann. Chim. Fui.m., 13, 273-280).-Bearing in mindtlic fact that potassium ethoxide and carbon bisulphide react withformation of potassium xanthate, the anthor studied the reactionbetween potassium hydroxide and carbon bisulphide.Solid potas-sium hydroxide, l e f t in contact with carbon bisulphide, rtactsgradually ; tho bisulphide becomes coloured a t first yellow, whichdeepens into red, and, finally, a reddish-brown mass is produced.After washing with alcohol and drying over sulpliuric acid, a crystal-line, reddish-brown powder is obtained, which is readily soluble i nwater. With dilute acids, it is decomposed with formation of hydrogensolphide, carbonic anhydride, carbon oxysulphide, and sulphur. W it11mlts of the metals, precipitates are formed ; and with diazo-deriv-a tives, compounds are produced similar to those obtained by Leuckartwith potassium xanthate.With diazobenxene nitrate, two newcompounds, the one crystalline and the other liquid, are formed.Both have the empirical formula COSLPh2, and are phenyl clithio-carbonates. In order to determine which has the formnlaOPh-CS-SPh, and which the formula CO( SPh),, the author treatedboth with alcoholic potash. The following reaciions would take place:-C. P. 13.Dithiocarbonic Acids.OPh-CS-SPh + 2KOH = PhSH + PhOH + K,CO,S.CO(SPh), + 2KOH = 2PhSH + KZCOs.In neither case, however, was the formation of phenol observed,nor was there any carbon oxysulphide liberated from the prodnct bytreatmenti with acid ; only tliiophenol and potassium carbonate couldbe detected.It is suggested, therefore, that a molecolar changetakes place in the one or the other during hydrolysis, as Solomon hasalready noticed in the case of the hydrolysis of ethyl xanthate.By treating the crystalline product of the action of potassium hydr-oxide on carbon bisulphide with mctachlorodiazobenzene, a reddish-brown oil, c7ilorophenyl dithiocarbonate, is obtained which also graduallyseparated into a crystalline and a liquid portion, and these both reactwith alcoholic potash, forming potassium carbonate and meta-chlorothiuphenol. Paradiazotoluene behaves in an exactly siniilal-m anne r . J . W. L.Metachlorothiophenol. By G. DACCOMO (Ohem. Centr., 1891, i i,533-534 ; from A m . Chim. Farm., 13, 343--352).--The author haORGANIC C HEMISTRT.307carefully examined the metrtchlorothiophenol mentioned in the pre-coding abstract, since it differs from the one obtained by Otto fromchlorobenzcnesiilphonic chloride. The method of preparation was asfollows :--Nitrobenzene was treated with chlorine in presence ofiodine, according to Laubenheimer's method (Ber., 8, 1621). Itwas reduced with fuming hydrochloric acid and tin, and a very puremetachlorauiline boiling a t 230-232" was obtained. From this,the corresponding diazochlorobenzene was formed by the action ofpotassium nitrite. Lastly, the metachlorodiazobenzene was treatedwith potassium dithiocarbonate, yielding chlorop henyl dithiocarb-onate, from which metachlorothiophenol was obtained by hydro-lysis.Ch Zorop7aenyZ dithiocarbonate is a dark-coloured oil, readily solublei n ether, benzene, chloroform, and carbon bisulphide, sparingly solu-ble in alcohol, and insoluble in water.It may be distilled in ncnrrentl of steam, but it is readily decomposed by heating. Potassiumxanthate reacts wi t,h metachlorodiazobenzene in a similar maiiner t othe dithiocarbonate.Metachlorothiophenol is a colourless, limpid liquid which refractslight strongly, aiid has an especially penetrating odour. It is in-svlublo in water, but readily soluble in alcohol, ether, chloroform, andcarbon bisulphide. It is readily soluble in alkalis, and is precipitatedfrorri the solutions by acids. Theethereal solution reacts with mercuric oxide, and a thick, crystallinemass of the mercury salt is formed.The neutral solutions of thepotassium or sodium salts precipitate solutions of lead salts, lightyellow ; copper salts, dirty yellow ; mercury salts, white ; silvernitrate, yellow. With concentrated sulphnric acid, no reaction takrJsplace in the cold, but, on warming, a beautiful, l i g h t violet colora-tion suddenly appears.With chloral, a chemical change is indicated by the development ofheat, but no defiuite product could be separated. The potassiumsalt, C,H,ClSK, consists of small, prismatic, colourless needles,readily soluble in water, sparingly so in alcohol ; the barium salt,(C6H:aC1S)2Ba, consists of shining scales, little soluble in water ;the mercury salt, (C,H,ClS),Hg, pearly scales, almost insoluble inwater and alcohol.,111 the salts have the characteristic odour ofmetachlorotliiophenol.With acid chlorides, metachlorothiopbenol reacts readily, hydrogenchloride being liberated, and the corresponding salt produced. l'hcacetyl derivative, C6114ClSAc, is a culoourless, strongly refractiveliquid which distils between 255" and 26d". The b e m o y l derivative,C6H4C1SBz, forms triclinic prisms mcltiiig at 72.5".Its sp. gr. is 1.2637 a t 12.5".J. W. L.Ortho- and Para-chlorothiophenol. By G. DACCONO (Chem.Cerh-., 1891, ii, 656-657 ; from Ann. Chim. Furm., 14, 1--13).--'l'h3author has obtained ortho- aiid para-chlorothiophenols by the sntiiemethod as that employed for the preparation of the meta-derivative.Parnchlortiphenyl dithiocarbonnte, obtained from diazochlorobenxeriechloride, prepared from parachloraniline, forms white, pearly scales,which are readily Hobble in most organic solvents, but the compoun308 ARSTRACTS OF CHEMICAL PAPERS.does not melt a t a definite tempmatnre.The author conwidem itToPsible that it i s a mixture of the isomerides co(k+c6&cl), andC,H,Cl-S*CS*OC,H4C1. If diaznbenzene chloride is added to ptaRsiumua,ntha t e instead of t o the di thiocarbonate, the chloro~~heirylxanthate,OEt.CS~YG,H,Cl, is obtained ; this forms white crystals which melta t 124-126" to a colourleas liquid. By hydrolysing each of f.hesecompounds wi th alcoholic potash, parachErothir,phe?zol, C,H,Cl.SH,is obtained, which possesses all the characteristics of Otto's cornpound(Annalen, 143, 109).With sulphuric acid, it produces the sameviolet coloration as the meta-compound does.Acefylpm-achlorothiophenol, obcained by the action of acetic chloride,is c r j stalline, readily soluble, and hoils at 255" under ordiiinry atmo-spheric pressure. The benzoyl dcriva-tive forms large crystals, and melts a t 75.5".OrthochZol.othiopheno1 is prepared in a n exRctly similar manner fromorthodiazochlorobenzene. It forms R cnlourlew, strongly refractiveliquid, of penetrating, but not disagreeable, odonr; boils a t 204-2206',and has sp. gr. 1.2i52 a t 19.5". I t resembles the meta-derivative inits reaction,s, but is less stable, and gradually evolves hydrogen salpliidewith formation of chlorophenyl sulphide. The ncetyl compound bi~ilsat 254-258"; sp. gr.1-2659at 19.S". The benzoyZ compound boils a t335--340", sp. gr. 1.2785.For the sake cif compmiaon, the author prepared the three corre-sponding chlorophenols ; the ortho- and para-compounds, by the actionof dry chlorine on pheiiol a t the ordinary temperature; the meta-compciund according to the methods of Beilstein and Knrbatoff, andof Utilemann. The follawing derivatives are described : acefylorfho-chlorophenol, liquid, boiling point 20.1.2(18" ; sp. gr. 1.1709 at 19.5".RenzOyEor2hochlor~phenol, liquid, boiling point 308-312" ; sp. gr. 1.19 74at 19.5". Acetylmetach lorophenol, liquid, boiling point 226-2523" ;sp. g r . 1.2165. Benzoylm~tach7o~-o~hFno1, solid, melting point 71".Ar,etyZparachEnrophenoZ, liquid, boiling point 23U-232 ; sp.gr. 1.2404at 19.5.Action of Methylchloroform and E thylchloroform on AlkalineSolutions of Phenols. By F. HEIBER (Ber., 24, 3677-3687).-Yhenyl orthacetate, CMe(OPh),, ifi obtained when methylchloroform(16% parts) is gr~dually added in the course of sever;l days to a hotsolution of phenol (38.4 parts) and sodium hydroxide (22.6 parts) inwater (22.6 parts). It crystallises from hot alcohol in transparentplates, melts a t 98--98.5", and is readily soluble in ether, chloroform,and benzene, but almost insoluble in water ; it dissolves in concentratedsulphuric acid with a red coloration, and on prolonged boiling withal(.oholic potash, i t is decomposed into phenol and acetic acid. Thetribrnmo-derivative, C,,H,,O,Br,, is formed when phenyl orthacetateis treated with bromine in cold glacial acetic acid solution ; it crystal-liFes from hot alcohol in transparent plates, melts a t 132-13~3", isvery stable towards acids and alkalis, and is moderately easily solublein ether, chloroform, and benzene, but insoluble in water.OrthonitrophenyE orthncetrde, C&1e(O*C6H4aN0,),, prepared fromniethylchloroforni and orthonitrophenol in like manner, melts a tIts sp.gr. is 12629 at 19.5".Benzoylparachlorophenol., solid, melting point 8i".J. W. TJORGANIC CHEMISTRY. 309167-168", and is only sparingly soluble in most ordinary solventswith the exception of boiling benzene ; it is veiny stable towards diluteacids and alkalis.ParacresyZ orthacetate, CMe ( O-C6H,%~e),, crystnllises from alcoholicether in rhombic plates, melts a t 135.5" (?), and is soluble in all theoydinary organic solvents, but insoluble in water ; i t ia only slowlyacted on by boiling acids and alkalis.The tribromo-derivative,C23Hz10,Br3, separates from boiling acetic acid in crystals, melts a t160-161", and is insoluble in water, but more 011 less readily solublein all the ordinary organic solvents.Metncresyl orthacetate, C23H2403, crystallises in needles, melts a t99-100", and is insoluble in water, but readily soluble in ether,chloroform, and boiling alcohol ; the tribromo-derivative, C231€2103Br3,melts at 151.5-153".Orthocresyl orthacetate, C2:3H2403, forms transparent crystals, meltsa t 87.5--89", and is readily soluble in all ordinary organic solvents,but only sparingly in water.ResorcinyZ orthacetate, CMe(O-C6H,*OH),, is a yellow powder, meltsa t about 155-159" with decomposition, and is readily soluble in coldalcohol, ether, and glacial acetic acid, but only sparingly in hotwater, and insoluble in benzene.Hlldrozybeiazo~henon~, COPh*CaH,*OH, is obtained, together withphenyl benzoate (m.p. 70.5-71.5') and a yellowish-red, resinoussub-tance, when an alkaline solution of phenol is warmed with benzo-trichloride (phenylchloroform) ; it crystnllises from dilute alcohol incolourless plates, melts a t 41.", and is readily soliible in alcohol, ether,glacial acetic acid, and alkalis, but insoluble in water.F. S. K.Derivatives of Carvacrol. By G. MAZZARA and G. PLAECHER(Gazzetta, 21, ii, 155-157) .-Patern6 and Canzoneri obtained nitroso-carvacrol by the action of potassium nitrite on carvacrol, b u t theyield was very small ; 70 per cent.of the theoretical may be obtained,however, by slowly dropping amyl nitrite (35 grams) into an ice-cold solution of carvacrol (50 grams), and soda (15 grams) in thesmallest possible quantity of alcohol. The ethyl alcohol is eliminatedby spontaneous evaporation, the solution diliited with much water,separated from the precipitated amyl alcohol and resin, and acidifiedwith sulphuric acid. The nitrosncarracrol, which separates, is dis-solved in ammonia, reprecipitated with sulphuric acid, axid finallycrystallised from benzene.Diacetylwmidoetlaenylarnidocarvacrol, N A c ~ - ( & H M ~ P ~ < ~ > C B ! ~ , isobtained by heating ace tic anhydride with monacety lnrnid oe then yl-amidocarvacrol in molecular proportion a t 180-190" ; the excessof acetic anhydride is evaporated off, the product cooled to 60", andwashed with water.After recrystallisation from boiling alcohol, it isobtained in transparent tables which melt a t 123-125", and losetheir transparency on exposure to light.Acetyldinitrocaruacrol, C6H (NO&PrMe.OAc. is prepared by heat-ing a mixture of dinitrocarvacrol with acetic chloride f o r some houmin a reflux apparatus. The product is washed with dilute sodium310 ABSTRACTS OF CFfEMICAL PAPERS.carbonate solution, and dissolved in boiling Rlcohol ; on cooling, itseparates as an oil which soon solidifies.By ci~ystallisation fromlight petroleum, it is obtained in yellowish rhombohedra, which turnred on exposure to light, ; it melts a t 72-73".The acetyl and benzoyl derivatives of dinitrothymol melt a t highertemperatures than those of dinitrocarvacrol, whilst the ethenyl andbeneenyl derivatives of carvacrol melt a t higher temperatures thanthe isomeric thymol derivatives.- Action of Dinitrochlorobenzene on Polyhydric Phenols. ByR. N~ETZKI and B. SCH~NDLLEK (Her , 24, 3j85--3589).-~'etral./,itr.o-diphenylresorcinol, C6H4 [0.C6H.,(N0,)a]2, is formed when niolecularproportions of resorcinol, sodium ethoxide, and chlorodinitrobenzene[Cl : (NO,), = 1 : 2 : 41 interact in alroholic solution at the ordinarytemperature. It crystallises from glacial acetic acid in almost colour-less plates, melts a t lb4", and is insoluble in alkalis, and only verysparingly solnLle in most ordinary organic solvents ; it seems 'to becompletely decomposed by reducing agents, and when boiled withaniline, i t yields dinitrodiphenylamine.On treatment with coldf nrning nitric acid, it is converted into pentanitrodiphenylreuorcinol,C1BH9N5012r but with a warm mixture of nitric and sulphuric acid, ityields the /iezanitro-derivat,ive, C,sHaN,Oi, ; the former melts at 68",the latter a t 220", and both compounds are decomposed by boilinganiline with formation of dinitrodiphenylamine.Il'etranitrodiy hen y lquinol, C 1aH ,,N40 10, prepared from q ui no1 inlike manner, crystallises from glacial acetic acid in lustrous plates,melts a t 24O0, and is very sparingly soluble in most ordiiiaryorganic solvents ; i t is not decomposed by boiling aniline.Itsdinit.r.0-derivative, CleHsNsOlr, cry~t~allises from glacial acetic acid iiialmost colourless plates, and melts a t 130" ; its trinitro-derivativemelts at 220'; both these compounds are decomposed by boilinganiline with formation of dinitrodiphenyltimine.Hydromyrlinit~odi~Iien~larnir~e, C,,HgN,05, is obtained by treatingorthamidophenol with chlorodini trobenzene in presence oE sodiumacetate ; it crystallises in brownish-yellow needles, and melts a t 190'.Di~liydro.eydinit~~odipAerLylamii~e, C 12H9N306, prepared from amido-resorcinol in like manner, crystallises iu brown needles, and melts a t163". F.a. I(.W. J. P.Oxidation of Aromatic Compounds containing the SideChain C,,H,. By G. WACKER (Uer., 24, 3488--3491).---Wheusnfrole is oxidised in the cold with a 1 per cent. solution of potassiumpermanganate, it yields the corresponding glycol, CIOH1204, whichcrystallises from ether in prismatic .needles, melts a t 78.5", and givesa diacetyl derivative boiling a t 262" under a pressure of 90 mm.(compare Tiemann, this 1-01,, p. 47). Resides the glycol, which,oontrai-y to Tiemann's statement, is more soluble in cold alcohol thani n boiling ether, piperonal, piperonylic, a-homopiperonylic, formic,and other acids are produced, but not acetic. When jsosafrole isoxidised, i t yields a glycol crystnllising in thick prisms and meltingat 101-102".The glycol obtained from xnethyleugenol crystalliseORGAXIC OHENISTRT. 311in prismatic needles, melts at 68-69', and gives a diacetyl derivatireboiling at 268" (35 mm.) ; whilst the glycol from methylisoeugonolcrysta.llises in rhombic plates and melts at 88".Myristicin and its Derivatives. By F. W. SRMMLER ( R e r . , 24,3818-3823).-1n a previous communication, the author has shownthat myristicin has the composition C12HL10J,, and is a derivative ofbenzene containing an unsaturated Bide chain (Abstr., 1890, 1150).To obtain further information as to its constitution, it was subjectedto the action of oxidising agents ; nitric acid and chromic acid act intoo violent a manner, but the oxidation may be readily carried out bymeans of dilute potassium permanganate. The liquid is filtered hotfrom the manganese precipitate, allowed to cool, and the white,crystalline compound which separates collected and recryatallisedseveral times from water.I t has the composition C9HB04, melts a t130" (uncorr.), boils at 290-295', reduces silver solution, and com-bines with hgdroxylamine and phenylhydrazine. It i N , therefore, analdehyde C8H,03.CH0, and may be termed myristicinaldehyde ; it i.9also found to contain one methoxyl group, and, as already stated, is Rderivative of benzene ; the formula may therefore be further resolvedinto CH302:C6H2(OMe).CH0. The oxygen must; be present in theform of an oxymethylene group, for neither myristicin nur myristicin-aldehyde behaves as a phenol ; hence myristiciiialdehyde has the con-A.R. L.-stitutional formula, CH,<~>C,Hz(OMe)mcHO, and occupies an inter-0 mediate position between piperonaldehyde, CH,<O> CGH3*CH0, and0 apionaldehyde, CHz<O>C6H(OMe),.CH0. The constitution ofmyristicin itself is, themfore, CH,<O>C6H,(Onle)*CIH,, 0 and itmay be termed oxy m ethylenemethoxybuteny lbenzene.The filtrate from myristicinaldehyde contains the correspondingmyristic acid, C HS<O> C,H,( OMe)-COGH, which separates in white,crystalline fla)kes on the addition of phosphoric acid, and, afterrecrystallisation from hot water, forms lung, yellowisli-white needles.It melts a t 208-210" (uncorr.), does not boil without decomposition,even in a vacuum, and is only sparingly soluble in water.I n order to ascertain the positions occupied by the side chains inthese compounds, myristic acid was heated with phosphorus andhydriodic acid i n a sealed tube ; the product of the reaction was foundto be gallic acid, showing that the methoxyl and oxymethylene groupsmust occupy the positions 3 : 4 : 5, the carboxyl, aldehyde, or butenylgroups occupying the position 1.When myristicin is treated wit.h bromine in acetic acid solution,carbonic a,nhydride is evolved, and a voluminous precipitate sepa-rates ; this, after recr-y st allisation from alcohol, forms slender, snow-white needles, and melts a t 159-160" (uucorr.). It has the composi-tion C,H,O,Br,, and appears to be methyZoxymethyZenetribroniop?jro-yallol. H.G. C.312 ABSTRACTS OF CHEMICAL PAPERS.Action of Carbonyl Chloride on Benzylamine.By B. K ~ H Nand J. I t r E s E N F E r a (Ber., 24, 3815-3818).-Hitherto, benzyl iso-cyanate has not, been prepared in the pure condition, the productobtained by acting on silver cyanate with benzyl bromide or chloride(this Jcurnal, 1872, 446 ; Ber., 10, 46) always containing chlorineor hromine. $The authors have endeavoiired to prepare i t by theaction of carbonyl chloride on benzylamine hydrochloride ; the pro-duct is, however, a mixture of varying quantities of benzyl isocyanateand be~izylchloroformamide, CHI,Ph*NH.COCI, which cannot beseparat,ed by fractional distillation, nor can the latter derivative, likemethylchloroformamide (Abstr., 1887, 569), be converted into theformer by distilling with potash, benzyl cyanurate being thus ob-tained.The same compound is precipitated when a large quantity oflight, petroleum is added to the mixture of beiizyl isocyanate andchloroformamide. When the mixture is treated with aniline, the soleproduct is phenyl benzylcarbamide ; methylanilin e converts it intobenzylphe?zylmethyZcai.bamide melting at 84", metanitraniline into benz y l -met~nnitrophennylcarbamide melting a t 188", a-naphthylamine intohenzy 1-a-naph thylcw*banlide melting a t 203', is0 butylamine into berrzyl-isobutylcarbamide melting a t 78-79", and piperidine into beneyl-piperid y lcarbamid e me1 t ing a t 10 1-1 0 2 '. H. G. C.Nomenclature of Stereoisomeric Nitrogen Compounds andof Rings containing Nitrogen.By A. HANTZSCH (Bey., 24, 3479-3488).-The author proposes to distinguish the stereoisomeric nitro-gen compounds by the Greek prefixes syit, anti, and aw,phi, thesebeing equivalent to cis, trans, and cistrans, which are eniployed byv. Baeyer for certain other stereoisomeric conipounds. The prefixsyn is used with those compounds containing certain groups whichare capable of inti~amolecular change, whilst, anti is employed witlithe isomeride containing the same groups which are iricapxble of it ;for example, syn is prefixed t o that benzaldoxime from which benzo-nitrile is obtainable, thus :-P h * s * H Ph-5 *HN-OH ' HO-NSpbenzaldoxime. An tibeiizaldoximc.For distinguishing such compounds as the three isomeric benziledi-oxinies, it is necessary to employ also the prefix amphi, as follows :-Synbenzileclioxime.Antibenziledioxime. Amphibenziledioxime.The acthor is of opinion that the term " azo," in its applicationt o closed-ring compounds, should be restricted t o those containingtriad nitrogen, whilst, for such as contain the group NH, the termL 1 imid 3 7 should be employed. He proposes the following alterationsin nomenclature :-Iinidole for pyrroline, tliiole for thiophen, anORGANIC OHNMISTRY. 31 3oaaTe for furfuran ; derivatives obtained by displacing a CH gronpin theHe by N are designated imidnzols = C,H3(NH)N, orazole =C,H,(O)N, aiid thiuzola = C3H3(S)N respectively. The isomerism ofthese compounds may then be indicated by the above-meritioned pre-fixes; thns, the two imidnzolea [NH : N = 1 : 2 and 1 : 33 are callc dsy nirnidazole and anLp?&nidazolr respectively, whilst Wid man's tri-azoles, C,H,(NH)N,, are named imidodiazoles or azirnidazoles, and thethree isornerides [NH, : N, = 1 : 2 : 5, 1 : 2 : 3, and 1 : 3 : 51 are dis-tinguished as synazinziduaole, synimidodiaxole, and arnphimidodiazolc.The three six-memhered ring compounds C,H,N, are designatedsyn dinzine, amphidiazine, and ant idiazine, according as they have theconstitutions [N : N = 1 : 2, 1 : 3, and 1 : 41.A. R. L.Action of Benzyl Chloride on Ortho- and Para-toluidines.tolxidina, C6HIMe*5Me-CH,Ph, is obtained by heating a mixture, inmolecular proportion, of benzylorthotoluidine and methyl iodide for40 hours. The product is heated with dilute s>,diuro carbonate aildextracted with benzene.At 210-215", under 15.2 m u . pressure, ayellowish oil passes over ; this is insoluble i n nater, soluble i u alcohol,benzene, kc., and has no basic character.The sulphonic derivative of benzylorthotoluidine is obtained hyheating benzplorthotoluidine for two hours a t 185-1 30" with sulph-uric acid containing 15 per cent. of anhydride; its lead and bariumsalts are soluble in water and crjstallise well. The acid is a crystal-line powder, fioluble in water. Its aqueous solution, when treatedwith lead dioxide, becomes first green and then blue.Benzy1parntoluidine.-A mixture of parntoluidine (2 mols.) andbenzgl chloride (1 mol.) is maintained at 155-165" for 40 hours. Ayellowish oil is separated, as ahow; this distils a t 205-5215" under10-15 mm.pressure, and darkens in colour on coolitig. It, remainsliquid, even i n melting ice, whereas the dibenxyl derivative melts a t54 5-55', and benzoylorthotoliiidme melts a t 56-57'. The jield inthe case of benzylorthotoluidine is 40 per cent., whilst in the case ofbenzylparatoluidine it is only 30 per cent. A t a temperature higherthan 170", large quantities of a black, resinoils product are formed;this does not distil up to 270" under 20 mm. pressure.The salts of benzylpzratoluidine are white and well crystallised, butlittle soluble in cold water, more soluble in, and readily decomposedby hot water. The methyl and ethyl deyivntives of this base areobtained by heating it with the corresponding alcoholic iodidtis.Benzylethy~uratoluidinn is a jellow liquid boiling at 200-210" under10 mm.pressure. neurylnrethylparatoluidi~re is a slightly yellowliquid boiling at 210-2'20" under 30 mm. pressure. These derivatives]lave no basic characters.Benzoylbenz~lparatoE~~idine.-This compound is formed by the actionof benzoic chloride on benzylparatoluidine. The product, if distilledwhen hydrochloric acid ceases to be disengaged, yields a thick liquid,which passes over at) 2i5--285" under a pressure of 20 mm., and rapidly~olidifies. No salts have been obtained with acids. When dissolvedi n glacial acetic acid and added drop by drop to fuming nitric acid, a,By C. RABAUT ( BuU. SOC. Chim. [3], 6 , 1 3 7 4 4 0 ) .-1C~ethylbeiirylorti~(,31 4 ABSTRACTS OF CHEMICAL PAPERS,nitro-derivative is obtained, which is precipitated by the addition ofwater.It dissolves in alcohol and crystallises in yellow needles, 1 em.long, which melt at about 135-137'. I t appears to cow& of twosubstances, into which it separates on fusion ; that in greater quantitymelts at 135-137". W. T.Action of Benzyl Chloride on Metaxylidine. By JABLIE-GOX'NET (Bull. Xuc. Chiin. [ 3 ] , 6, 2l).-A mixture of benzyl chloride(1 mol.) and metaxylidine (2 mols.) is heated in a, reflux apparatus at160-165" for 50 hours. The resulting crystalline mass is boiled withsaturated sodium carbonate solution, and the oily, brown layer whichseparates is, after extraction with benzene, distilled under reducedpressure.Benzylmefaxylidilze, C,H,Me,*NHBz, passes over at200-210" under a presslire of 15 mm. a s a pale yellow liquid,which is soluble in alcohol and benzene ; with acids, it foyms white,unstable salts, which are decomposed by water. Methyl, ethyl, andacetyl derivatives have been made and will be described later.Action of Hydroxylamine Hydrochloride on Acetomesitylene.By E. FEITH and S. H. DAVIES (Bey., 21, 3546--3548).--Acetyl-mesidine (rri. p. 216-217") is formed, when an alcoholic solution ofacetomesitylene is heated at 160" for six hours with hydroxylaminehydrochloride and sodium acetak, the oxime which is first producedimmediately undergoing intramolecular change.Acetophenone and acetopseiidocymene are not acted on by hydroxyl-amine under the conditions just stated, but propiomesitylene, at arather higher temperature (ISO"), yields, on prolonged heating, a verysmall quantity of a crystalline compound which melts at 154*5",and is insoluble in potash.T.G. N.I?. S. K.Derivatives of Trinitroquinol. By R. NIETZKI and H. KAEFMANN(Bey., 24, 3824--8830).-Twelve years ago Nietzki showed that oneof the nitro- groups in trinitrodiethylquinol may be readily replaced byan amido- or substituted amido-group ; thus aniline yields a diethoxydi-nitrodiphenylamine. The latter, on boiling with alkali, was found toyield a substance having acid properties, which was regarded asdiethyldinitro tri hydroxy benzene ( Abstr., 1878, 866).Further investigation has shown that this supposition is incorrect,the substance having the compoRition C1J3,,NzO6, instead of ClOHl2O7N2;i t must, therefore, be formed by the hydrolysis of one of the ethoxy-groups, and is an ethozy h y d r o z y d i n i t r o d ~ h e ~ y l a ~ ~ i n e ,OE t*CsH (OH) (NO,) ,*NHPh[OEt : NHPh : NOz : OH : NO, =1 : 2 : 3 : 4 : 51.It crystallisesfrom alcohol in yellow needles, and melts at 152".When diethoxydinitrodiphenylamine is reduced with tin and hydro-chloric acid, it yields the corresponding diethoxydiamidodi~~~~e~~ ylaniinr,CsH(0Et),(NH,),*NHPh, which crystallises in almost colourlessneedles, and melts at 77" ; its hydrochzoride, C16Hz,Ns0,,2HC1, formscolourless needles, which become blue on drying, and are less stablethan the free base. On boiling with acetic anhydride, it yields a derivaORGANIC CHEMISTRY.315tive which is simultaneously an acetyl compound and an anhydro-base, and h a s the constitution N H ~ C ' C ~ H ( ~ C , H , ) , < ~ ~ ~ ~ - ; i tforms colonrless needles, melts a t 162", and is readily soluble in hotwater, alcohol, ether, and dilute acids.T rinitrodiethylyuinol also readily reacts with an excess of dimetbyl-paradiamidobenzene, the reaction proceeding in the same manner a swith aniline ; the nitro-group is evolved as nitrous acid, and convertsR portion of the diamine into dimet,hylaniline. The chief product ofthe action, which has the constitutionC6H( XO,), ( oEt),*NH*C6H4*N&fe2,has distinctly basic propert?ies, and crystallises from alcohol in beauti-ful, red needles nielting a t 148".I t s hydrochloride forms needles whichhave a green surface lustre, and are decomposed by water. It isreadily reduced by tin and hydrochloric acid, but the resulting tri-amido-compound cannot, be isolated, as i t rapidly undeygocs oxidation ;if manganese dioxide be added, and the mixture boiled till theoriginal blue colour has changed to brown, the residue, 011 extractionwith boiling alcohol, yields the product of oxidation in beautifulneedles havirtg a green lustre. The analysis showed that it has thecomposition ClsH2?N4O2, and i t is, therefore, a s would be expectedfrom its mode of formation, a dietho1:ydimethyldia?.ilidophenazine,NH,-C,H(OEt),<.&>C,H,*NMe,, and has all the properties of a,eurhodine.It dissolves in concentrated sulphuric acid with a preencnlour, which, on dilution, passes through blue into red, and colourssilk with a slightly violet-red nuance.crystalIises in needles having a green lustre ; the acetyl derivative,ClaHz,N402Ac, crystallises in pale red needles melting at 179", andyields red salts wit12 acids.Paradiamidobenzene does not undergo condensation with hinitrodi-ethylquinol so readily, but, its acetyl derivative gives more satisfactoryresults ; the product of tlte reaction forms pellow, silky needles, meltsa t 199", and has the constitution C,H(O Et)2(N0,)2.NH.C6H4*NHAc. Onboiling with dilute alkali, the acetyl group is not eliminated, butinstead one of the etbpl groups is removed, with formation of a sub-stance having the constitution OH.C,H(OF:t) (N02)2*NH*CsH4.NHAc,which forms yellowish-brown crystals, readily soluble in alcohol, andmelts a t 206".More concentrated alkali converts it into a dinityo-eth y Ztrih y drox y benzene, OE t*C6H (OH) (NO,) 2, which forms ye 110 wneedles, and melts a t 210" ; it is not identical with the dinitroethyltri-liydrox ybenzene obtained by Nie teki from diamidodinitrophene toil(hbstr , 1883, 466).TrinitrodiethylquinoI also undergoes condensation with dim ethyl-metadiamidobenzene and a-naphthylamine ; the first yields a com-pound of slightly basic properties, having the constitutionC,H (OE t),_( NO,),*NH- CsH4*NAfs2,NThe p i c m t e ,C1~H22N402~ C6H3N307,1 316 ABSTRACTS OF CHEMICAL PAPERS.which crystallises i n orange-yellow needles and melts at 106".compound obtained from a-naphthylamine,fwms yellow needles melting at 128", and may 'be separated from thea-arnidoazoniiplithaleiie siriiultaneously formed by tzLkiiig advantageof its Iesser solubility in alcohol.Diazobenzene Perbromide.By C. E. SAUNDERS (Amer. Chem. J.,13, 486-490).-0n treating an aqueous solution of diazobenzenesulphate, best prepared by Knoevenagel's method (Abstr., 1891,54), with an excess of cold solution of bromine i n moderittely stronghydrobromic acid, diazobeiizene perbromide separates as a dark,pasty mass, which, when repeatedly washed with ether and driedbetween filter paper, loses most of i t s colour, and almost ceases tosmell of bromine. The liquid product o~iginally obtained by Griess( P h i l .Trccr,s., 1864, 673), which was probably a mixture or compoundof the perbromide with free bromine, mas be fortried by exposing thedry solid to bromine vapour, of which i t absorbs a very large quantity ;the perbromide may be recovered by treatment with ether. In t h epreparation of the perbromide, symmetrical tribromobenzene occursa s R bye-product ; i t is dissolved, however, by the ether.When diazobenzene perbromide is treated with bromine-water, it,yields tribroniophenol, and when boiled with water alone, it yields i naddition phenol, hydrogen bromide, and bromine. When boiled withalcohol, i t gives, not bromobeiizene alone, as stated by Griess (loc. cit.),but a mixture of this substance with parabromophenetoil, melting a t4" (compare Remsen and Orndorff, Abstr., 1888, 268).With boiliiigetEer and wit.h glacial acetic acid, it yields bromobenzene, mixed, iuthe latter case, with another compound of much higher boiling point.Intramolecular Formation of an Azo-group. By E. LELLMANNTheC,H( OEt), (N O,),.NH*C,oH,a,H. G. C.JN. W.and R. ARNOLD (Ber., 24, 3557-3.560 ; compare Tauber, this vol., p.1 1 , is obtained when an 183) .- Oyt hazodibenx y lamine,CH2*CF,H,-N "< c H,*c,H,-Nalkaline solution of t h e theorctical quantity of stannous chloride isgradually added t o a hot alcoholic solution of orthodinitrodibenxgl-amine; i t crystallises in small, orange needles, melts at 230", and isonly very sparingly soluble in dcoliol, but, more readily i n benzene.The hydrochloride, C,,H,,N,,HCl + H,O, crystallises i n slender,orange needles, and is converted into the base when heated at SO".tained from orthodinitrodibenzylparatoluidine in-like manner.F.S. K.Alkyl Derivatives of Hydroxylamine. By R. KOTHE (Annulen,266, 310-323 ; compare Behrend ai~d Kijnig. Abstr., 1891, 1032).-When a-benzylhydroxylamine is oxidised w i t h potassium dichromateand glacial acetic acid, it jields benzyl alcohol and traces of benzylnitrite and benzjl acetate, nitric oxide being evolvedORGANIC CHEMISTRY. 317When a-dibenzylhydi.oxgls.nine is treated with potassium dichrom-ate and sulphuric acid, it yields benzylbenzaldoxime and small quan-tities of benzaldehyde and benzoic acid ; if the potassium dichromateis added very gradually to a very dilute sulphuric acid solution of thea-dibenzylhydroxylamine, the yield oE benzylbenzaldoxime is niuchsmaller, but benzyl alcohol and other compounds are formed i n itsplace.Tribenzylhydroxylamine is not acted on by potassium dichromateand sulphuric acid under the conditions employed by the author.When tribenzylhydroxyiamine is distilled under reduced pressure,it is decomposed into P-dibenzylhgdroxylamine, stilbene, benzylamine,p-benzg lhydroxylamine, and ammonia.Amidoximes and Azoximes.By I?. T~EMANN (Be?., 24, 3648-3650).-General remarks on the papers of Marcus, Goldbeck, Paschen,and Richter. (Compare following abstracts.) F. S. K.F. S. K.Nitrogenous Derivatives of some Aromatic Dihydroxyalde-hydes.By E. MARCUS (Ber., 24, ~650-~~657).-~-ResorcylaZdoxime,CsH,(0H),*CH:NOH [CH : (OH), = 1 : 2 : 41, prepared from/3-resorcylaldehyde, crystallises in colourless needles, me1 ts at 191",and is readily soluble i n alcohol and ether; it gives with ferricchloride a brownish-red coloration, and with Fehling's solution agreen precipitate. The corresponding hydrazone (111. p. 158-159')was also prepared. (Compare Rudolph, Abstr., 1889, 251.)Diacety Z-P-resor~yZonitr~Z~, CN.C6H3( OAc),, is formed when thealdoxime is boiled with acetic anhydride ; it crystallises from alcoholin colourless prisms, melts at 72", and is readily soluble in alcohol,ether, chloroform, and benzene./3- Resorcy lonitvile, C7H5N02, i n produced when the diacetyl deriva-tive is hydrolysed with dilute potash.It separates from a mixture ofether and light petroleum in crystals, melts at 175', and is readilysoluble in water, alcohol, and ether ; its aqueous solution gives a redcoloration with ferric chloride.p-IZesorceny lamidoxime, C6H3( OH) 2*C ( NI12):NOK, prepared bytreating the nitrile with hydroxylamine a t the ordinary temperature,turns brown at 160", melts at 166", and is reedily soluble in water,alcohol, and ether ; it reduces Fehling's solution, and gives a browncoloration with ferric chloride.The dioxime, (OH),C6H2(CH:NOH), [ (CH), : (OH), = 1 : 6 : 2 : 41,is obtained when resorcyldialdehjde is tibeated with hydroxylnmine ;i t melts at 209", and is readily soluble in alcohol, ether, and potash,but only sparingly in water ; in its aqueous solutions, ferric chlorideproduces a black, and copper sulphate a blue, precipitate.Orthornethoxyparahydmxybenzoplwaylhydrazone, Cl4H,,N20,, preparedfrom the corresponding aldehyde, is a yellow, crystalline substancemelting at 151-152" ; it is readily soluble in alcohol, ethei-, benzene,and chloroform, but insoluble in water.The corresponding aldoxime,C,H,NO,, melts a t 171", and is soluble in water, alcohol, ether, andsoda, its solutions giving it brownish-red coloration with ferricchloride.YOL Lxzr. 2318 ABSTRACTS OF CJEMJCAL PAPERS.Acet~lvaiza'ltonitriZe, CN.C6H,(OMe)*OAc [CN : OMe : OAc =1 : 3 : 41, prepared by heat,ing vanillinaldoxime (m. p. 117") withacetic anhydride, crystallises from hot watcr in colourless needles,melts at 110", and is soluble in alcohol, ether, and benzene.Vanillonitrile, C8H7N02, i s formed when t'he acetyl derivative is dis-solved in cold, dilute potash ; i t crystallises from hot water in colour-less needles, melts at 87", anfd is soluble in alcohol, ether, and benzene.3n its aqueous solution, ferric chloiide produces R blue coloration, and,on warming, a crystalline substance is precipitated.VuniZlan?jZamido~:i?lze, CpHloNz03, prepared f rorn the nitrile just de-scribed, crystallises from water i n prisms, melts below loo", and dis-solves freely i n alcohol, hydrochloric acid, and soda, but is onlysparingly soluble in ether, and insoluble in benzene ; i n its aqueoussolntions, ferric chloride produces a reddish-violet, and Fehling's solu-tion a green, coloration.Piperonalaldoxime, CH2< o> C6H3*CH:NOH, cry stallises from hotwater in lustrous needles, melts a t l l O o , and dissolves freely i n alco-1101.ether, benzene, chloroform, and carbon bisulphide. The corre-sponding nitrile, C8H,NOZ, is readily solub!e i n alcohol, ether, andbenzene, and crystailises fibom water i n lustrous needles melting at95'. The anzidoxime, CHH8N203, melts at 151", and is soluble i nh o t water, alcohol, ether, acids, and alkalis ; i t s hydi.ochloride,C,€T,N,03,HC1, is a colourless, crystalline compound- melting at 193".E t h e n y l p i p e r o n m ylaxoxiine, CH,<, >C6H3*C<- X->CMe, is formedwhen piperonenylamidoxime is heated with acetic anhydride ; i t meltsa t 110", and is readily solulde in alcohol, ether, and benzene, but in-soluble i n water.F. s. K.00 NONitrogenous Derivatives of Parahomosalicylic Acid. By0. GOLDBECK (BAT., 24, ~658-~667).--Parahomosalicyl~~Zdoxi~i,t.,OH-CoH3Me*CH:NOH [Me : CH : OH = 1 : 3 : 41, crystallises i n long,colourless needles, melts a t 105", and dissolves freely in hot watei.,nlcohc;:, ether, chloroform, and benzene, b u t is only sparingly soliiblei n light petroleum and cold water ; its aqueous solution gives a dirtyviolet coloration Kith ferric chloi+le.Acet~j~~arahomosal&cylonitri~e, CloH,NO,, prepared by boiling t h ealdoxime with acetic aiihjdride, melts at 56-57', and is readilysoi nble in alcohol, ether, benzene, acetone, chloroform, and hot lightpetroleum, but only sparingly in water.Ya.l-ahomosalicylamide, CPH9NO2, obtained by heating ethyl para-honiosalicylate with concentrated amrnonin, crptallises from dilutealcohol in coloarless needles, melts at 177-1 78", and is readilysoluble in alcohol and ether, b u t more sparingly in benzene andchloroform ; its aqueous solution gives with ferric chloride a dark-violet coloration.The cori esponding thiamide, CsHSNOS, wasobtained in an impure condition by melting the amide with phos-I horus pentasulphide ; it dissolves freely in alcohol, ether, chloroform,benzene, alkalis, and h o t water, melts at 126-127", and gives withferric chloride R dark-violet coloration, with copper sulphatle a greenORGANIC CHEMISTRY.319and with silver nitrate a reddish-brown, precipitate. The nitrile,CRt17N0, is formed, with evolution of hydrogen sulphide, when thethiamide is snbmitted to dry distillation. It melts a t lOO--lUl", dis-Iqolves fineely in alcohol, ether, benzene, and chloroform, and is clecom-posed by boiling alkalis ; in its aqueous solution, ferric chloride pro-duces a violet coloration.Parahomofinlicenyla~~~o~;me, CsH,,N2Os, prepared by heating thethiamide with hydroxylamine in dilute alcoholic solution, crptt"l1isesfrom hot benzene in plates, arid from hot, waker in needles, melting at123-124"; it is readily soluble in ether, alcohol, hot water, aidchloroform, and in its aqueous solution ferric chloride produces areddish-violet coloration, and copper ~ i i l phate a light-green precipi-tate.The I,~/lldrachlorirle nielts at 215" with decomposition. Tlielrenr0~2 derivative, C,sH14N,03, obtained by triturating thc arnidoximew i t h benzoic chloride, melts a t 181--152", and is readily soluble inaretone, but otily sparingly in alcohol, ether, and benzene, and in-siil~rble in water and light petroleum ; its alcoholic solution gives a,green coloration with ferric chloride.Benieny~al.aho?izosaZicenylazoaime, OHC6H3MemC< - N>CPh, isformed when t h e benxoyl derivative (m. p. 181-183") is heated.withwater at 100'; i t melts a t Id", dissolves freely in ether, alcohol,~!~1oi-oform, benzene, ligii t petroleum, and alkalis, and gives w i t hferric chloride in alcoholic solution a green coloration.Dib~~~zoylparahomo.salicenyl~~naiJoxime, C2zHlsN,0i,.prepared by shak-ing the amidoxime with potash and benzoic chloride, melts a t l43".,and is readily soluble in hot aicohol, ether, chloroform, and benzene,b u t insoluble iu water, acids, and alkalis.Acetylpa~ahonzosulicenylanz~rlox~me, C,,,H,,N,O,, is obtained when theamidoxime is treated with acetic anhydride a t t h e ordinary tempera-tiire ; i t crjstallises from hut benzene in plates, melts at 148-149",and dissolves frrely in alcohol, ether, cliloroform, benzene, diluteacids, and alkalis ; its dilute alcoholic solution gives a violet colora-tion with ferric chloride.Etheii~~lpnruhomosaliceizylazozime, ClnHION202, separates from etheri n prisrnahic crystals, melts a t 45", and is readily soluble in etliei.,alcohol, benzene, chloroform, and alkalis, but iiisoluble in water anddilute acids j i n its alcoholic solution, copper sulphate produces areddish-brown precipit,ate, and ferric chloride a blue coloration.NOYrop~n~lparahomosalicenylaaoxime-w-carboxyl,ic acid,can be obtained by heating t h e amidoxime with succinic anhydride at&bout 115".It crystnlliszs from dilute alcohol in slender, colourlessiieedles, melts at 103", aud is readily soluble i n ether, benzene! and hotwater, but more sparirigly in cliloroform, and insoluble in light petr-oleum ; its Rqueous solution gives a viulct coloration with ferricchloride, and in its neut,ral sJutioiis silver nitrate produces a colo~ir-less, ci-jstalline precipitate.F. ,S, K.a:320 ABSTRACTS OF CHEMICAL PAPERS.Derivatives of Orthohomosalicylaldehyde and of Ortho-homoparahydroxybenxaldehyde. By E. PASCHEN (Bw., 24,3667-3675) .--tholLomosnlic~~henylh~Jdraaone,OH.C6H3Me-CH:NzHPh [Me : OH : CH = 1 : 2 : 31,crystallises from alcohol in colourless, rhombic plates, melts at 95",2nd turnfi greenish on exposure to the a i r ; i t i.9 readily soluble indcohol, ether, and chloroform, but more spaririglv in hot water, andiiisolublo in light petroleum. The aldoxinte, CEHgNO,, crystallise~ inlong, colourless needles, melts a t 99", and dissolves freely in hotwater, alcohol, ether, benzene, and chloroform, but is insoluble inlight petroleunl and cold water; in its aqueous sdutiom, ferriccll loride produces B violet coloration, and Fehling's solution abro wnish-red precipitate.Orthohomosal;icyZonitrile, CBH7N0, is obtained when the aldoxime isboiled with acetic anhydride, and the oily product decomposed withcold, dilute soda ; it crystalliseR from hot alcohol in colourless plates,melts a t 88.5", and is readily soluble in alcobol, ether, benzene, chloro-form, and hot water, but insoluble in liqht petroleurn.Ortho/, c712osaZiceiiyZamii.loxime, CEHJT202, crystallises from alcoholin large, colourless plates, melts a t 126.5", and is insoluble i n lightpetroleum ; it dissolves freely in alcohol, benzene, chloroform, andhot water, and gives a dirty-preen precipitate with Fehling's solution.The diberazoy Z derivative, C23H,6Nz04, separates from alcohol in small,colourless needles, melts at 164', and is readily ~oluble in ether,benzene, and chloroform, but insoluble i n light petroleum and coldwater.Benzeizylorthohomosa7icenylazoxhne, C15HlzNzOz, prepared by boilingthe dibeuzoyl derivative (m.p. 1 6 4 O ) with soda, forms colourlessneedles, and melts a t 150" ; it is insoluble in light petroleum, but dia-bolves freely in most of the other ordinary organic solvents.Orthohomoparah ydrozybenzophenyl}~ydrazone, C14H14N,0, melts at 151",and is readily Moluble in alcohol, ether, benzene, and chloroform, b u tonly sparingly in hot water, and insoluble in light petroleum, Thenldozime, CBHgN02, ci-ystallises in colourless needles, and melts a t143.5" ; it gives with ferric chloride a dark-green, and with Fehling'ssolution a light-green, coloration.Acetylorthohomoparah~drox~jber~zonttri~c, CIOHgNOZ, is formed whenthe aldoxime (m.p. 143.5") is boiled with acetic anhydride; itcryvstallises in colourless plates, meits at 75-76', and is irisoluble inlight petroleum, but readily soluble in ether, alcohol, benzene, andchloroform. The nitrile, CBH7N0, prepared by hydrolysing t8he ncetg 1derivative with dilute soda, crystallises in colourless needles, melts a t93", and resembles the preceding compound in its behaviour withsolvents.Ort hohoinoparn h ydToxyb enzeny lanaidoain I el C,H,,NzO,, forms colour-Irss scales, meltB a t 152" with decomposition, and turns bluish-greyon exposure to the a i r ; i t is readily soluble in alcohol, but moresparingly in ether and hot water, and insoluble in benzene and lightl~etroleum ; it gives a.bluish-green coloration with Fellling's solution.'Ihe hydrochloride, CBHloN,Oz,HCl, crystalliees in needlesORGANIC CHEXISTRY. 32 1Ethenylorthohoiiioparahydroxybenxenylazo~~~e, C,,R,,,N,02, .preparedby heating the amidoxime with acetic anhydride, crystallises fromIiot, dilute alcohol in small, colourless needles, melts a t 89", and is i n -solubie in water and light petroleum, but readily soluble in alcohol,ether, benzene, and chloroform.p-Trichloro-a-hydroxypropenylamidoxime. By E. RICHTER(Rer., 24, 36'76-367 7) .-p- TrichEoro-a-hydroxypropen~lamidoxi.nL,(:CI,-CH(OH)*C(NH,):NOH, can be obtained by treating the nitrilc:oE trichlorolactic acid with an aqueous solution of hydroxylamine atthe ordinary temperature ; it crystallises from hot wat,er jii plates,melts a t 145" with decomposition, and is almost insoluble i n benzeneand ether, but more readily in alcohol.C3HE,N2C1302,HCl,cryxtallises in plates.F.S. K.The hydrochloride,Et hen y Z- P- trich toro-a-hy drox ypropeny lazoxirne,prepared by warming the amidoxime with ace tic anhydride, crystal-lises from hot water in needles, melts at 160-161", and is readilysoluble in alcohol and ether, but only sparingly in benzene.F. S. K.Phenylglyoximes. By A. RUSSAKOW (Ber., 24, 3497-3511).-is best prepared by treat-Ph* C --C*H##OH #.OH1 Ant kp hen y lamp hig l y ox inae ,Ing sodioisonitrosoacetophenone (1 mol.) with hydroxylnmine hydro-chloride (1 mol.) and sodium hydroxide (1 mol.) in aqueous solutionat the ordinary temperature (compare Scholl, Abstr., 1891, 28i) ; theproduct is precipitated with acetic acid, washed with chloroform, andrecrystallised from ether.It melts a t 168", is almost insoluble inchloroform, and is identical with the phenylgl yoxirne previouslydescribed by Scliramm (Bey., 16, 2186) and by Strassmann (Abstr.,1889. 610). , r Ph*E-EmH is precipitated, as hydrochloride, PheNy la& iglyoxime,0H-N NmOH'when hydrogen chloride is passed into an ethereal solution of thepreceding compound ; this salt is stable in dry air, but in a moistatmosphere i t is quickly converted into the glyoxime with elimina-tion of hydrogen chloride. This glyoxime is also formed when iso-nitrosoacetophenone is treated with hydroxylnmine hydrochloride indilute alcoholic solut,ion ; it crystallises in well-detined prisms meltingat 180".It is stable in acid solution, but it is very readily con-verted into its isomeride (m. p. 16Sa) by most ordinary neutralsolvents, except ether, from which it cr~stallises unchanged ; itrefiernbles its isomeride very closely in appearance and in properties,but differs from i t as regards melting point.The diacetyl derivative, Cl5Hl2N2OJ, is formed when either of thoglyoxirneb: described above is treated with acetic anhydride at O", buta slight difference in the behaviour of the two compounds, as regard322 ABSTRACTS OF CHEMICAL PAPERS.the rapidity of solution, is observed. It cryFtallisea in well-defined,highly refractive prisms, melts at 93", and is readily soluble in mostordinary organic solvents, except etlier.?H:N>O, is formed when theCPb:NPJt en y 1 azoxazol e ( p heny lfurazan),diacetyl derivative is kept in contact with sodium carbonRte until i tis completely converted into an oil, and also, but only slowly and to FLlimited extent, when either of the glyoxirnes or the diacetjl deriva-tive is distilled with steam ; i t is best prepared hy precipitating a nalkaline solution of the glyoxirne with carbonic anhydride, andextracting the precipitate with cliloroform (see below).I?i crystal-lises from dilute alcohol in needles, melts a t 30" (36"?), is volatilewith steam, and volatilises very readily at the ordinary tempernt ure -it is insoliible in water and cold alkalis, b u t very readily soluble inether, chloroform, and benzene, end it dissolves unchanged in concen-trated sulphuric acid.Phenylvximidoacefonitrillp, NOH:CPhGN, is formed when phenyl-nzoxazole o r the diacetyl derivative (m.p. 92") is warmed with sodaor sodium carbonate, and also when phenylglyoxime is boiled withsodium carbonate ; when the glyoxime is boiled with soda, i t is onlyvery slowly converted into the nitrile. Phenyloxirnidoacetonitrile isalso the principal product (50 per cent. of the theoretical) of theaction of hydroxylamine 011 dibromacetopheiione in alkaline solution,a fact which was overlooked by Strassmann and by Schramm. Itci-ystztllises in plates, melts a t 128", dissolves freely in hot water andiu the ordinary organic solvents, arid is not volatile with steam; it isnot hydrolysed by boiling, concentrated hydrochloric acid, and whenheated with concentrated soda, it is only very slowly converted intophenyloximidoecetic acid, with evolution of ammonia.The a c e q lderivative, NOAcXPh-CN, prepared by boiling the nitrile, or eitherof the gljoximes, with acetic anhydride, separates from dilute alcoholin well-defined, rhombic crystals, melts a t 68", dissolves freely in allordinary solveiits, and is decomposed by soda, yielding the nitrile.The following observations Doint to the existence of a third u I R'H. Ph- c ----&OH OH-Nglyoxime, which is probably pkenylsynglyolm'me,When eit,her of the qlyoximes described above is dissolved in Podn,and carbonic anhydride passed through the solntion cooled to -lo",a precipitate, containing about 3:3--3t3 per cent. of the theoreticalquantity of phenylazoxnzole, is produced ; after extracting t,his COT-pound by shaking with chloroform, there remains undissolved a sub-stance which melts at 148-154"; this, on being dissolved in a verysmall quantity of acetic anhydride, yields an oily product.Whenthis oil is distilled with water, it yields in the first few minutes a farlarger quantity (above 51 per cent. of the theoretical) of phenylazox-u o l e than is obtained in the same time from either of the glyoximes,or from the acetyl derivative (m. p. 92") described above, and thenthe rate of formation of this compound quickly diminishes ; this oilis also very quickly converted into phenylaxoxazole on treatment withcold soda, whereas the diace tyl derivative yields phenyloximidoacetoORGANIC CHEMISTRT.323nitrile under the same conditions. These facts seem to show that theprecipitat,e produced with carbonic anhydride consists principally o Ephenylrtxoxa~zole, and contains, in addition, a plienylglyoxime whichdiffers from the other two compounds in properties, and probablyhas the configurahion given. above.No evidence of the existence of the fourt,h theoretically possibl,:isonieride was obtained. I?. S. K.Action of Nitrous Acid on Bensenylamidethoxime. By F.TIEMAKN (Bey.. 24, 3453-3433 ; compare Tiemann and Kruger,Abqtr., 1884, 1325 ; 1885, 790).-The author finds that when sodiumnitrite is added in molecular proportion to a solution of benaenylamid-(.thoxime acidified with a mineral acid or a strong organic acid, thecharacter of the product depends on the acid employed.Benzenyi-et,hoxime chloride (Zoc. cit.) is formed in tho presence of hydrochloricacid.Benspnylethorinze bromide, CPhBr:NOEt, is obtained by dissolvingthe smidethoximc (1 mol.) in liydrobromic acid (2 mols.), cooling,crtutiously adding a solution of sodium nitrite (1 mol.), gently heatinga t 40" until the evolution of nitrogen cexses, extracting with ether,and, after evaporating the solvent, distilling in a partial vacuum ; i tis an oil, insoluble in water, but readily soluble in alcohol and ether,and boils a t 150" (45 mm.).Beizzenylethoxinze nEtrtfe, NO,*CPh:NOEt, is formed when a solutionof the arnidethoxime (1 mol.) in dilute snlphuric acid is treated withsodium nitrite (2 mols.) in the cold.It is an oil of little stabilitj,which dissolves in hot alkalis with decomposition, and is quickly con-verted into benzoic acid and ethoxylamine by hydrochloric acid ;when i t is sbaken with cold potassium hydroxide solution and cnrh-onic anhj dride passed through the solution, ethyl benzhydroxamaLe isf orrried.Beiizen ylethoxime acetate, OA c*CPh:NOE t, is prepared by dissolvingbenzenj lamitiet hoxime in conceri trated acetic acid, adding sodiu i t 1nit1 itc solution a t the temperature of the room, carefully neutralising,and extracting with ether ; it is an oil which does not solidify decom-poses into phenyl isocyanate on distillation, undergoes partial decom-position OIL boiling with water, and is readily soluble in alcohol andether; when carefully warmed with a solution uf potassium hgdroxidein dilute alcohol, the potassium derivative of ethyl benzhydroxamatcis obtained.A. B. IA.Dyeing with Aniline-black in the Dry Way. By S. GRAWITZ(Compt. rend., 113, 746--747).-1t is well known thRt dyeing withaniline-black in the dry may seriously weakens the fibre, and thatthis resuit cannot be avoided by using a neutral salt of aniline.According to Nietzki, aniline-black is a monobasic tetramine, and,if this be so, its formation will be represented by the equation4CsH,N,HCl + 4 0 = C24H20N4,HC1 + 3HC1 + 4HE,0.The hydro-gen chloride liberated in conbact with the dry cellulose converts iti n t o hydrocellulose and weakens the fibre. The remedy lies in addingacetates, o r other organic Palts of the alkalis o r alkaline earths, t 324 ABSTRACTS OF CHEM[CAL PAPERS.the mixture for producing the black. Roechlin has stated that thepresence of acetates prevents the formation of the black, but theaiithor finds that this is not the case wheu the quantity of acetateadded contains less than one equivalent of base for each equivalent OEacid present in the form of aniline salt. Half an equivalent givescomparatively little protection, Gut the maximum benefit is obtainedwith a quantity of acetate equivalent to three-fourths of the anilinesalt present, a result which supports Nietzki's view, according towhich three-fourths of the acid in the aniline salt is liberated in theprocess of oxidation.Thiophenylcarbamides.By S. PASCHEOWEZKY (Ber., 24, 3492).-The author has received a private communication from Bernthsen,in which he points out that the differences in the melting points1 ecorded for thiodiphenylcarbamide chloride and dithiotetraphenyl-carbamide by Paschkowezky (this vol., p. 164)) and by Frankel(Abstr., 1885, 1130), are due to the latter having neglected to correctthe values he obtained.C. H. B.A. R. L.Action of Potassium Cyanide on Halogen Derivatives ofKetones, By A. OBR~GIA (AnnaZen, 266,324-358) .--The potassiumderivative of cyanacetophenone is formed, with evolution of hydrogencyanide, when bromacetophenone (1 mol.) is treated with potassiumcyanide (2 mols.) in dilute alcoholic solution ; after evaporating thealcohol and taking up the residue with water, the filtered solution isacidified, and the precipitated cyanacetophenone recrystallived fromboiling water.The yield of pure cpnacetophenone (m. p. 8O-8lY)is 64 per rent. of the theoretical; its aqueous solution has a.n acidreaction. The sodium derivative crystallises i n small, nacreous plates,is readily soluble in alcohol, and is only slowly decomposed by carbonkanhydride ; the ammonium derivative is unstable ; on treating a solu-tion of the sodium derivative with metaliic salts, the correspondingmetallic derivatives are precipitated. The hydrazone separates fromalcohol in almost colourless crystals, melts at 134-135" with previoussoftening, and is very readily soluble in ether and chloroform, but onlymoderately easily in cold alcohol, a d insoluble in cold water.A compound of the composition C9H,N20 is formed when an alkalinefiolution of cyanacetophenone is treated with hydroxylamine at theordinary temperature ; it crystallisev in colourless, lustrous, rectangularplates or short needles, melts a t 110-112", and is readily solnble inchloroform, alcohol, benzene, ether, and acetone, but almost insolublein light petroleum, cold alkalis, and conceiitrated ammonia ; it has aneutral reaction, and crystallises uncbanged from hot soda.'I'hehydrochloride melts at 98-100" ; the sulphate decomposes at 169-173",and is resolved into its components by cold water. When boiled withdilute acids, it yields ~cyanacetopher~one and phenylisoxazolone ; thelast-named compound is also formed when an alcoholic solution ofcyanacetophenone atid hydroxylamine hydrochloride is kept for R longtime. It will be seen that the conipound just described does not showall the properties of a true oxime ;*its coktitution is probably repre-sented by the formula >NH.?H,-COCPh : OHQ AN10 CHEMISTRY.32 5Benzoytacetantide, CH, BzCOmRH2, is ohtained when cyanaceto-phenone is treated with concentrated sulphuric acid at the ordinarytemperature, and, after keeping for about 48 hours, the product pre-cipitated with ice ; it crptallises from hot water in lustrous needlesor prisms, melts a t 111-113", and is almost insoluble i n lightpetroleum, and only moderately easily soluble in benzene and ether,but readily in alcohol, chloroform, acetone, alkalis, and ammonia ; ithas a neutral reaction, and its solutions give an intense violet colora-tion with ferric chloride.It is decomposed by boiling alkalis withformation of ammonia, acetic acid, and benxoic acid, and when heatrdalone or with water, it yields carbonic anhydride and acetophcnone,The hydrazone crystallises from dilute alcohol i n yellowish neediep,melts a t 128-130", and is soluble in ether. When benzoylacetamidais treated with hgdroxylamine hydrochloride in alcoholic or ammonia-cal solution, it is converted in phenylisoxazolone.The crystalline compound (m.p. 179-180") obtained by treatingchloracctone with potassium cyanide in aqueous solution (compareHantzsch, Abstr., 1890, lU94) has the molecular formula C,H,,NaOz,as was proved by molecular weight determinations, by Raonlt'smethod, in glacial acetic acid solution, and its constitution is prob-ably that of a p-)neth~lhydroxy-y-cyanacetobutyronitrile,CN GHAcm CMe (OH) .CHX.CN.C Me (0 H) . $: H,Hy &ox y h y drocy ano nze8itenelacton e, C N-CGCMe- o- , thed r i l e of hydroxylhydroisodehydracetic acid, is obtained when the crystal-line compound (m. p. 179-180') just mentioned is dissolved in verxdilute sulphurio acid ; it crystallises from hot water in colourless,lustrous needles, melts at 65", and is very readily soluble in alcohol,chloroform, benzene, acetone, and boiling water, but only moderatelyeasily in ,ether, and almost insoluble in light petroleum.Its aqueoufisolution gives, with ferric chloride, first a brownish, and then tt violet,coloration ; the freshly prepared solution in dilute alcohol has only avery feebly acid reactiou, hut after keeping for some t,ime the acidityincreases very considerably. It dissolves unchanged in cold, con-centrated acids, and also i n alkalis, ammonia, and alkali carbonates.The bromo-derivative, CBH6BrNO9, can be prepared by treating thelactone or the crystalline compound (m. p. 179-180") with brominein alcoholic solution ; it crptallises from dilute alcohol in slender,lustrous needles, melts at 98-100", and is readily soluble in benzene,chloroform, ether, alcohol, and boiling water ; its aqueous solutionhas an acid reaction, and only gives a slight violet coloration withferric chloride after having been boiled.6-Hy drox!/-y-acetoisoual~r~c acid, C HzAcm CMe( 0 H) GHz- C 0 0 H, isformed, with liberation of carbonic anhydride, when the lactone isboiled with barium hydroxide until the evnlution of ammonia is a t auend ; it irc a thick, yellow, odourless liquid, readily soluble in water,alcohol, and ether.The phenylhydrazone is an oil; the paratolyl-hydrazone is a yellowish, very unstable substance, and decomposes a t81-85". The barium salt is a yellowish, amorphous powder, readilysolubh in water and alcohol; it seems to have the compositio32 6 ABSTRACTS OF CIEMICAL PAPERS.(C7Hl,04),Ba + C7H,(,0,Ba.The silver salt, 2C,H,,O,Ag + Ci.H,,,04Ao, + H20, is very unstable, and very readily soluble in cold water. Thecopper s d t is a green, vitreous, hygroscopic s i i bstance.A compound of the composition C,H,,N,O, + SH,O is obt,ainedwhen hydroxjhydroc-jxmomesitenelactone is treated with hydroxyl-ainine in very dilute alkaline solution, and the precipitate recqst a'-lised from boiling water, from which it separates in colourless, lustrousneedles; it slowly loses the whole of its water over sulphuric acid,the anhydrous crystals decomposing a t 184-185". I t is very spar-ingly soluble in ether, acetone, light petroleum, and cold water, butmore readily in alcohol, chloroform, benzene, and boiling water ; it3aqueous solution has a pronounced acid reaction, and gives, withferric chloride, a brownish-violet coloration.This compound is prob-nbly the lactam of P-methjlhydroxy-yacetoxitne-A-isonitrosoamido-valeric acid. and its constitution may be rewesented bv the formula YF. S. K.Action of Amrr onia and Aniline on Halogen-substitutedNitrobenzoic Acids. By A. G ROHMBNN (Bey., 24, 3808-3815).-I n a previous communication (Abstr.: 1891,305), the author has skownt h a t the halogen in, the etliyl salt, amide, and anilide of 4 : 3-bromo-nitrobenzoic acid may be readily replaced by the amido- and anilido-groups ; in the present paper h e describes similar experiments madewith 2 : 5-bromonitrobenzoic acid.2 : 5- Brornonitrobenzoic chloride, NO2*C6H,Br.COCI, is readily ob-,tained by the action of phosphorus pentnchloride on the acid, andcrystallises from alcohol in greSish crystals melting at 63".l'hca x i d e , No2*C6H3Br*CONH2, is prepared from the chloride by warm-ing wit8h ammonium carbonate on the water-bath, and crystallisesfrom alcohol in white, lustrous needles which melt at 197-198 ;the anilide, Ko2*c6kT3Br*cO*NH Ph, obtained by gently warming tlwchloride with aniline, forms yellowish- white, acicular crystals, andmalts a t 166"; both compounds are soluble in alcohol and acetonc,and insoluble in water and benzene.When ethyl 2 : 5-bromonitrobeneoate is heated i n a sealed tube withalcoholic ammonia, i t is converted into ethyl 'L : 5-nniidon.;trobenroate,NO,*C,H,(NH,)*COO~t, which crjstallises from alcohol in pale-yellow needles melting at 148".If aniline be substituted for ammonia,the corresponding ethyl 2 : 5-anilidoi~itrobenzoate is obtained ; it sepa-rates from alcohol in small, yellow plates, and melts a t 118". Thcamide and anilidc above described also readily react with ammoniaand anilire respectively, forming the cori*esponding amido- a danilido-compounds. 2 : 5-Amidonit.1.obenztlmide,NO,*C,H,(NH,)*CONH,,crystallises in orange-yellow needles, and melts at 230" ; 2 : 5-andido-nitro benzanilide, N 0,*C6H3( N H P h) *CO.NH P h, separates from alcoholin tuf'ts of very slender, yellow needles, resembling silk fibres, andmelts a t 159".ft : 4-Chlol.onitrobeizzo;c chloi-ide is prepared from the acid in thORGANIC UHENISTRT, 32 7usnal manner, and is a yellowish-brown sabstance melting a t 115".I t is converted by ammonium carbonate and aniline respectively intothe arnide and anilide; the former crystallises from alcohol in greyscales, and melts at 172", whilst the latter is a white, amorphons snb-stance melting a t 168".In these compounds, unlike the 4 : 3- an(12 : 5-compounds, the halogen cannot be displaced by further heatingwith ammonia or aniline. The same is also true of 4 : 2-chEoroizitro-benzoic ucid, which was prepared by displacing the amido-group in3 : 2-amidonitrotoluene by chlorine and oxidising the chloronitro-toluene thus obtained.From these resuits, it appears that when the nitro- and carboxyl-groups are simultaneously in the ortho- and para-position relatively tothe halogen, the latter.may be readily displaced, but that this isno longer possible when one of these groups takes up the metit-position.To his preyious commniiication on 4 : 5-bromonitrobenzoic acid(Zoc. cit.), the author adds that this acid is converted by alcoholicrimmonia a t 170" into fhe 4 : 3-arnidonih*obenzoic acid described byGriess (Ber., 5, 855) and Salkowski (Annalen, 173, 53).H. G. C.Oximes of some Ketonic Acids. By F. GARELLI (Gazzefta, 21,ii, 173-188).-1n a previous memoir (Abstr., 1891, 711), the authoryeported his inability to prepare the oximido-compounds of dioxy-nietJh~lenephenylglyox~lic acid, apionylglyoxylic acid, and para-methoxpglyoxylic acid ; he has, however, since succeeded in preparingthem, and finds them to be very unstable, readily losing the elementsof water and carbonic anhydride, and yielding the correspondinkiiitriles.Methyl diozyrnet7~ylenephenylglyox~late, CH2<O>C6H,-CO*COOMe, 0is prepared by saturating a solution of dioxymethylenephenylgly-ovylic acid in methyl alcohol with dry hydrogen chloride.Thoalcohol is distilled off and water added ; the salt sephrates as an oilwhich soon solidifies, and is crystallised from dilute alcohol. Smallcolourless needles, melting at 66", soluble in alcohol an4 ether, and:tlmost insoluble in water, are t h u s obtained. The alcoholic solutiono f this ethereal salt is treated with a slight excess of hydroxylaminehydrochloride and heated in a reflux apparatus on the water-bathfor t w o hours.The alcohol is distilled off, the residnal oil dis-solved in dilute potash, filtered from a small quantity of piperonyl-nitrile, and the solution saturated with cwbonic anhydride ; methyldioxynzethylenephemjloximidoacetate is. then 'thrown down, and OTIrepre~ipitation from its solution in benzene, by the addit.ion of lightpetroleum, is obtained in tufts of small crystals melting withoutdecomposition :it 102". This substance is soluble in water andnlcohol, and on hydrolysis with dilute potash a t a temperature belowGOo, yields diozymethylenephenyloxinzidoacetic acidas a whiteish mass ; on precipitation from its acetic solution by ligh328 ABSTRACTS OF CHE-\IICAL PAPERS.petroleum, it may be obtained in minute rrystals, soluble in sodiumcarbonate solution, alcohol, ether, benzene, and water.It melts wit t:decomposition a t 150-151", and its aqueous solution gives whiteprecipitates with lead and mercury salts and a green precipitate withcopper acetate in concentrated solutions. This acid may also be pre-pared by heating a dilute solution of dioxymethylenephenylglyoxylicacid at 60-70" with the calculated quantity of hydroxylaminehydrochloride. It, is readily converted into piperonylonitrile by pass-ing a, current of dry hydrogen chloride into its ethereal solution ; theconversion also proceeds spontaneously in dilute aqueous solutions,and is hastened by the presence of acids or of hydroxylamine hydro-chloride. The acelyl derivative is obtained on heating it with aslight excess of acetic cliloride ; on cooling, colourless, rectangularprisms separate, melting with decomposition at 139-140".Whenhydrolysed at 0" with dilute potash and extracted with ether, theoxime is regenerated; at. higher temperatures, the nitrile is theprincipal product of the action.Compounds analogoils to those of dioxymethylenephenylglyoxylicacid may be prepared from apionylglyoxylic acid by the same0 met hod s . Met h y Z apiony Zg I! y ox y late, c H,< > C6H ( OMe) 2* C 0 C 0 0 Me,crys t.allises from dilute alcohol in needles melting at 62" ; it is very sol-uble in alcohol and ether, sparingly in benzene, and insoluble in water.minute, colourless crystals melting at 129" without decomposition ;on hydrolysis, it yields opionyloximidoacetik acid in splendid, whitescales, very soluble in alcohol, spariiiglp in boiling water, less so inbenzene, and insoluble in ether. I t s aqueous solution gives no pre-cipitate with salts of lead, copper, or mercury.No acetyl derivativecould be prepared.Yuramet huxyp hevr ytoxirnidoacet ic acid, 0 Me* CsH,*C (KO H ) fi*C 0 0 H,is prepared from pa~*amethoxyphei~ylglyoxylic acid in the manneritidicated above, and separates from ethyl acetate in large, colourlesscrystals, very soluble in water, alcohol, and ether; it melts a t145-146" with couiplete decomposition. T tie a-oximido-acid cannotbe prepared by carrying out the reaction a t 0". On Iieat,ing withacetic anhydride or acetic chloride, a small quantity of an acetylderivative is obtained.It me1 ts with complete decomposition a t118", is decomposed with formation of anisonitrile by cold solutionsof the alkali carbonates, and on hydrolysis a t U", yields only theoriginal p-oximido-acid.Giarnician aud Silber (Abstr., 1890, 965) found that isosafroleyielded piperonylic acid and dioxymethyleriephenylgljoxylic acid onwxidation with perrnanganate, the author finds that a small quantityof dioxymethylenephenylglycollic acid is also produced (30 grams ofisosafrole yield 0.5 gram of the acid). This acid is separated bymeans of its solubility in water, and melts at l56", not a t 152-153',as found by Lorenz (Abstr., 1881, 727).The ketonic acids obtained from safrole, anetho'il, metbyleugenol,and apiole, when dissolved in benzene and treated with thiophen iORQANIC CHEMISTRY.329concentrated sulphuric acid solution, impart an intense red colora-tion to the thiophen, the benzene solution remaJning colourless ; ondilution, the solution becomes successively violet, and dirty green.The solutions of these acids in phenol, when heated with conccntratedsulphuric acid on the water-bath, soon t n r n blue ; gas is then abund-antly evolved and the solution becomes r e d ; on pouring the productinto water, the colouring matter separates as a floccnlent precipitateinsoluble in water, but readily soluble in soda, arid in solutions of thealkali carbonates. A preen colouring matter is produced on heatingthe acids with dimethylaniline and zinc chloride.Derivatives of Mesitylene.By E. FEITH (Ber., 24, 3542-3545 ; compare Claus, Abstr., 1890, 979, and Dittrich and Mejer,Abstr., 1891, 12d4).-The air-dried barium salt of mesi tylglyoxylicwid contains 3 mols. B20, of which it loses two over sulphuric acid.The zinc salt, with 4H20, crystalliscs in lustrous plates and loses3 mols. H,O over sulphuric acid. The methyl salt, C12Hlr03, hoils a tabout 170" iinder a pressure of 1GO mm. When mesitylglyoxylic acidis heated, it is decomposed into trimethylbenzaldehyde and trimethyl-benzoic acid, the methyl salt of which crystallises in colourless platesmelting at 139-140".~rimeth?/Zben~atdehyde, C6HzMe3*CH0, is an oil, boils at 235--240",and gradually oxidises on exposure to the air ; its oxime,C6H&f e,*CH:NOH,crystallises in small needles, melts at 127", and dissolves freely inalcohol, ether, and alkalis ; its hydrazone, C,H,Me,*CH:N,HPh,separates from dilute alcohol in colourless crystals, and is very un-stable.MesityZgZyco7Zic; acid, C6H,Me3*CH(OH)*COOH, prepared by re-ducing mesitylglyoxylic acid with sodium amalgam in alkaline solu-tion, crystallises from water in large, well-defined, transparent plates,melts a t 147", and is readily soluble i n alcohol and ether, but onlysparingly in cold water.The silver salt, CI,HI3O3Ag, is amorphous.The nzethyt salt, C,2H1603, prepared from the silver salt, separatesfrom light petroleum in colourless, - nodular crystals, and meltsW. J. P.when the acid is heated a t 120-130" f o r two days with anhydrouschloral ; it crystallises from light petroleum in well-defined plates,nielts a t 125", and is readily soluble in benzene, chloroform, andether, but more sparingly in alcohol.By F.ALDKIxGEN (Bey., 24,3 i.jg-3466).-'l'ieniann has shown (Abstr., 1886, 880) that tbio-cournarin is formed when coumarin i s fused with phosphorus penha-sulphide. The object of the present work was to examine thebehaviour of certain homologues of coumarin and of some otherF. S. K.Thiocournarin and its Analogues.6- lactones.CH'CMecr-JIet7c ylthioeoumarin, CGHH,<oibs is prepared by heatin330 ABSTRACTS OF CREYICAL PAPERS.a-methyl-coumarin (m. p. 90") with phosphorus pentasulphide, boilingthe melt with benzene, crystallising from absolute alcohol, and washin<the crystals with carbon bisulphide ; i t forms yellow needles, melt3a t 12i?", sublimes without decompositlion, and is insoluble in wateiaand light petroleum, b u t xadily soluble i n alcohol, ether, antibenzene ; it yields m-met,hylcoumarin on boiling with alcoholic pot,ash.CH:FMea-lkIethylcoumaroxime, c~H4<<0--c:.0H7 is formed when the a-methylthiocoumarin is boiled with hgdroxylamine i n alcoholic solo-tion ; i t crystallises from water or dilute alcoliol in coluurless needlw,and melts at 166".Ferric chloride does not. give a coloration as withcoumaroxime (see Tiemann, Zoc. cit.), atid t h e same is true of thehomologous compounds to be described ; they are also without acttionon Fehling's solution.It dissolves in alkalis amd acids, is stabletowards the former, but yields a-methylooumarin when boiled withconcentrated hydrochloric acid ; the acetyl derivutive,CH:? MeC6H'<O-N~OAc,obtained by dissolving t h e osime in an excess of warm acetic chloride,is produced by melts at 56". The hydrazone,CH:yMeC"H'<O-C:N,HPh,boiling a-methylthiocoumarin with pbenylhydrazine in alcoholicsolucion for about a week; i t crystallises from alcohol i n yellowi,eedles, melts at llG", is irisoluble in water, and dissolves in con-centrated salphuric acid with an inteiise green colour.The following derivatives of a-ethylcoumarin (in. p. 71") wereprepared in a similar manner t o the methyl compounds :-u-Eth!/l-ihiocounlal.i?z forms small, y.ellowish-red plates, and melts at 93-94O ;a-ethyZcoumai.oxi~ze crystallises i n long, white needles, melts a t 157",and yields an acetyl dericatise melting a t 61" ; whilst a-ethy1coumai.o-phenylhydi*azone melts a t 115".Derivatives of a- Isopropylcoumarin (m.p. 54") .-a-TsopmpyZt!iio-eoumarirc forms reddish-yellow needles, arid melts at 81" ; a-isopiwpyl-ihiocoz~ircaroxime crjstallises in white prisms, melts at 171", and yieldsan acety 1 derivative mrlting at 85" ; whilst a-isop~o~ylcoz~nzarop~~en~l-hydraxclne melts at 7 12".Derivatives of Metlrylumbellifei*one (m. p. 7 14").-Urnbelliferoneis not readily converted into the thio-derivative by fusion withphosphorus pentasnlphide, whereas the niethjl derivative exhibitsthe same behaviour as coumarin. , 1Methylthioumbell~fe~one, OMe*CGHZ< CH:FH, forms yellow needles,4 0-cs 3melts at 114", and dissolves in boiling alkalis with decomposition.N e t h yluiii brlliferonozin? e crys t alli ses from water i n long, feltedneedies, melts at 138", and gives a brownish-red colour with ferricc h 1 o r i d e ..Me f h y Zu 11 I be 11 lye r o ti ep he 11 y 1 h y d r a x I ) ne i s obtained by b o i 1 i 11 gjor a fortnight a mixture of methyl thioumbelliferone with pbenjl-hjdrazine in molecnlar proportion, dissolved in alcohol ; it cryst alliseORGANIC OEE3IZSTRY. 331fiom alcohol in thick, yellow needles, melts at 115", and dissolves i ncoucent rated sulphuric with a bluish-green colour.Action of Ammonia and Aniline on Negatively-substitutedHalogen-benzenesulphonic Acids.By P. FISCIIER ( B e y . , 24,3785-3808).--lt was found t h a t in the case of the two chloronitro-benzenesulphonic acids NOz*C6B3C1*S0,H [Cl : NO, : SO,€€ = 1 : 2 : 4and 1 : 4 : 2 respectively], the two bromosulphobenzoic acidsCOOHmC6H,Br*SOJH [Br: COOH : S03H = 1 : 2 : 4 and 1 : 4 : 2respectively], and bromobenzenedisul phonic acid, C,H,Br( SO,H),[ H r : (SO,H), = 1 : 2 : 41, the action of ammonia or aniline is tod i s p l a ~ e the halogen by the amido- or anilido-group. I n all of theseacids a para- and an ortho-position, relatively to t h e halogen atom,aye occnpied by negative groups.2ll~tnnitro~aramidobenzenesul~~~onic acid, NHZ.C6H3(NOL)*SO3H[I 1 : 2 : 41, is obtained as the ammonium salt by heating metanitropam-c*hloroberizenesulphonic acid with alcoholic ammonia at 120-140".The barivnz salt, (C6H,N,SO,),Ba + 2$H20, forms yellow crystals ;the acid itself forms an amorphous, yellow precipitate.When heatedwith concerltrated hydrochloric acid at 150", t h e sulFhonic groiip isremoved, and orthonitraniline is formed ; this proves that the NO,group and the chlorine atom in the original nitrochlorosulphonic acidoc.cupy the ortho-positions relatively to each other. Paramidometa-1~1frol,enzenesiiZp~onamide, NII,.C,H3(N0,).SOz.WHz [ 1 : 2 : 41, is ob-t ;tined by heating paraclilorometanitrobenzen esulplionamide mi t tialcoholic ammonia at 120". It crystallises from alcohol or water iudeep yellow needles or lustrous, golden plates, melts at 2Oti-207",and is such a feeble base that i t forms no salts with acids.Metatiitro-orthamidobenzenesulph~~~ic acid [NH, : NO, : SO,R =1 : 4 : 21 was obtained in the same way a s the isomeric acid.Thebarium salt, ( C6H,N,S05),Ba + H,O, forms yellow crjstals. The acidit,elE crystallises from water in sinall, yellow crystals, and yield3)mraphenylenediaminesulphonic acid, C,H,( NH2),.SOJH, on reductionby CIaisen's method. Its sulyhonnmide forms yellow needles or platesmelting a t 210".With parachlorometanitrobenzenesul phonic acid, aniline jieldsa11 aniline salt, NO2.CbH3CI*SO3.NH3Ph [= 2 : 1 : 43, in lustrous,white crj-stals. Tklis, when heated with excess of aniline, yields theanil iite salt of nzetaiaitro~aranilidobenz~nesul~honic acid,N0,*C6H3(NHPh)*S03*NH3Ph [= 2 : 1 : 41,which forms large groups of yellowish- brown needles, and dissolves inalcohol, acetic acid, acetone, and hot water, but not in ether or benzene.The bariiinz salt, (C,,HSN,SO,),Ra + H 2 9 , forms lustrous, dark golden])kites. The acid forms orange-coloured crystals, decomposing at 200"without melting, and dissolves readily in water, alcohol, acetic acid, andacetone, but not in benzene and ether.The alkali salts, C,,H,N,SO,Na, + HzO, kc.. are 01-ange-yellow, but at 110" lose wbter and becomcbrick-red ; tlip anhydrous sHlt$, however, take up water from the air,becoming again orange-yellow.A. R. L.The ammonium salt,C12HgX\TZ$Oa*NH* + +HAO332 ABSTRACTS OF OHEMIOAL PAPERS.forms lustrous, yellow plates.By the action of phosphorus penta-chloride on the acid, the sulphochloride is obtained ; it crystallises fromether in yellowish-brown needles, aiid with ammonium carbonate yieldsthe sulphonamide, RS lustrous, red crystals melting a t 162". The yulph-nnilide is best obtained by the action of aniline on the chloronitro-benzenesul phonic chloride ; it forms long, orange-yellow needles, meltsat 157", and dissolves readily in alcohol, acetone, and acetic acid.Paranilidometaniidobenzenes2dlphonic acid, NHPh*C,H,(NH,)-SO,H[=1 : 2 : 41, is prepared by reducing the barium salt of the corre-sponding anilidonitro-acid by Claisen's method ; it forms a crystallineprecipitate, which darkens in the air and gives a violet-red colourwith ferric chloride.The barium salt, (C12H,,N2S0,)2Ba + 2Hz0,forms tiny, brownish needles. The sulphanilide, prepared by re-ducing the corresponding nitrosnlphanilide with alcoholic ammoniumsulphide, forms colourless, lustrous needles melting at 157", and givinga, deep violet colour with concentrated snlphuric acid. The hydro-chloride forms white needles melting at 181-182" with decomposi-tion. Metanitroparanilidobenzenesulphonic acid yields orthodinitro-d iphenylamine when heated at 130-1 40" with concentrated hydro-chloric acid. By adding potassium nitrite to an acetic acid solutiono€ this base, orfhoizitrodiplzenylniti.osamine, N02*CsH4.NPh*N0, is ob-tained. It forms nearly colourless plates melting at 99-100"; i tdoes not give Liebeymann's nitrosamine reaction with phenol andsulphnric acid, but yields a deep violet, and not a deep blue, colour.Ort hochlorom et ani tro ben zenes ul ph onic acid yields.with aniline, theaiziline salt, which forms long, lustrous, white needles, decomposingabove 200" without melting. When heated with aniline, this yieldsmrtanitro-ol.tha?zilid~ benzsnesulphonic acid, as the aniline salt, in large,brown needles with zt violet lustre ; i t dissolves in water, alcohol, andacetone, but not in cther or benzene. The barium salt,forms lustrous, orange needles. The acid itself crystallises in small,lustrous, olive-green plates. The potassium salt forms anhydrous,orange needles, and with phosphorus pent>ach loride yields the sulph-onic chloride, as greenish-yellow needles melting a t 102-104" andreadily soluble in ether, benzene, and chloroform. With ammoniumcarbonate, it yields the szdphonamide, which separates from alcoholi n reddish-yellow crystals melting a t 173", and insoluble in water.The sulplinnilide was obtained from aniline and the chloi*onitrosulph-onic chloride ; it crystallises from alcohol in lustrous, greenish-yellow11 eed 1 es melting a t 164".Orth anilidometamido benzcnesulp/ionic acid,NHPh*C6H3(NH2)*S03H [= 1 : 4 : 21, is obtained as the barium salt,(CI,H,,N2SOa)2Ba + HyO (lustrous, silver-grey plates), by reducingthe barium salt of the corresponding nitro-acid by Claisen's method.I t yields highly-coloured oxidation products ; for example, with ferricchloride, it gives a red colour passing into violet.The acid formsdark-coloured plates. The sulphnnilide, obtained by reducing t h ecorresponding nitrosulphanilide with alcoholic ammonium sulphide at1.10-130", forms lustrous pIates melting a t 171", and gives a violetcolour with strong sulphuric acid. I t s hydrochloride blackens a t 200°ORGAN I0 0 H EBIISTRY. 333rind melts with decomposition a t 215", niid gives an olive-green colourwith ferric chloride.P a r a m idomet asiclphobenzoic acid,NH2*C6H,(S03H)*COOH [l : 2 : 41,is obtained as the diammonium salt by heating the correspondinqhromosulphobenzoic acid with alcoholic ammonia at 160- -180". Tliebnrizbm salt, C,H,NSO,Ba + 2H20, forms large, colourless cr.ysta1.1,the pofassium salt anhydrous, transparent needles. The acid itselfcrystallises from water in slender needles.Parabromometasulplio-berizoic acid yields with aniline the aniline salt, which crystallisesfrom wat,er in long, lustrous, white needles, decomposing above 200"without melting, and when heated with aniline yields the aniline saltof paranil icEumetasulph,,henzoic acid, N H Ph.ChH3 (S 0,H) * C 0 O*NLT,Ph.The barium salt, C,JHgNSO,Ba + 3$H20, with sulphuric acid, yieldsthe free acid as small, lustrous, nearly colourless plates,Orthohromoinetasulphobcnzoic acid, S03H-C6H3Hr*COOH [ A : 1 : 21,was prepared by treating orthobromobenzoic acid (obtained by oxidis-ing orthobromotoluene) with fuming sulphuric acid. When heatedwith xlcoLlo1ic ammonia at 160-180", it yieltls the amrrionium mlt ofthe amido-acid.The barium salt, C,H,NSO,Ba + 2$H20, formscolourlejs crystals. With aniline, the bromo-acid yieltls an anilinesalt, and this, when heated with aniline in glycerol solution, yieldsthe aniline sctlt of orthadidometasulphoberlzoic acid,NHPh.CsHf,(S03H)*COO*NH3Ph [I : 4 : 21,in brownish plates.lustrous, yellowish plates.needle3 which decompose w itliout melting.The hnriunz suh, C13H,NS0,Ba + 5H20, forcrisThe acid crystallises irom water in fineAmidobenzenemelndistilphorric avid (disullphanilic acid),NH2*CsH.j(SO,H)2 [l : 2 : 41,was obtained as the neutid ammonium salt by heating the corre-sponding bromodisnlphonic acid with alcoholic ammonia a t 160-180".The amidodiszcl~honamide, NH2*C,H,(S0,*NH2)2 [I : 2 : 41, was ob-tained fkom ammonia and the bromodisulphonxmide.It crystallisesfrom water in lustrous, white plates melting at 235". The bromodi-sulphonic acid yields with aniline the diaitiline salt, which formstransparent, colourless plates soluble in water and glycerol, but notin alcohol. When heated with aniline in glycerol solution, it yieldsanilidobenzeneme fadisulyhonic acid ~ ~ ~ ~ p h ~ ~ ~ ~ ~ a r n i n e ~ r ~ h ~ p acid), which is ver.y soluble i n water, and could not be obtained crys-talline. The barium s d t , C,,HgNS,06Ba + 3H20, is a yellowish,amorphous substaiice. The disulphunilide is best obtained by heatiLgthe corresponding bromobenxenedianlphonic chloride with aniline. Itforms large, yellowish crystals melting at 821-222", and dissolvesreadily in alcohol, less readily in acetic acid, spariiigly in glycerol,and not at all in water.c. 1'. B.Acetoximes. By H. WEGE (Bey., 24, 3537--3540).-The acetyland the isobutyl derivatives of acetoxime were prepared from theoxirue by Hinsberg's method (Abstr., 1891, 49) ; they are both oils.VOT,. LXIL. 2 334 AUSTRAOTS OF OHEMIOAL PAPERS.Acetoxheplien y Isulphoize, CMe2:N* 0 S 0,P h, is easily obtained byshaking a concentrated aqueous solution of acetoxime with soda andphenylsulphonic chloride ; it crystallises from a mixture of ether andlight petroleum in long, colourless needles, me1 ts a t 52.5". and explodesa t 128", with formation of phenylsulphonic acid, ammonia, and smallquantities of nitrogen.Acetosimppuru toly lsulphone, C Me,:N.O S O,-C,H,Me, prepared in 1 i kemanner, crjstalliees from dilute alcohol in colourless scales, melts a t89", and decomposes a t 135" with a slight explosion.The correspond-i n g Pnuphth yl derivative, Cy3HYJNO3S, crystallises from alcohol incolourless or reddish plates melting at 87".When camphoroxime is shaken with soda and phenylsulphonicchloride, it seems to be converted into campholenonitrile. Benzo-phenoneoxime, under the same conditions, is converted into benz-anilide; a similar intramolecular change also takes place wheii thechlorides of paratoluenesulphonic acid and naphthalenesulphonic acidare employed in the place of phenylsulphonic chloride.F. S. K.Action of Sulphonic Chlorides on Orthamidobenzamide.By E. FRANKE (J. pr. Chma. [2], 44,417-432 ; compare Abstr., 1887,1043, 1044 ; 1890, 1289) .---Renzenesul phoneorthamidobenzamide(Abstr., 1890, 1289) is insoluble in cold water and light petroleum,but dissolves in alcohol ; it does not yield an anhydride when heatedwith water.Ethyl bewenesulphoneorthamidobenzoate, COOEt.C6H4*NH*SO2Ph,obtained by the action of ethyl orthxmidobenzoate (Abstr., 1885, 665)on beuzenesulphonic chloride, crystallises from aqiieous alcohol inwhite, quadratic prisms, melts a t 92.5", and dissolves easily in absolutealcohol, but not in water.When heated with aqueous ammonia a t140" for seven hours, or with alcoholic ammonia at 160" for 12 hours, itis converted into benzenesulphoneorthamidobenzamide ; with alcoholicmetbylamine at 140°, it yields benzenesulphoneorthamidobenzomethyl-amide (see below).The potassium and siker compounds of benzenesulphoneorthamido-benzamide are described, and the precipitates which the base givc swith several of the salts of the heavy metals are detailed ; the metalsdisplace 1 atom of hydrogen from a molecule of the amide.Theauthor retracts his former statements as to the obtaining of st hydro-chlol ide and methyl derivative melting at 116" from benzenesulphone-orthamidobenzarnide (Abstr., 1890, 1289).The author did not succeed a second time in obtaining an anhydrideby acting on beiizenesulphoneorthainidobenzamide with phosphoricanhydride, or by dissolving it in dilute sodium hydroxide solution andprecipitating by hydrochloric acid, or by heating it in alcohol a t210" (Abstr., 1890, 1289).Anhydrobenzenesulphoneodhamidobenz-is, however, readily obtained by heating amixture of benzenesulphoneorthamidobenzamide and phosphoric chlor-ide in molecular proportion, first at 60-?O", and finally at 175" ; themass is afterwards extracted with benzene, the solution precipitatedco*r;irr.N : SOPh' am&, C,H,OHGANIC OHEMISTRY. 335with water, and the compound recrystallised from dilute alcohol. Iticrystallises in pale yellow needles, melts a t 145", is very soluble it\alcohol and hot benzene, less FO in chloroform, ether, and water ; i talso dissolves in alkalis, and is precipitated unchanged by acids.When heated with concentrated hydrochloric acid, i t is decomposed,Its sodirm, silver, and potassium compounds were prepared.Benzenesub? honeorthnmido benzonz et h y lumid e,NHMe*CO.C,H'r*NH.SOzPh,is obtained as described above, or by heating anhydrobenzenesnlphone-orthamidobenzamide with potmsium hydroxide arid methyl iodide inalcohol iu a sealed tube at 120", or by bringing together orthamido-benzomethylamide and benzenesulphonic chloride i n molecular pro-portion.It crjstallises from aqueous alcohol in white needles,melts a t 114", and is insoluble in cold water and light petroleum, buteasily soluble in hot benzene, ether, and alcohol.NHz*C0.C6H4*NMe.S0zPh,is prepared by heating molecular proportions of orthomethamidobenz-amide (Ahstr., 1887,1044) and benzenesulphonic chloride together 011the water-bath; the new compound is extracted from the productby very dilnte alcohol, and recrystallised from hot benzene.Itforms beautiful, rhombic lamin=, melts at 154Q (uncorr.), and dissolvesreadilyin warm alcohol and in warm, dilute allrdis ; it is precipitatedunchanged from the alkaline solutions on the addition of an acid.Benzenesulphoneorthomet hamidobenzamide,Benzenesulphoneort hamido beiazop hen y lamid e,NH Ph*CO*C6H4*NH*S0,Ph,prepared from benzenesulphonic chloride and orthamidobenzophenyl-amide, crystallises in needles which melt a t 144-144.5". Renzenesulph-oneorthamidobenzoylphen!/lliydrazine, N,H,Pli*CO.C,H,*NH*SOzPh, wasobtained by heating benzenesulphonic chloride and orthamidobenzoyl-phenylhydrazine together a t 130 -140" ; the dirty-white needleswhich crystallised from water melted a t 140-142", but the yield wasvery small, and further investigation is needed.Methylsu7phoneorthamidobenzamide, NH2G O*C6Hd*NH*S0,Me, is ob-tained by the action of methylsulphonic chloride (b. p.160-161')on orthamidobenzamide ; it crystallises from hot, dilute alcohol inalmost white, very slender prisms, which melt at 156-157"; ananhydro-derivative could not be prepared.When sulphuryl chloride and orthamidoberizamide react, dichlor-anthranilamide, NH2*CO*CsHzCl2~NH2, is produced ; this crystallisesin dirty-yellow needles, and melts at 175-176" ; on hydrolysis, ityields Dorsch's dichloranthranilic acid melting at 223-225" (Abstr.,1886, 360). Dorsch, however, gives the melting point of the amidecorresponding with his acid as 284".Displacement of Halogen Atoms in the Benzene Ring.ByM. SCHOPFF (Ber., 24, 3771-3784 ; compare Abst'r., 1891, 304).-The general result of this research may be expressed thus:-If inA. Go B.2 a 336 ABSTRACTS OF CHEMICAL PAPERS.the benzene r i n g in which the halogen atom is contained there arealso t w o negative groups, like or nnlike, in t,he ortho- and para-positions relatively to this atom, then other groups, such as .NH,.NHR, and *OH, can easily be substituted for the halogen; but iFonly one negative group is present, no such replacement occurs,exccpt when this one group is *NO,. The negative groups may be*NO2, *SO,H, *COOH, *CO.R, or *COH.l'a7.abrc,,lornetanitrobenzophenone, NO,*CEH,Br.COPh [Br : NO, : CO= 4 : 3 : 11, is obtained by heating benzene with parabromometa-nitrobenzoic chloride in the presence of aluminium chloride.It formswhite plates melting a t 112-113", and dissolves easily in benzentb,acetone, chloroform, ether, and acetic acid, less easily in light petr-oleum. When heated with alcoholic ammonia a t 130", it yieldsparamidom etnnitrobenzophenoiie, N H2*C6H3 (N O,)*c)O Ph, a s small,yellow needles melting at 135", and dissolving very readily in water.IVith alcoholic cthylaniine, it yields yarethy1rrmidonaetanitrobertz.r~-p'renone, NHEt.C,H,( NO,)*COPh, as yellow needles melting at99-loo", and with aniline, parnnilidometanitrobelLxophe?LoiLe,N PH h*C6H3 (N 0,) *C 0 P h ,as orange-coloured needles melting a t 157".NO2*C6H3Br*CO*C6HIBr [Br : NO, : CO = 4 : 3 : 1 and CO : Br = 1 : 41,is obtained by warming parabromometanitrobenzoic chloride andbromobenzene with aluminium chloride in carbon bisulphide. Itforms needles melting at llS", and has the same solnbility as themonobronio-compound. With alcoholic ammonia at 130", it yiel(1sya?.amidomefanitroparabromobenzoph~none, NH2* C6H,( NO,) *CO*CsHIBr,as a, yellow substance melting a t 171".The corresponding crnilido-derivative, NHPh*CBH,(No,)*CO*C6H~Br, forms yellow needles melt-ing at MU".Diparabrom ometanitrobeizzophe?lolLe,Dzparabromodimetanitrobenzi yhenone,CO(C,H,Bi*NOL)2 [Br : (NO,) : CO = 4 : 3 : 11,is obtained by treating either diparabromobenzophenone or dipara-bromoruetanitrobenzophenone with fuming nitric acid.It formsneedles melting a t 152-155'. With aniline, i t yields diyarardidodi-i,ietanzt?.obenzophenone, CO [ C6H3(NOz)-NH Ph],, melting at 219".Urthobl.omo~ietanitroben zoyhenone, N02-CsH ,Hr- COPh, melting at115", was prepared in a similar manner to the isomeric parabrumo-compound, and resembles the latter in its chemical behaviour ; wit 11aniline, it yields ortlLanilidometanitrobenzoy henniie in lemon-colouredneedles melting at 135O.Parab7.omonnzefariilrobenzaEdehyde, NO,*C,H,Br.CHO [Br : NO, : CO= 4 : 3 : 11 (the aldozime of which, N02.C,H3Rr*CH:NOH, foimsyellow needles melting at 145-146', and dissolves readily in alcohol,less readily in water), when boiled with aqueous soda, yields para-hydroxymetanitrobenz/rldehyde, OH.C6H3(NOz)*CH0, which crjstallisesfrom Mnter in yellowish-brown needles melting a t 139-140 5".Thehydyazune: 0 H*CoH,( XO2)*CH:N2HPh, crys tallises from alcohol i n sruallORQAX IC CH-EAIISTRT. 337dark-red needles meltin,q at 175-1i6°. The aldehyde is identical withthe substance obtained by nitrating parahydroxybenzaldehyde.When asymmetrical bromoxylene, C6H3Me,Br [Br : Me2 = 1 : 2 : 43,is boiled with aqueous potassium permanganate, it is oxidised t otasy/umetricnZ bromisophthnlic acid, C6H3Bi*( COOH),, but a little asym-metrical hydroxyisop h thalic acid, OH*C,&( COOH),, is also formed.To separate these, they are converted into their ethereal salts, ofwhich that of the hydroxy-acid may be removed by dissolving i t indilute aqueous soda, which does not dissolve the other salt.Asym-metrical ethyl broririsophthalate, C,H,Br(COOEt),, is thus obtainedpure ; it is a colouyless oil with an odour like that of rum,; it boils at520-325" under 365 mm. pressure, and, when treated with concen-trated hydrocliloric acid, yields usyrnmetrical bromi.yophtIzalic acid,C6H,13r(COOH)2 [Br : (COOH), = 1 : 2 : 41. This forms whitenoedles melting a t !283", and sublimirig without decomposition ; itdissolves readily i l l alcohol, sparingly in water. It is identical withthe acid obtained by oxidising a- and ,8-bromocymene with nitric acid.The ammorrivm saZt forms fine, colourless, asymmetric cr7stals(u : b : c = 1*50:30 : 1 : 0 9753 ; = 70") which decompose a t 100".The ba&m scllt is white ;.the copper and silver salts form respectivelylight-blue and white precipitates.The acid may also, although lessconveniently, be obtained tiy saponifying parabrcmonietacyanobenxoicucid, CN*C6H313r*COOH, with concentrated hydrochloric acid. Thisacid is obtained from parabi~oinon~etarnidobenzoic acid by the actionof sodiiitn nitrite on an aqueous solution in the presence of coppet-cyanide, It forms white needles melting a t 186", and sublimingwithout decomposition. It dissolves readily in hot water and al(.ohol ;the copper and lead salts foi-m respectively light-green and yellowish-brown precipitates. Asymmeti.ica1 bromisophtltalic acid yields thecorresponding bydroxy-acid with alkalis or alkaline carbonates, andwith ammonia the corresponding amido-acid.Parahi-om o m etusulp ho beizxcdd elL y d e,is obtained as the barium salt, (C,H,BrS04),Ba + 5H20, by heztingpqrabromobenzaldehyde with fuming sulphuric acid at 150".andsaturating with barium carbonate. It does not lose all its water untilheated to 220". When boiled with aqueous sodium carbonate, i tyieldfi the sodium salt of pai*ahydroxymetasuIphobenzaldehyde,So,Na'C6H3( ONa)*CHO. C. F. l3.Friedel-Crafts' Synthesis. By M. S c H i j P m (Ber., 24, 3i66-3770).-When halo'id derivatives of benzene are treated with aceticor benzoic chloride in the presence of a.luuiinium chloride, the acetylor benzoyl group takes the para-position relatively to the halogen,forming respectively parabromacetophenone, C6HI,Br*COMe (t,hchydrazone of which, C6H4Br.CMe:N?HPh, forms yellowish platesme1 ting at 126"), and parachlorobenzophenonp, C6H,Cl*COPh.Ifthe para-position is already occiipied, no i*eaction occurs, as in the caseof pnradibromo- and parndiiodo-benzene, and of 1 : 4-dibromo-naph t Lalene338 ABSTRACTS OF OHEMICAL PAPERS,With parabromobenzoic chloride and bromobenzene, the reactiontskes place much less easily, and besides diparabromobenzophenone( ilhe hydrazone of which, C ( CGH4Br)2:N2HPh, forms yellow platesuielting at 1 38"), some monobromobenzophenone is also formed.The homologues of the halogen benzenes react, although lesseasily than these, if the para-position to the halogen is still nn-substituted; in the opposite case, no reaction takes place, as, forexample, with parabromotoluene and unsymmetrical bromometa-xylene, C6H,BrMe2 [Br : Me2 = 1 : 2 : 41.Orthobromotoluene andacetic chloride yield parabromometatoluyl methyl ketone,C6H,BrMe*COMe [Br : Me : COMe = 4 : 3 : I],as a yellowish oil with a feeble-greenish fluorescence boiling a t269-272" ; when oxidised with permnnganate, it yields parabromo-metnt oluic acid. Bromoparaxy lene and acetic chloride yield a smallquantity of bromoparaaylyl methyl ketom, C6H2BrMe2*COMe[Br : Me2 : COMe = 4 : 3 : 6 : I], which melts at 39".Deoxybenzo'ins. By H. W EGE (Ber., 24, 3540--3542).-Benzybortholcry ZyZ ketone, CH2Ph-COC6H,Me2, prepared by Friedel and Crafts'method from orthoxylene and phenylacetic chloride, crystallises i nyellow plates, melts a t 95", and boils at 210-220" under apressure of2.5 mni.; it is soluble in alcohol, ether, and light petroleum, and itso;~ inze crystallises from light petroleum in lustrous, colourless needles.The henzyl derivative, CH2Ph*CHPh*C0.C6H,Me2, obtained by boilingthe ketone with an alcoholic solution of benzjl chloride and sodiumetboxide, crystallises from light petroleum in lustrous needles meltingat 75". The isobutyl derivative, C4H,-CHPh*C0.C,H,Me2, formscolourless or yellowish crystals, and melts a t 91.5".Ilenzyl metaxylyl ketone is a thick, yellow oil, boils at 206-208"iinder a pressure of 22 nim., and is readily soluble in ether, but moresparingly in alcohol ; its benql derivative boils a t 365-375".Benzyl partrxylyl ketone boils a t 220-250" under a pressure of26 mm.; its ozime, CIGHl,NO, melts a,t 99", its hydmzone a t 96", andits benzyl derivative a t 60.5".Stereochemical Isomerism of Nitrogen Compounds. By A.HANTZSCH and F. &<AFT (Ber., 24, 3511--3528).-The authors haveprepared a number of compoutids, other than oximes, having thegeneral formula $>C:NZ, with the object of ascertaining whethersuch substances are capable of existing in stereochemically isomericforms; if such were the case, there would be strong grounds forthinking that Auwers and Meyer's explanation of the isomerism ofoximes is incorrect, because their hypothesis is based on the supposi-tion that this isomerism is due to the peculiar constitution of hydroxyl-amine.Puramethoxyheizz7tydryZamine, NH2*CHPh*C6HI*OMe, is obtainedwhen either of the stereochemically isomeric paramethoxybenzo-phenoneoximes is reduced with sodium amalgam in the cold; it is athick, optically-inactive oil, yields a sparingly soluble crystallineC.F. B.P. S. KORGANIC CHEMISTRY. 339hydrochloride melting at 191", and a crystalline acetyl derivative whichmelts at 159". The formation of a base isomeric with the above wasnot observed,Imidobenzophenone hydrochloride, CPh,:NH,HCI, is formed whenbenzophenone chloride (1 mol.) is heated with ethyl amidoformate( 3 mols.) a t about 130" until the evolution of hydrogen chlorideceases ; it is a colo~rless, crystalline powder, sublimes when heated,and is insoluble in ether and benzene, and only moderately easilys )luble in chloroform ; it is quickly decomposed by cold water, yield-ing benzophenone and ammonium chloride.Imidobenzophenone, pre-pared by passing anhydiwiis ammonia into a chloroform solution ofthe hydrochloride, is a colourless oil, and is decomposed by water.I'aramethoxyberuophenowe chloride, CPhCI,*C,H4.0Me, can be ob-tained by warming paramethoxybenzophenone with slightly more thanthe theoretical quantity of phosphorus pentachloride. It crystal-lises in colourless plates, melts at 54", and is readily soluble inbenzene, chloroform, and ether ; it is decomposed by warm water andby alcohol into hydrochloric acid and paramethoxybenzophenone.Paramethoxy b~nzophenone~~rachlorariil~ne,OMe*C6HI* C Ph: N* C6H rC1,is formed when the preceding compound (1 mol.) is warmed withparachloraniline (3 mols.) in chloroform solution.It crystallises inyellow plates, melts at 104', and is readily soluble in benzene, ether,and chloroform, but more sparingly in alcohol ; it is quickly decom-posed into its components by hot dilute acids, but is not acted onby boiling water. All attempts to obtain an isomeride of this com-pound were unsuccessful.Yaramethoxybenxophenoneparatohidine, OMe*C,H,*CPh:N*C,H,Me,prepared in like manner, separates from chloroform in yellow crystals,melts at, 96", and resembles the preceding compound in its behaviourwith acids. The chloroform mother liquors obtained in the prepara-tion of this compound yield, on evaporation, not inconsiderablequantities of an oily product which does not crystallise when kept at0" ; it is possible that this oil coutains an isomeride of the crystallineproduct (m.p. 96").Paramst hoxy benzophen 011 e- /3-napht hy lamine, OMe* C6H4*C P h : F C,,,H,,prepared from paramethoxybenzophenone chloride and /3-napht hyl-amiiie, is a crystalline cornpound melting at 132", but the productsobtained in like manner from berizytamine and from pwramidophenol:rre oils, as is also the condensation product of paratolyl phenylketone chloride with paratoluidirie.An additive product of the composition OHGHPh-NH*C,Hk*COOHis obtained, together with the condensation product immediatelydescribed below, when metamidobcnzoic acid is shaken with waterand benzaldehyde; i t separates from ether in crystals, is readilysoluble in chloroform, and is decomposed by warm diliite hydrochloricacid.The condensation product CHPh:N*C,H,*COOH is graduallyJeposited from the mother liquors of the preceding compound ; it is Hyellowish, microcrystalline powder melting at 119" ; the formation ofan isomeride of this condensation product WiL6 not observed340 XB3TRXi;TS OF CHEMCAL PAYERS._Renzop7,enon~aramidobeirzoic acid, CPh2:N*C6H4*COOH. prepared byheating beiizophenone chloride with paramidobcnzoic acid in chloro-form Polution, crystallises frt)m chloroform in yellow prisms, melts a t240°, and is only sparingly soluble in ether, benzene, and cold alcohol,hut inoderately easily in hot C I ~ C O ~ I O ~ , aiid very readily in chloroform ;it is slowly decomposed by cold alcohol, and quickly by boiling diluteacids, yielding benzophenone and the amido-acid.Paramefhoxy benzophen oneparami(?obenzoic acid, CllH1,N09, is formedwhen pwmmethoxg benzophenone chloride is treated with pnramido-benzoic acid in chloroform or toluene solution ; i t crystallises in yellowplates or microscopic needles, melts a t 21G0, and resembles the preced-i n g compoiind in its behaviour with solvents and with dilute acids.The chloroform mother liquors from this compouucl contain a sub-stance melting at about 164O ; this, and the fact that the crude con-densation prodnct has no well-defined melting point', whilst thatobtained from benzophenone chloi ide under like conditions meltsquite sharply a t 240°, lead the authors to conclude that possihly anisomeric paramcthoxybenzophenoneparamidobenzoic acid is praducedin the above reaction.Two isomeric h!ydrazones of the composition C2,,HIRN20, are pro-duced when paramethoxgbenzophenone chloride ( I mol.) is graduallyadded to a chloroform solution of phenylhydrazine ( 3 mols.) ; afterkeeping for some hours, the filtered solution is evaporated a t t h eorditiarg temperature, and the two products separated by fractionalerystnllisa,ti m.The one melts at 132O, crystallises from alcoliol insmall prisms, and is only sparingly soluble in cold alcohol, butmoderately easily in ether, and very rradily in cliloroform anflbenzene ; it is decomposed into its components by concentratedhydrochloric acid. The other hydrazone, which forms at the most,only about 10 per cent.of t,he crude product, is a colonrlem powder,and melts at' 90" ; it resembles its isomeride verg closely i n appear-ance, and has approximately the same solubilities, except, that it ismuch more readily soluble in ether. The only notable difference inchemical properties is, that the rornpound of lower melting point isless stable tjhan the other, and resinifies more readily ; under certainconditions, the componnd of lower melting point seems to be con-verted into tbe isomeride. F. s. K.By B. GOLDBERG (Ber., 24, 3.552-3553).-Bidet's statement (Abstr., 1889, 59.5) that a mixture of pure(thiophen-free) aniline, orthotoluidine, and parntoluidine only yieldstraces of rosaniline on heating with arsenic acid is incorrect; ttieauthor's experiments have showii that, practically, the same qnantityof rosaniline is obtained from the thiophen-free, as from the corn-mercial bases.F. s. K.By V. MEYER andH. WEGF, (Rer., 24. SSS5--3536).-Desaurin can be easily prepare11by mixing deoxyhenzoyn (1 mol.) with finely-divided potassiumhydroxide (4 mols.), and boiling the mixture with carbon bisulphide(15-20 parts) fnr 2 i hours ; t h e carbon bisulphide is then distilled,the residue washed with alcohol and ether successively until theFormation of Rosaniline.New Method of Formation of DesaurinsORGANIC CHEMISTRY. 341washings are no longer coloured red, and then recrystallised fromcehlorofortn or xylene ; the yield of t h e pure product is about 45 percent'. of the deoxybenzoyn employed.F. S . K.Studies in the Induline Group. By 0. PISCHER End E. HEPP(Annulen, 266, 249-263 ; compare Abstr., 1891, 1044) .-Whenphenjlinduline is heated a.t 160-170" for 5-6 hours with glacialacetic acid (5 parts) and 20 per cent. hydrochloric acid (20-30 parts),o r dilute (1 : 5 ) sulphuric ncid, i t yields aniline, a base of t h ecomposition C,,H,,N,O, benzeneindone!, a hydroxy-compound of thecomposition CleB11N202, and a small qusntit$y of a brownish-redsubstance ; these products are isolated as follows :-The brownish-redsolution is filtered from a considerable quantity of a brown, crystal-line substance, which consists essentially of the hydrochloride of thebase C,rH,,N,O, b u t contains also a small quantity of the brownish-red substance ; t h e last-named compound is probably a salt of carb-azolefluorindine (Zoc.c i t . ) , judging from the fluorescence of i t s s o h -tions ; i t can be easily separated from the other hydrochloride, owingto its insolubility. The acid filtrate is then treated with excess ofalkali, the precipitated benzeneindone separated by filtration, thealkaline solution treated with acetic acid, and t h e precipitatedhydroxy-compound extracted by shaking with ether.'l'he base of the composition C2$H ,,N,O, obtained by decomposingthe hydrochloyide with alcoholic soda, crjstallises from hot, benzenei n +mall, brown crystals h a v i n g a steel-blue reflex ; i t melts at about218" with evolution of a, red vapour, and, when heated more strongly,i t is converted into the brownish-red substance referred to above,It dissolves in glacial acetic acid and in dilute niineral acids yieldingbrownish-red, in concentrated hydrocliloric acid and sulphuric acitLyielding dirty-violet,, solutions ; when heated with concentratedhydrochloric acid, it ia decomposed into aniline and t h e hydroxp-conrpound referred t o above, and more fully described below.The hydr-oxy-compound of the composition C,,Hl,N2( l2 is obtainedi n reddish-yellow crystals on evaporating its ethereal solution (seeabove) ; it crystallises from benzene o r alcohol in brownish-yellowprisms o r plates, gives off R brownish-red vapour when heated at230", and melts at about 280"; i t imparts t o textile materials abrownish-orange colour. I t dissolves in concentrated sulphuric acidwith a brownish-yellow coloration ; its hydrochZoride crjstallises inthick prisms having a greenish-blue reflex, and is decomposed by water.Benzetieindone, Cl,-,H12N20, crystallises from alcohol in lustrous,well-defined plates, dissolves in benzene and alcohol with a yellow, i ndilute hydrochloric acid with a rose red, and in concentmted sulph-uric acid with a, green, coloration ; when distilled with zinc-dust, i tyields phenazine (m.p. 171") and benzene.A compound of t h e composition C18Hl5N:jO2 is formed, togetherwith a violet. base, aniline, atid a sparingly soluble, almost black com-pound, when amidophenylinduline sulphate is heated with dilutesulphuric acid for 4-5 hcu1-s a t 160-170"; t h e acid solution istiltered from the sparingly soluble sulphate of t'he violet base,mixed with soda, again fillered, the filt ate acidified with acetic acid342 ABSTRACTS OF OEICMICAL PAPERS.and the precipitate rccrystallised from 70 per cent.alcohol, fromwhich i t separates in small, nodular crystals, or in plates, showing Rgreen reflex. It sinters together a t about 230°, and melts completelyat 270-280" with evolution of brown vapours; it dissolves inbenzene, yielding an orange-red solution which shows a p e e n fluor-escence, and its solution in acetic acid is rose-red, that in concentratedsulphuric acid greenish-brown. The sulphnte crystallises from hot,dilute sulphuric acid in red needles, and is moderately easily solublein water.Phenylarnidophemjlinduline, C3,H2,N4, is formed, together withmuch smaller quantities of anilidophenylamidophenylinduline (seehelow), when amidophenyliriduline is heated with aniline (2 parts) at150-160" for some hours.It crystallises from hot benzene in smallnodules or plates having a green reflex, and melts at 245-250" ; itssolution in benzene is reddish-violet, that i n alcohol, blue, and thati n concentrated sulphuric acid, greenish-blue. The hydrochloride,CmH22N4,HC1, forms lustrous, greenish crystals. This induline canalso be obtained by heating an alcoholic solution of phenylamidoazo-benzene (136 grams) with aniline (140 grams) and aniline hydro-chloride (65 grams) a t 150-160" for a day ; the yield of the hydro-chloride is about 100 grams.AnilidophenylumidopJr,enylinduline, CJ6H27N5, is best prepared bylieating a mixture of azobenzene (12 parts), aniline (48 parts),aniline hydrochloride (24 parts), and nitrobenzene (12 parts) foreight hours a t 170".It crystallises from boiling xylene in nodules orplates having a green reflex, and meltiiig at 286-288"; it is moresparingly soluble than any other known induline. The hydrochloridec.rystallises in lustrous needles, and dissolves in alcohol with a green-is h- blue coloration.The molecular weight of phenylinduline was determined by Raoult'smethod in benzene solution: the results were in accordance withthose required by a compound of the inolecular formula C,,H,,N,.F. S. I(.Homologues of Acridine. By A. VOLPI (Gazzetta, 21, ii, 228-237).-EthyZacridine, C6H4<&->C6H4, is prepared by Bernthsen'smethod (Abstr., 1884, 1356) by the action of propionic acid on amixture of dipheny!aniine and zinc chloride.When pure, it crys-iallises in lustrous, white plates with a yellowish tinge, melts at 11Cjo,and dissolves freely in alcohol, benzene, and light petroleum, formingsolutions with a blue fluorescence ; i t is only very sparingly solublei n water. The dilute solutions of its salts all have a p e e n fluor-escence. The plutinocli loride, (C,,H,,N),, H2PtCI6, forms minute,yellow crystals, which decompose at 215" without melting. Theuurochlmide, CIbHI3N,HAuCl4, crystallises in needles melting at170". The hydrochloride, <116H,3N,HC1, crystallises in yellow, mono-clinic prisms, u : 6 = 1.5199 : 1 ; p = 83' 07'.It dissolves freely i nwater, and the solution is brownish-yellow when concentrated, andjellow, with a green fluorescence, when dilute. It is readily solublein alcohol, and decomposes when heated, without previous melting ;CEORGANIC CHEMISTRY. 343the sulphate, (Cl5HI3N),,H,SO4, is pale-jellow in colour, and melts a t2 10".Propylacridine, C,H4<CPr> CsH4, prepared in a manner similar toN-the previous compound, by the action of butyric acid on a mixture ofdiphenylamine and zinc chloride, crystallises from alcohol in colour-less, monoclinic plates, n : 6 : c = 2.015 : 1 : 1.998 ; p = GI" 07'. Itmelts a t 72-75", dissolves freely in alcohol, and is almost insolublei n water ; its solutions have the characteristic green fluorescence, andin other respects it has the general properties of the acridines. Thek~ydrochloride, CIsH,,N,HCl, forms yellow crystals which, when heated,decompose without previously melting ; the sulphate, C,,H,,N,H,SO,,forms greenish-yellow crystals, readily soluble in water and alcohol,but insoluble in ether.It darkens a t 245', and melts at 249".Pentadecy lacridine, CsH4< c I (C15H31) > C6&, is prepared from palmi- N--tic acid by the same method as the preceding compounds. It separatesfrom alcohol as a crystalline mass of a buttery consistency, but may\ e obtained in white or yeilowish plates by slowly evaporating thoalcoholic solution. It melts a t 65', and dissolves in alcohol, ether,Ineiizene, and light petroleum, but not in water. The alcobolic Eolutionof the base has a blue fluorescence, whilst the alcoholic solutions of itssalts have a green fluorescence, and are decomposed by water.Thej'latin ochloride, (C,,H,,N),, H,Pt CI,, forms minnte, orange-yellowc*rystals melting at 185". The hydroclLZoride, C?8H39X,HC1, is a yellowsubstance which melts a t i9', dissolves in alcohol, and is decomposedwater. The s+hate, C,,H,N,K,S04, crjstallises in tufts of>ellowish-red needles, melts at 150-151", and dissolves in alcoholand beiizene, but is insoluble in ether, and is decomposed by water ;its solutions have a feebly acid reaction.Stearic acid also yields an acridine by Bernthsea's reaction, so thatif the reaction does not apply to the entire series of fatty acids, thelimit must lie beyond stearic acid.Acridines may also be preparedfrom lactic, succinic, and tartaric acids, and will be described hy theauthor in a future paper. S. B. A. A.Methylcarbazacridine. By D. BIZZARRI (Gaxzetta, 21, ii, 1 5 8 -N-C,€I, .I I 163).--~ethyZcarbazucrid~ne, 1 X I , is obtained by a methodMeC-csH3analogous to that used for the preparation of phenylcarbaz-acridine (Abstr., 1891, 219). A mixture of carbazole (8 grams),glacial acetic acid (7 grams), and zinc chloride (15 grams) is heateda t 150-155" in ti sealed tube for eight hours, The bluish-green,pitchy product is extracted with boiling absolute alcohol, the liquidtiltered into concentrated ammonia solution, and diluted with water.The bright-red precipitate is collected, washed, dried, and repeatedlyextracted with dilute alcohol (47 per cent.) ; on cooling, the solutiondeposits a yellowish-white substance, which, after being washed wrthdilute alcohol, dried, and dissolved in the least possible quantity o344 ABSTRACTS OF CH~MLCAL PAPERS.glncial acetic acid, is reprecipi tat ed by ammonia.and finallyfractionally crystallised from benzene and alcohol. Minute, colour-less, uniaxial rhombohedra are thus obtained, soluble in acetic acid,sparingly so in alcohol, benzene, ether, chloroform, and carbon bi-sulphide, and insoluble in water and light petroleum. Whcn heated,the substance shrinks a t 150', softens a t 175', melts at 1i8', anddecomposes a t higher temperatures.When its acetic acid solution istreated with zinc-dust, filtered. and the filtrate precipitated withwater, a white, crystalline powder is obtained, melting with deconi-position a t 206" ; this dissolves in acetic acid, yielding a colourlesssolution, which, on t i eatment with potassium dichromate, gives thecharacteristic cherry-red colour of the original substance. Acidsalso, especially hydrochloric and sulphuric, rapidly reconvert i t intornethylcni*bwzacridine, of which it is, doubtless, the hydro-derivative.The compounds of methylcarbazacridine with acids have the sameinstability as tlie corresponding phenylcarbazacridine compfiunds,being decomposed by water, alcohol, excess of acids, or by drying.The h y d r o c k l o d e fornis beautiful, indigo- blue plates, the sulphategreenish-blue plates, the n i f m t e light-blue plates, atid the chromatebrownish-green plates.Picric acid forms an unstable compoundcrystallising in 1-ubj-red needles. Methylcarbazncridine is obtainedin small quantity by heating acetylcarhazole with zinc chloride fortwo hours a t 150-1.55", and proceeding as above indicated. Theaqueous alcohol used in the preparation cf the substance retains insolut,ion a compound melting a t 137-138", and crystallising iiiminute prisms, soluble in acetic acid. W. J. P.Aromatic Nitriles. 13s F. J. ZIKSSER (Ber., 24, 3556-3557;compare Freund and Immerwalir, Abstr., 18W, 1407).-A more con-venient method for preparing dipheiiylacetic acid than th8t usuallyadopted is to boil benzilic acid with hydriodic acid (b.p. 127') aiitla little amorphous phosphorus for four hours ; the nitrile of this acidis best prepared by quickly distilling a mixture of the amide anclphosphorus sulphide from a small retort.Diphenjlacetonitrile does not react with fatty hfllogen compoundsuuder various conditions ; on reduction with sodium and amyl nlco-hol, i t is converted into diphenylmethane and hydrogen cyanidc.IVhen phenylcinnamonitrile, cHPh:CPh.CN, is treated with sodiumand amyl alcohol, i t yields a large quantity of dibenzyl.1 : 3' : 4-Dichlor~naphthalenesulphonic Acid. B.y P. T. CLEVI:I?. S . I(.(Rer., 24, 3477--347!)).- 1 : 3' : 4-l)ichloronaphthaler/esul~honic acidis obtained by dissolviiig 1 : 3'-dicliloronnphthalene (m.p. 48") in ;Lirlixtnre of fuming and concentmted sulphuric acid (equal parts) anclgently waiming, when a pasty mass is produced, which, on dissolutiotiin wdm, yields microscwpic needles of the acid ; i t is very sparinglysoluble in dilute sulphnric acid. A second product, probably adisulphonic acid, is also obtained in small quantity. The potassiumsalt crystallises in flat, needles and tablets of' a silvery lustre with1 mol. H,O ; the u?nnioniicm salt resembles i t ; the sodium salt formsthin needles with 3 mols. H,O; the silver salt lustrous scales witORGXNTC CHF JI[STRY. 345I mol. H,O; the calciiini and ba&m salts crystnllise with 3 mols.H,O; whilst the ziric salt crystallises with 5 mols. H,O. All thesesalts are readily soluble in boiling water, and, for the most p a r t ,sparingly so in cold water.The lead salt crystallises with 4 mols. H,O ;the noppw salt with 6 mols. H,O ; whilst the niethyl and ethyl salts formdelicate needles arid melt a t 138" and 154" respectively. The sulph-onic chloride crystallises from glacial acetic acid in needles, and melts at151", whilst the ~ulpkonanzi~~e forms long, flat, satiny needles, antimelts a t 217". 1 : 4 : 3'-Trichloronaphthalene (m p. 65") is formedwhen the sulphonic chloride is heated with an excess of phosphoruspentachloride. A. R. L.1 : 2-Amidonaphthalenesulphonic Acid. By P. T. CLEVE (Be?..,24, 3472-3477) .-Landshoff and Meyer (D.-R. P. 56,563) describea naphthylaminesulphonic acid, obtained by heating at 200-250" at1alkali salt of naphthionic acid which contains the amido-group in ana-position.The sulpho-group must occupy the @-position adjacentto the amido-group, as it can be converted iuto 1 : 2-dichloronaphthal-ene (m. p. 34'). The new acid forms long, anhydrous needles orsmall, rhombic cr-ystals, a : b : c = 0 79401 : 1 : 0.36429, and is moresoluble than its isomeride, dissolving in 34 parts of boiling water anrl225 parts of cold; if allowed to slowly crystallise a t the ordinarytemperature, long needles containing Q mol. H,O are obtained. Thepotassium salt, sparingly soluhle in cold water, the sodium salt, dis-solving in 60 parts of cold water, the ammonium salt, readily solublein water, the silver salt, a white, sparingly soluble precipitate, arid thecalcium salt, sparingly in water, are anhydrous, whilst the mrsgnesiumsalt crystallises with 8 mols.H,O, the zinc salt with 5 mols. H20, andthe barium, lead, and manganese salts with 1 mol. H,O. The acetylderivative dissolves easily in water and separates in small, lustroiisneedlrs containing 1 mol. H,O. The diaxosrdphonio acid is a greenish,crystalline powder, and yields a hydrazinesulphonic acid crystallisingin micacous plates. The chlorosulphonic acid, obtained by boilingthe diazo-derivative with cuprons chloride, crystallises in plates of ~tsilvery lustre, and yields a suZphouic chloride me1 ting at 80", anhydrouspotassium, sodium, siluer, and barium salts, a calcium salt containing1 mol. H20, and an ethyl salt crystallising in small, colourless needles,and melting a t 104".1 : 2-Dichloronaphthalene passes over on dis-tilling the chlorosulphonic acid with an excess of phosphorus penta-chloride. 1 : 2-Naphtholsulphonic acid is produced by adding thediazo-derivative to boiling dilute sulphuric acid, and is purified byfirst converting it into the barium salt and then into the lead salt; itforms small, lustrous, rhombic tablets, is readily soluble in boilingwater, sparingly ira cold, and does not melt at 250" ; its solution giveswith ferric chloride an indigo-blue colour, which soon changes todirty red. The sodzum salt is readily soluble i n water; the leod andcalcrum salts crystallise with 1 mol. H20, and are sparingly soluble inwater, wliilst the barium salt crystallises with 1i mols.H20, and isalso sparingly soluble in water. Further experiments are in progress.A. R. L346 ABSTRACTS OF CHEMICAL PAPERS.Nitrosonaphtholsulphonic Acids. By 0. HOFVMANN (Bern, 24,3741--3746).-Sodium ferriizitrosonnphtholsul~hor~afe,Fe(NO*CloH50*S0,Na), [0 : NO : SO, = 1 : 2 : 41,is prepared by adding ferric chloride in excess to nitroso-a-naphtliol-sulphonic acid and treating t.he solution with soda; the compoiindcrystallises from water in dark-green plates. The correspondingpotassium salt, Fe(NO*C,oH50*S03K),, is more unstable t.han thesodium compound, and does not give constant arialyticd results.Cup& Ititros~naphtholsulphonate, C,,H50<"o >Cu + 3H20, is ob-tained from nitroso-x-naphtholsulphoiiio acid and cupric sulphate, andcrystallises in groups of brown needles.Nitroso-/3-naphtholsu! phonicacid gives an insoluble, amorphous precipitate with ciipric sulphate.SO,Cupric anzmoizionitrosonaphtholsulpl~onate,C10H50<so3.NH, N0*NH3>C~ + H20,is formed from nitroso-a-napbtholsulphonic acid and cupric ammonio-sulphate, or by heating tbc preceding copper salt with ammonia, andcryetallises in small, brobn plates, which exhibit an intense, bronzelustre in reflected light: The compound from nitroso-p-naphthol-sul phonic acid resembles the a-derivative in properties and composition.+ + H,O [O : NO : SO, = 1 : 2 : 41, crystallises in lustrous, brownish-red needles, which are somewhat soluble in dilute ammonia. Thecorresponding compound [O : NO : SO, = 2 : 1 : 3'1 is deposited inyellowish-green, lustrous plates.The cadnzium ammo&-salts are crystalline ; the a-naphtholsulph-onic acid derivative is deposited in long, orange-coloured needles,whilst that from /3-naphtholsulphonic acid is obtained in yellowish-green, microscopic plates.All the above ammonio-derivatives decompose, with evolution ofammonia, on heating in aqueous solution.Sodium Izitrosona~hthnlsul~~onute, NONa:C,oH50*S03Na + 2H20[0 : NO : SO, = 2 : 1 : 3'1, is prepared by adding concentrated sodato a hot saturated solution of sodium nitroso-P-naphtholsnlphonate,and orystallises in small, slender, green needles.Hydroxyanthranol. By C.E. LINEBARGER (Bull. SOC. chi^. [ 3 ] ,6, 92-94) .-Benzylhydroxjanthranol,Zinc ammonionit rosonapht hols ulphonate, C ,oH,O<so,.N0.NH,>Zn NH3J. B. T.is best prepared by boiling for three hours a mixture of 5 parts ofsoda, 50 parts of water, 10 parts of zinc-dust, and 3 parts of anthra-quinone, and then adding 3 parts of benzyl chloride in small portionsand continuing the boiling for fivc hours. The product, after b&gpurified by crystallisation from nlcohol, is recrystalhed from benzene.It then forms very pure but small prisms, melts at 60-61", anORGANIC OHEMISTRY. 347begins to decompose at 100". It is insoluble in water, soluble inalcohol, benzene, and chloroform. I t s solutions have a bliiishfluorescence. Anthraquinone is obtained by oxidation with chromicacid in acetic solution. Benzylanthracene is obtained by reductionwith hydriodic acid and amorphous phosphorus.The production ofdiacetylbenzSlhydroxyanthrano1, by boiling 3 parts of benzylhydroxy-antbrano1 with 6 parts of sodium acetate and 20 parts of aceticanhydride for bale an hour, proves the presence of two hydroxvlgroups. The purified product forms small, greenish tables, insolublein water, soluble in alcohol, very soluble in benzene. It melts at126". W. T.Paranthracene. By K. ELM (J. p r . Chem. [Zl, 44, 467-469).-The paranthracene was prepared by exposing a benzene solution of90 per cent. anthracene, saturated at 40-60°, for B week to sunshine,and then gently warmirig it on the water-bath t o dissolve any an-thracene which might have crystallised out together with the par-anthracene. The precipitate was then filtered, washed wi t,h benzene,and crystallised either from boiling xylcne or dimethylaniline.Fromxylene, paranthracene generally crystnllises in colourless, lustronsneedles, and from dimethylaniline in lamine. The crystals melt, butnot sharply, between 272" and 274", and become converted into anthrac-ene. Paranthracene does not fluoresce, whether as 8olid or in eolu-tion; it remains unchanged at 260°, and when a solution of i t indimethylaniline is heated; on the other hand, a solution of it inllaphthalene and in diphenylamine rapidly becomes fluorescent fromits conversion into anlhracene, the former solution when boiled, andthe latter when heated a t 260".The solubility of paranthracene in various solvents at their freezingpoint is very slight ; naphthalene proved the best solvent for det.er-mining the molecular weight of paranthracene by the cryoscopicmethod, and even this only dissolves 0.229 per cent.at its meltingpoint. A large number of determinations were made with the soh-tion in naphthalene, and the results showed values varying between276 and 344 as the molecular weight of paranthracene, whose fortnulamay, therefore, be allowed to be (C,dHlo)Z. Graebe and Liebermannassert that. paranthracene is stable towards bromine in sunlight. Theauthor finds that a mixture of paranthracene (1 part), bromine (10parts), and carbon bisulphide (100 parts), exposed to sunlight, rapidlyevolves hydrogen bromide, and yields dibromanthracene tetrabromide.Anthracene behaves similarly under the same circumstances, althoughstatements as to the bromination of anthracene take no account of thefact.A. G. B.Terpenes and their Derivatives. By J. W. BRCHL (Ber., 24,3701-3737 ; compare this vol., p. 'LOO).--This paper describes someof the physical constants of the compounds described i n the previouscommunication.The specific gravity was determined a t '20" aud compared withwater a t 4". The refractive index (11) was usually determined forthe potassium, sodiuifi, lithium, and tliallium flames, and also for th3 48 ABSTRACTS OF CHEMTCAL PAPERS.lines in the hydrogen spectrum, Hz, HP, H*/, Hfi. The term “specificdispersion ” is applied to the difftwnce in the specific refractive powersof the compounds in the region of the spectrum between Hy and Ha,9 i x denotes the molecular refractive power for the hydrogen line a.The sp.gr. of merithyl ethyl ether, C,,H,,OEt = 0.8513; 93tz = 56.96,and the molecular dispersion = 1.38; these numbers agree closelywith the theoretical values. Ethyl camphor could not he obtainedquite pure ; its sp. gr. = 0.9:372 ; 9tz = 53.4(! ; 9h, = 53.64 ; mole-cular dispersion = 1-29 ; the compound, therefore, contains noethylene li n kaqe.E thy1 cam phocarboxylate, like the preceding compound, containsno ethylene linkage ; the sp. gr. = 1.0563 ; 93tz = 59-48 ; 92-i - 9Ra= 1.45. The molecular dispersion of these compoiinds is thus seento be unaf3fected by the closing of an open chain ; in this respect itresembles molecular refraction, nor is i t influenced by a para-linkagein the benzene nucleils ; that is to say, by the formation of a doubletetramethylene ring.Ethyl cnmphocnrboxylttte ethyl ether isrepresented by the formula alrrady given, and is not a camphordi-carboxylic acid ; its sp. gr. = l.Oi59 ; 9;s = 76.92 ; %-/ - 9ia = 2-20.The theoretical values are 74.61 and 1.177, the difference is probablydue to experimental error.Bornjl ethyl ether, C,,HI7*OEt, was prepared by the mutual actionof borneol, sodium, and ethyl iodide, and also from camphor \)yBsubiqny’s method; the sp. gr. = 0.9008; 9iz = 54.88; 9iy -= 1.31.Bornyl methyl ether, C,,H,,*OMe, like the preceding compound, hasno ethylene linkage, the sp. gr. = 09162; 9b = 50.36 ; %by - 9iz= 1.26.Bornyl methylene ether, ( C1,H,,O),CH,, crjstallises in rhombicprisms, a, : b : c = 0*91:34 : 1 : 0.565; the sp.gr. = 1,0735 ; $ 1 ~ 1 ~ =92.77 ; % l l ~ , , - WH, = 2.16 ; this value was obtained indirectly ; thenumber required by theory is 2.14, and i t appears to be the firstknown example of a compound urystallising in any but the regularsystem, the molecular refraction and ~iiolecular dispersions of whichagree with the values deduced from its chemical composition and con-sritution ; for details of the measurements and calculations, the originalpaper should be consulted.The const ants for diethyl camphorate also agree with theoreticalnumbers; the sp. gr. = 1.0298; $?a = 67.32; 9t-i - ’3ta = 1-57,l’he compound contains TJO ethylene linkage.On Ftc-count of the extreme viscosity of ethyl hjdrogen camphorate,the sp.gr. was determined by means of the vacuum pjknometer(Abstr., 1891,520) ; the sp. gr. = 1.09977 ; 9la = 57.84 ; 9 i y - 9lz= 1.37; the acid, therefore, contains 110 ethylene linkage, and thephysical properties agree with the formula already proposed for it.‘l’he molecular heat of combustion of camphoric acid = 1243.6 cal.and of camphoric anhydride = 1252.4 cal. ; the small difference betweenthese numbers indicates that the carboxyl groups are in the ortho-position.The author considers that the low electrical conductivity ofcamphoric acid is the only fact which can be urged against his formula ORQANIO CHEMISTRY. 349after pointing out that this may be due to the presence of the basicgroup CH2-CH2, he discusses the general effect of substitution onthe electrical conductivity of acid@, and enumerates a number ofapparent anomalies ; since no analogue of cnmphoric acid is known inthe succinic acid series, it is impossible to foresee how the electricalconductivity would be affected- by the introduction of the groupCZH,.J. B. T.Crystalline Products from Lemon and Bergamot Oils. ByL. CRISMER (Bull. Soc. Chim. [3], 6, 30-33 ; compare Tilden and Beck,Trans., 1890, 323).-The residue from the distillation of lemon oil ata pressure of 10 mm. is dissolved in liglit petroleum, and this solutiondeposits nodular crystals of the composition C1OH1OOd, which are puri-fied by recrystallisation from anhydrous ether, and then form a white,inodorous powder which melts a t 144", and neither decomposes norsublimes when heated to 240".Sulphuric acid colours this substance,which is, perhaps, hesporetic acid, golden-yellow : a trace of nitric acidconverts this to green, or a trace of potassium permanganate 80 blue,which subsequently becomes green. On evaporation, the light petr-oleum leaves a butter-like mass, melting about 50°, and this, afterpurification by recrystallisation from alcohol, has a lernon-like odour,and gives a dark brown coloration (this vol., p. 386) with am-moniacal mangnnous solutions, differing in this respect from thesubstance Cl0HI,,O4. Bergamot oil, when similarly treated, affordswhite, crystalline needles which melt at 184O, sublime at 230-240",and have the centesimal composition C 65.24, H 3.78, 0 30.98.This substance does not appear to be the bergaptene of Mulder andOhme, which melts at 206".T. G. N.Action of Hydriodic Acid and Amorphous Phosphorus onPicrotin. By A. OGLIALORO and 0. FORTE (Gazzetta, 21, ii,213--'L15).-~icrotozic acid, Cl6HI8O4, is obtained by warming a mix-ture of picrotin (prepared by the action of potash on picrotoxin),amorphous phosphorus, and hydriodic acid, allowing the brisk effer-vescence which takes place at first to subside, and then boiling for about10 hours in a reflux apparatus. On diluting the product with water,steam-distilling, and filtering the residue, the filtrate, on cooling,leaves a white deposit of picrotoxic acid. This crgstallises from dilutealcohol in lustrous, white needles, melts at 134", dissolves readily inalcohol, but only sparingly in hot water.It bas a feebly acid reaction,and dissolves in alkalis, but is reprecipitated from its solutions onthe addition of an acid. The silver salt, C15Hn04Ag, is a white, crys-talline powder, sensitive to light. The formation of this acid affordsadditional proof of the formula, C16H1807 for picrotin.S. B. A. A.Constituents of theBuds of Chrysanthemum Cinerarizefoliurn.By H. THOMS (Chein. Cent?.., 1891, ii, 670-671 ; Phnrm. C'enkralhulte,32, 471--472).--Continuing his examination of the constituents ofthe buds of Chrysanthemum cinerariEfoliurn (see also Abstr., 1891,333), the author describes one of the new compounds, pyrethrosilb,VOL LSII.2 350 ABSTRACT8 OF OHEMTOAI~ PAPERS.more fully. The light petroleum extract of the buds was cmcen-trrtted, and a golden-yellow, soft residue obtained, which, after beingwashed with alcohol, remained as colourless, bitter crystals. Thecrystals are elongnted, rhom bic octahedrons, me1 ting a t 188-1813’It, is readily soluble in chloroform and in hot alcohol, less soluble inether and light peti*oleum, insoluble in water. I t s formnln isC3,H,,0,, (?). It dissolves in concentrated sulphuric acid with yellowor weak redish- brown coloration. I n 25 per cent. hydrochloric acid,the substance becomes red or violet, and the solution is violet coloured ;water precipitates yellow plates. The filtrate, after treatment withl~gdrochloric acid, does not reduce B’ehling’s solution, so that pyrethro-sin cannot be considered as a glucoside ; but if the yellow compound betreated with concentrated hydrochloric acid, and the solution be neu-tralised.it then reduces Pehling’s solution. The author suggests thatthe yellow substance is nearly related t o phloroglucinol, and thatpyrethrosin is a phloroglucide.Agrostemma Githago (Corn Cockle). By N. KRUSKAL and R.KOBERT (Chem. Centr., 1891, ii, 545-546 ; Arb. pharm. Inst. Dorpat,6 , 89-145, 146-148) -The sapotoxin of Apostemma has the samecomposition as those of radix saponaria a2bm and of quillaja bark, butdiffers from them in its physiological properties. Hydrolysis withacids causes the formation of glucose (4 mols.) and sapotoxin (1 mol.).The corn cockle contains about 6.17 per cent.on the average.4groste?nma-sapotos:in has an irritating action on the mucousmembrane of the nose, mouth, and eyes; it affects the nervessimilarly to that of the quillaja bark. When in solution (1 : 15000),it dissolves blood corpuscles of both carnivorous and herbivorousanimals. It appears to act differently on animals when taken in-wardly, the Herbivow being relativelv unaffected, provided that thedoses are not too large and not taken for too great a length of time,whilst, on the other hand, the CarnivorE are seriously affected andreadily succumb to its action. On man it has an intermediate effect,b u t doses of 0-1 gram are sufficient to cause illness. The authorpoints out t h a t the bread which the Russian military authorities pro-vide for the soldiers may contain as much as 0.5 per cent.of corncockle, and this corresponds with a dose of about 6 grams of corncockle per day, a quantity which may readily produce serious toxicale ffec t s .Kobert poiiits out that the simple term “ ssponin ” is not sufficient,and the source from which it has been obtained should be stated,since the several different snponins have such varying physiologicalactions. The several saponins appear to belong to series of com-pounds which have different generic formulae. Stutz’s saponin,C19H2~~OH)50~, belongs to a series the formula of which would beC,iHZn-eOlo. The lowest member of the series is isomeric withsyringin, and bas the formula Cl,H2M0,0.Constitution of the Ethylpyrrolines.By C. U. ZAYETTI(Gazzetta, 21, ii, 163--173).---The author aspplies the method givenby him (Abstr., 1891, 1387) for the determination of the constitutionJ. W. L.J. W. LORGAXIC CHEMISTRY. 831of pyrroline derivaiives to the case of the ethylpyrrolines obtained bythe various known methods.Ethglpyrroline (1 vol.), obtained by passing a mixture of equalyolumes of ethyl alcohol and pyrroline through a, heated tube con-taining zinc-dust (Abstr., 1890, l4%3), is dissolved in alcohol (10 vols.)nnd boiled with the calculated qufintities of hydroxylamine hydro-chloride and anhydrous sodium carbonate for six hours. The solventis distilled off under reduced pressure, the residue treated with cold,dilute aqueous potash, and the unaltered pyrroline extracted withether.The solution is now saturated with carbonic anhydride, andagain extracted with ether ; on evaporating the ethereal solution, asyrup is left which solidifies almostJ completely after a time. Theresinoiis matter is removed from this by washing with cold ether, andthe residue dissolved in boiling ether; on cooling, the solutioqdeposits a small quantity (0.2 gram from 11 grams of ethylpyrroline)of a dioxime, C6HI2N2O2, which, after recrystallisation from ether,f l ) r m s colourless scales, and melts at 134-135". The ethereal solu-tion, on concentration, yields a quantity (4 grams from 11 grams ofethylpyrroliue) of an isomeric dioxime, \v hich, on being repeatedlyrecrystallised from anhydrous ether, is obtained in splendid, colourlessscales melting a t 84-85" ; this compound is very soluble in water,alcohol, benzene, and ethyl acetate, somewhat less so in ether. Theformation of these two dioxirnes shows that the ethylpyrrolirie is a,mixture of two isomerides.The oxime melting a t 84-85" (2 grams), when boiled with 30 perwnt.aqueous potash (50 c.c.), gives off ammonia; the brownish-redsolution thus obtained is saturated with carbonic anhydride, reppatedlyextracted with ether to remove the unchanged oxime, and decolorisedby animal charcoal. The solution is now exactly neutralised withsnlphuric acid and evaporated t o dryness, first on a water-bath andthen in a vacuum. On ext,racting the residue with anhydrous etherfree from alcohol, and evaporating the ethereal solution, a syrupy acidis left ; this does not solidify, dissolves with effervescence in solutionsof the alkaline carbonates, gives a violet coloration with ferric chloride,and yields an uncrystallisable hydrazone.With lead acetate solution,the ammonium salt gives a white precipitate, soluble in excess ; withmercurous chloride, a white precipitate, rapidly changing to metallicmercury ; with mercuric chloride, an opalescence ; and with silvernitrate, in concentrated solution, a yellow precipitate rapidly changingto metallic silver. The acid is probably normaZ propionylpropionicacid, CH,Me*CO.CH,.CH,-COCH, its d e e r salt having the com-position AgC6H,0,. The dioxime melting a t 84-85" has, therefore,the constitution CH,Me*C(NOH)*CH,.CH,*CH:NOH, and the pyrrol-ine from which it is obtained must be a-ethylpyrroline. The dioximemelting at 134-135" is probably NOH:CH*CH,*CHEt*CH:NOH,and is derived from p-ethylpyrroline.The ethylpyrroline obtained by the action of ethyl iodide onthe potassium compound of pyrroline boils 'at the same temperature(163-165') as the above, but, on treatment with hydroxylaminehydrochloride, yields nothing but a small quantity of the dioximemelting a t 134-135". The pyrroline obtained in this manner is,2 b 352 ABSTRACTS OF CHEMICAL PSPERS.therefope, /3-ethylpJrroline, that obtained from alcohol and pyrrolinebeing a mixture of a- and 6-ethylpyrroline, boiling at the same teni-perhture.The above experiments fully agree with the aiithors' previousobservation, that /3-pgrroline derivatives are much more stable thana-pyrrolines.Diethylpyrroline yields no trace of oximido-compoundon treatment with hydroxy lamine hydrochloride.( B e r . , 24, 3751-3765 ; compare Abstr., 1891, 1162).--Pyridii~ecarboql chloroplatinite, COPtC12,C5NH5, is obtained as a yellow oil l 1 ymixing an aqueous solution of pyridine with a hydrochloric acidsolution of carbonyl chloroplatinite, COPtCI,. It decomposes at loo",forms a hydrochloride, COPtCl,,C5NH5,HC1, and when treated withhydrohromic acid yields, not the hydrobromide, but the compoundCOPtBr,.C,NH,,HBr.W. J. P.Derivatives of Carbonyl Chloroplatinite. By F. FOERSTEEIt also forms a very unstable picrate.-, - - I C OrtC1, C&H5COPtCl,C,NH,'Dipyridine carboql ch loroplatinosite, is obtainedby mixing a fairly concell trxted hydrocbloric acid solution of carbonylchloroplatinite with an alcoholic solution of pyridine, shaking to redis-sol^ t he precipitate first formed, and recrystallising from alcohol thecrystals t,hat finally separilt,e. I t forms, when pnre, yellowish-greenneedles, dissolves readily in methxl and ethyl alcohol, chloroform, andbenzene, very sparingly in ether, carbon bisulphide, and light petrol-eum, decomposes a t 6U", and is decomposed by mere traces of moisture.I n the reaction mentioned above, carbonic anhydride is evolved, andout of the mother liquor from the substance last described there can beobtained, by evaporation at the ordinary temperature, first lustrous,yellowish-green crystals of a double compound,wbich dissolves without decomposition in hot hydrochJoric acid,and can be dried at 100".Then separate large, colourless, obliqiieprisms of ylatodipyridine chloride, PtCI,(C5NH5), + 3H20, and small,yellowish-brown needles, consisting €or the most part of platoso-&pidine chZorids, Pt (C,NH,CI),, but containing also a little plato-semidipyridine chloride, PtCl (C5NH5),C1. Platosopyridiue chlorideforms, with dipyridine carbongl chloroplatinosite, the double COIJI-pound mentioned above, and froni it, with excess of pyridine, theplatodipyridine chloride was doubtless derived. Dipjridine carbonylchloroplatinosite, when treated with chlorine, yields pyridineplatinochloride, (C5NH,),,H2PtCI6, and hydroplatinochloric acid,H,PtCl, ; when it is boiled with hydrochloric acid, platinum separates,and the hydrochlorides of pyridine carbonyl chloroplatinite and ofpgridine are formed.A compound COPtCl,, (C,NH,,HCl), appearst o he incapable of existence.Analogous bromine componnds were obtained in a similar manner.Pyridiize carbunyl bromoplatinite, COPtBr2,C5NHS, forms yellowneedles or plates melting a t 23-79" ; it dissolves readily in benzene,carbon bisnlphide, ethyl acetate, and hot alcohol, more sparingly incold alcohol, other, and light petroleum; it is decomposed by hoORQANIC CHEMISTRY. 353water. I t forms a hydrochloride, COPtBr,,C,NH,,HCl, and a veryu 11 st able pz crate.Dipyridiu e carbonyl brornoplatinosite, (COP tBr),( C5NH5),, is i n -soluble in most solvents, chloroform excepted.It forms triclinicc+ystnls, which are decomposed by water or when heated to 60".With hydrobromic acid, it behaves like the analogous chlorine com-pound with hydrochloric acid. Platodipyridine bromide,forms lustrous, rhombohedra1 crystals, which are soluble in water andalcohol, but not in ether; it decomposes at 130", forming platoso-pyritline &bromide, Pt( C,NH,Br),. This substance, which ia alsoiormed when an aqueous solution of platodipyridine bromide isallowed t o remain, or boiled with hgdrobromic acid, forms needles,or yellow aggregates of microscopic needles ; it is insoluble in water,and nearly so in aqueous ammonia. As in the case of the analogouschlorine compound, small quantities of an isomeric compound,PtBr2( C,NH,),, were also obtained.Attempts to see if the carbonyl group in these compounds willreact with hydroxylamine or phenylhydrazine, as i t does in ketonesand aldehydes, gave negative results.Hydroxylamiiie exercises areducing action. With an acetic acid solution of phenylhydrazine,carbonyl chloroplatinite yields an unst,able phenylhydrazine cccrboizylclt lor( Flat inite, COPtC12,C6H,N2H3, which crystallises from ethylacetate in jellow plates. It is decomposed by hot. hydrochloric acid,but dissolves in a hot hydrochloric acid solution of carbonyl chloro-platinite, and, on cooling the solution, the hydrochloride,separates out in orange-yellow needles, soluble in alcohol and ethylacetate, but not in benzene, carbon bisulphide, or ether; i t is decom-posed by water when heated a t 100'.Action of Bromine on Para- and Ortho-hydroxyquinoline.By A..CLAUS and H. HOWITZ (J. pr. Chem. [el, 44, 433-45lj.-4 : 3-Bromhydroayquinoline hydrobromide separates as a yellow, crys-talline precipitate when bromine (1 mol.) is added to a solutionof 3-hydroxyquinoline in 10-12 times its weight of glacial aceticacid. It is sparingly soluble in cold water, and crystallises from hotwater in siuall, hard, lustrous granules. It has no definite meltingpoint, bat dissociates when heated. When the aqueous solution ofthe hydrobromide is decomposed by potassium hydroxide or am monk,and acidified with acetic acid, 4 : 3-bromhydrosyqiLinoline is pre-cipitated in felted, small, slender needles ; it melts at 186" (nncorr.),and sublimes ; the platinochloride, with 2 mols.HzO, is described. By4 jxidation with permanganate, the base yielded pyridinedicarboxylicacid, which was converted into nicotinic acid (m. p. 227-229") whenheated; this is evidence that the bromine atom is not in the pyridinering. The orientation given is also supported by the fact that thisbromhydroxyq uirioline is one of the products of the quinolisation ofmefabromoparnhydroxaniline by Skraup's method, as will be shownC. F. B8.3 4 ABSTRACTS OF CHEMIOAL PAPERS.i n a future memoir. The hydrobromide is also formed when a solu-tion of bromine in chloroform is added to one of 3-hydroxyqninolinein the same solvent.B u t an intensely reddish-yellow precipitate isformed when the reaction t.akes place in a solution in concentratedhydrobromic acid, or when bromine is added to t-i solution of 3-hydr-oxyquinoline in chloroform ; this compound would appear to containmore hydrogm bromide than the yellow hydrobromide, into which itchanges, after a time, with evolution of hydrogen bromide.When bromine (1 mol.) acts on 1-hydroxyquinoline, a mixture ofthe hydrobromides of the unaltered base, and of bromo- and dibromo-1-hydroxyquinoline is formed. The product is boiled with water,and the solution, either before or after filtration, mixed with sodiumacetate ; the precipitate is dissolved in hydrochloric acid, and againprecipitated by sodium acetate.The bases are next dissolved inhydrochloric acid, and the solution mixed with suEcient water torender it turbid ; after some hours, the dibromo-derivative sepamtm,and is treated by the same process several times to purify it. Thebromo-derivative can be obtained pure from the solution after a very&mall quantity of sodium acetate has been added to precipitate theremaining dibromo-derirative. The two can also be separated byfractional distillation with steam, when the bromo-derivative passesover first .4 : 1-Brornhydroxyquinoline crystallises from hot water in small,colourless needles, melts a t 124" (uncorr.), sublimes in various but ill-defined forms, and is practically insoluble in cold water. The platino-chEoride was obtained.When oxidised by permanganate, the baseFields non-brominated pyridinedicayboxylic acid ; this settles itsorientation.4 : 3 : l-Dib?.om72.ydro;el~qzlinolilze crystallises in lustrous, slender,yellowish needles, melts a t 196" (uncorr.), sublimes in colourltissiieedles when heated, and dissolves easily in chloroform, acetone,benzene, +cia1 acetic acid, and alcohol, but only sparingly i n ether,and not a t all in cold water. When oxidised by permanganate, it yields~>yridinedicarboxylic acid ; this shows that the bromine atoms arenot in the pjridine ring. When the hydrobromide is suspended inc.hlorvform and acted on by bromine, a red additive compound isproduced, which easily decomposes, like that described above.A. G. B.Oxidation of Piperidine and Tetrahydroquinoline Deriva-tives.By C. SCHOTTEN and W. SCHL~~MASN (Ber., 24, 3687-3700).-€'icrylpiperidine (compare Turpin, Trans., 1891, 714) is hardly actedonat all by potassium permanganate, even on long-continued heating; onoxidation with nitric acid or chromic acid, i t yields rcsinous products.S 0, PhSNH [ C H?] 4*C 0 OH, isohtained, together with small quant itks of phenylsi~lphoiiamide, whenphenylsulphonepiperidine (compare Hinsberg, this vol., p. 64) isoxidised with potassium permangarlate. It' crystallises from hotwater in colourless, nacreous plates, melts at 97", and is readily solu-ble in alcohol, ether, glacial acetic acid, and light petroleum, but, onlysparingly in benzene and chloroform ; when boiled with ncrtic anhydl.iclr., i t is converted into a crystalline anhydride.The bn~*i?cnz. saltPhen y ZsuZpIi one- 8-amidovaZe?-ic acidORGANIC CHENISTHY. 355( C,1H,404NP)2Ba, zinc salt, with 2H,O, and copper salt (abhydrous)were prepared. The salver salt,, CI,HI4O,NSAg, crystallises in lustrousplates. When the acid is heated with concentrated hydrochloric acidat 180°, it yields 8-amidovaleric acid phenylsnlphonate,this salt begins to melt at about 1&O, and is not completely liquefieduntil the temperature has risen to ,I 45" ; when, after i t has solidified,the same portion is again heated, it melts quite sharply a t 10i".When phenylsulphone-6-amidovaleric acid is heated with concentrated,hydrochloric acid and barium chloride a t 2-50", it seems to be decom-posed into 6-amidovaleric acid, sulphuric acid, and benzene.Y heny ZsuZp honet et rahy d ropuinoli ne, C9N EX S O,Ph, prepared byshaking tetrnhydroquinoline with potash and phenylsulphonic chlor-ide, crystallises from dilute alcohol in large, colourless plates, meltsat 67", and is volatile with steam ; it is readily soluble in benzene andchloroform, but more sparingly in glacial acetic acid, ether, alcohol.and light petroleum, and insoluble in water.On oxidation withpotassium permangnnate, it yields very small quantities of an acid,the nature of which was not determined, and a little phenylsulphon-amide; with fuming nitric acid, it jields it yellow compound which isinsoluble in soda.MethyZ tetra11 ydroquinolinecnrboxylate, C9NH,,.COOMc, is obtainedwhen tetrahydroq uinoline is treated with methyl chlorocarbonate i nthe cold.It melts a t about 35", and is insoluble in water, alkalis,and acids, but soluble in the ordinary organic solvents ; on oxidationwith boiling potassium permanganate, it gives a substance which crys-tallises in red needles, melts a t 175', and gives the indophenin reaction ;when heated with potassium permanganate in the cold, it yields verysmall quantities of an acid which iiielts a t 155-156". The dinitn,-derivative, CI1 HIIN3Os, prepared by dissolving methyl tetrahydroquin-olinecarboxylate in fuming nitricacid, crystallises fromnlcohol in goldctineedles, melts a t 174" with decomposition, and is not decomposed bgboiling alkalis or acids ; it is insoluble in ether nnd light petroleum,and oclf sparingly soluble in alcohol, but readily in benzene.Synthesis of Phenylpyrazolidine.By A. MICHAELIS and 0.LAMPE (Ber., 24, 3738-3740).-Sodium phenylhydrazine (2 mols.),benzene, and trimethylene bromide (1 niol.) are mixed and allowe tto remain f o r some time a t the ordinary temperature, the reactionbeing completed by heating on the water-bath; the benzene solu-tion is treated several times with water, and fiiially with dilutehydrochloric acid ; the acid solution, alter ueutralisation with alkali, isextracted with ether. After the ether is distilled, and the residueC5H1IN O,,CJ&.S OSH ;P. S. K.fractionated, phenylpyraaolidine,colourless, or pale-yellow, liquid with a faint, charaacteristic odour ; itboils at 210" under a pressure of 165 mm., anti a t 160" under a pre+sure of 20 mm.The compoiznd has well marked basic properties,reduces alkaline copper solutions on warming, and is readily oxidisedeither by exposure to air or on treatment with mercuric oxide3.56 ABSTRACTS OF CHEMICAL PAPERS.forming phenylpyrazoline. The picrate crystallises in short, yellowneedles. The above synthesis probably proceeds in two stages, anin ternrediate compound, CH2Br-CB2*CH2-NPh*NH2, being first formed ;this is then condensed by the excess of sodium phenylhydrazine : thereaction is therefore analogous to the formation of pyrrolidine fromL-chlorobutylamine by the action of alkalis.A technical product, termed " phenylpyrazine," which is formed bythe action of ethyl f3-bromoyropionate on phenglhydrazine in alkalineco *yH2 The compoundNH*CH2'solution, is 1 : 5-phenylpyrazolidone7 NPh<C9H8N202, prepared by Michaelis and Burmeister from ethyl chloro-malonate and phenylhydrazine (compare Abstr., 1891, l068), provesto be 1 : 3 : 5-phenylpyrazolidone, NPh < J.B. T. CO -?HZNH. OH2'The Osazone of Hydroxypyruvic Acid, By W. WILL ( B e y . ,24, 3831--3834).--In a previous paper (Abstr., 1891, 542), theauthor described n substance obtained by the action of hydrogenchloride on an alcoholic solution of the osazone of hydroxypyruvicacid, which he regarded as its ethyl salt. After dissolving in alkaliand reprecipitating with acid several times, and finally recrystallkingfrom alcohol, it is obtained in reddish-yellow aggregates of needles,which, from the analysis and molecular weight determination, havethe composition C15H12N,0.It is therefore not the ethyl salt, asformerly supposed, but is obtained from the osazone by loss of theelements of water, and is iden tical with the pbenylhydrazineketo-phenylpyrazolone obtained by Knorr by heating the osazone withacetic anhydride (Abstr., 1888, 724). Its formation is represented asfollows :-It is insoluble in water, readily soluble in alcohol and ether, sublimesin small quantities, and colours wool and silk yellow in alkalines o h t i on.The osazone of hydroxypyruvic acid differs from the similar com-pounds investigated by Knorr, inasmuch as the solutions of its saltsdo not yield the pyraxolone directly on acidification.The osazoneitself yields a sodium salt, as already found by Nastvogel (Abstr.,1889,237). The pyrazolone, however, also yields a sodium compound,which crystallises in slender, yellow needles, and melts at about 300"with decomposition. It also forms a silver conzpound, C15H11AgN40,which crystallises in reddish-yellow plates, becomes brown at 206",and melts at 215".The etbyl salt of the osazone may be obtained by the action ofmethyl iodide and alkali on its alcoholic solution. It is a yellow,microcrystalline powder which melts at 222-223", and is insoluble inalkalis and dilute acids. H. G. C.Phenylguanazole. By G. PET~LIZZARI (Guzzetta, 21, ii, 141-154).-Phenylguanuzole is prepared by heating a mixture of dry dicyanoORGFANlC: CHEMISTRT. 357diamide with phenylhydrazine hydrochloride, in molecular proportion,at 150"; much ammonia is evolved during the reahon, and, asspontaneous heating occurs, the mixture must be cooled if the tempe-rature rises above 180". The vitreous, yellow product is crystallisedfrom dilute hydrochloric acid, dissolved in water, and decomposed byconcentrated caustic potash, when the base separates in red needles;on recrystallisation from alcohol, it is obtained in large, hard, slightlyyellowish crystals melting at 174+--175".It is very soluble i n alcoholand water, but only sparingly in chloroform, ether, or benzene ; i t isprecipitated from its aqueous solutions by caustic soda and causticpotash.The molecular formula, as determined by the cryosoopicmethod, is C8H,N,. The aqueous solution is neutral to test-paper.q'he hydrochlo~ide, C8HgN5,HCl, crystallises in thin, white scales, verysoluble in water and alcohol, and melts at 240". Theylutinochloyide,(C,H,N,),,H,PtCl,, forms' yellow, prismatic needles. The aqueoilssolution of the base gives a white, flocculent precipitate with silvernitrate, soluble in hot water, nitric acid, and ammonia; it is a mole-cular compound of phenjlguanazole with silver nitrate,Silver sulphate and mercuric chloride give white precipitates withaqueous solutions of the base ; mercurous nitrate gives a white pre-cipitate soon turning yellow ; and copper salts give a yellowish-greenprecipit,ate. These precipitates are all molecular compounds.Thereaction between dicyanodiamide and phenyl hydrazine hydrochloridemay be carried out in alcoholic solution by heating for eight hours ina closed tube at 100".C€B9N5,AgN03.The reaction is represented by the equationNHPh*NH, + ~H*C(:NH)*NH*C(:NH).NH, =$I (:NH)*NHNH*C(:NH) >NPh + NHpAnilbiguanidine is probably an intermediate product of the reaction,for if anilguanidine hydrochloride (1 part) and cyanamide (1 part) beboiled with water (8 parts) for six hours, and treated with potash,ammonia is evolved and phenylgumazole separates. Pheny lguan-azole is also obtained by heating together at about 160" eqnalparts of anilguanidine hydrochloride and guanidine carbonate ; jargequantities of ammonia are evolved ; the product is dissolved in diluteIiydrochloric acid, and filtered ; on treating with solid potash,crude phenylguanazole separates, and is purified by repeated extrac-tion with chloroform.A mixture of biguanide wit.h phenylhydrazinein molecular proportion, when heated at 120-160", evolves muchammonia, and, on extracting the product with alcohol, evaporating,dissolvirig in water, treating with a little potash, filtering, and addingexcess of potash, pheriylguanazole is obtained. The yield by thelast two methods is small, but they show the very great analogywhich exists between phenylguanazole and phenylurazole (Trans.,1888, 550).Ethylanilbiguanidine, NH,*C(:NH)*NH-C(:NH)*NH-NEtPh, is pre-pared by heating unsymmetrical ethylphenylhydrazine hydrochloridewith dicyanodiamide in molecular proportion, at 160-170", for hal858 ABSTRACTS OF CHEMICAL PAPERS.an hour.No ammonia is evolved. The product is dissolved in water,filtered, and treated with caustic potash ; the base separates as an oilwhich is extracted by agitation with ether, and the residue left onevaporating the ethereal solution is boiled for some time with waterto eliminate unaltered ethylphciiylhydraxine ; caustic potash is theriadded, and the precipitate again extracted witlh ether ; on evaporatingthe ether, the base is obtained as a vitreuns, friable mass whichsoftens a t about. 50". It is very soluble in alcohol, ether, and benzene,less so in water ; i t has a strongly alkaline renction, and absorbs carh-onic anhydride. When boiled with potash, it yields ammonia and ethyl-phenyl hydrazine. The sulplznte, ClnH16Ns,H,S04, is obtained in small,colourless crystals which are very soluble in water, but only sparinglyin alcohol.w. J. P.Tropine. By G. MERLING (Bey., 24, 3108--3126).-The experi-ments to be described, taken in conjunction with the facts alreadyknown, prove that neither the formula, proposed by the author, nrlrt h a t of Ladenburg, which Liebermann has already shown t o be un-tenable (Abstr., 1891, 749), represents the constitution of this com-pound. In the present research, the author commenced his experi-ments with Roth's methyltropidine (Abstr., 1884, i S l ) , a compoundwhich proves to have properties entirely different from those ascribedto it by Ruth, and piocec,ded on the lines laid down by him Tor the in-vestigation of certain bases allied to piperidine ( A m d e n , 264, 310 ;Abstr., 1891, 1.506).z-Methyltropidine (A8 "-dihydrobenzyZdimethlJlamine, see below),C6Hi*CH2NMe,, is prepared by distilling a dilute aqueous solutionof tropidinemethylammonium hydroxide until it reaches a conccntrii-tion of 1 : 10, and then driving the base over with a current ofsteam ; i t is a colourless, mobile oil, of a faint ammoniacal odour, andcannot be distilled, as it changes into /3-methyltropidine on heating ;the yield is equal to that, of the tropidine employed.The p f u t i n c -chlol-ide, (C,H,,N),,H,PtCI,, cr.ystallises from boiling water in orange-yellow prisms, and melts at 173-174" ; the aurochloride,is a golden-yellow, crystalline precipitate sparingly soluble in water,and decomposing when boiled with i t ; the methiodids, C6H9NMe31, isreadily soluble in hot water, sparingly in cold, and melts a t 162" withthe evolution of gas.Hydrochluru-a-methy Etropidine,C,H,H Cl-CH,*NMe,,is obtained as the hydrochloride, when a-methyltropidine is allowedto remain for some days at the ordinary temperature with a solutionof hydrogen chloride saturated at 0" ; the azwochloride,CgH ,~CIN,HAUC~~,separates as a yellow, crystalline precipitate on adding auric chloride,and the free base as a colourless, mobile oil on adding sodium hj-dr-oxide to the solution; the latter changes slowly a t the ordinal-gtemperature, or quickly a t the temperature of the water-bath, into ORGANIC CHEMJSTRY.359viscid syrup which consists essentially of t~ropidinemethylamnioniumchloride. It is poured into water and distilled in a current of steam,when a small quantity of a-methylpiperidiue passes over; the residueis shaken with ether to remove the resinous snbstances, solutions ofsodium hydroxide and potassinm iodide added, and the prcci pitatedtropidinernethylttmronium iodide orystallised from boiling alcohol ;it is next converted into the chloride by silver chloride, and this saltyields tropidine and methyl chloride on dry distillation. Thesereactions are analogous to the conversion of pentallylcarbindiniethyl-nmine into methyl-a-pipecoline, and indicate the presence of thegroup iC*NMe*CH(CH,R)- in tropidine.The formation of a-ethyl-pjridine from norhydrotropidine (Ladenburg) shows that the a-carbonatom carries an atom of carbon not belonging to the hydrngenisedpyridine nucleus; whilst that of the bibasic tropic acid, by theoxidation of tropine with chromic acid, proves that the second carbonatom of the side chain is also in combination with one of the nuclealcarbon atoms. When a-methyltropidinemethylsmmonium iodide isconverted into the hydroxide, and this is boiled with water, it decom-poses into tropiiidene, C7HS, trimethylamine, and water, a reactionwhich points to the presence of the group =CH.CH,*NMe, i na-methyltropidine. These facts are only to be accourited for byadopting the following formulae :-Tropine.,CH2 CH2CH-CHzCHLCH ; C O O H * C H < ~ ~ : : ~ ~ ~ > C H * C O O H .'CH,.N Me'Tropidine. Tropic acid.Methyltropine is, therefore, As-hydroxytetrahydrobenzyldimethyl-smine, and a-methyltropidine is As : 5-dihydrobenayldimethylamine.Tropilidene, C,H8, when dissolved in carbon bisnlphide and treatedwith brdmine, forms a dibromide which is an oil miscible with et,herand having a camphor-like odour ; when kept in a desiccator, it. resini-fies hy degrees, and, when heated on the water-bath for some hours,Iiydrogen bromide is evolved, and it is converted into a crystallinemixture of benzyl bromide and a substance separating from alcoholin yellow tablets, which is perhaps an isomeride of the dibromidc.When tropilidene (1 gram) is heated in a reflux apparatus for anhour with sulphuric acid (5 grams), water (20 grams), and potassiunidichromate (3.2 grams), a mixture of benzoic acid and benznldehydeis formed with evolution of carbonic anhydride. Tropilidene is,therefore, probably CH,:C<CH CH*:CHZ, -CH>CH.p- Methyltropidine, C7HaNMe2, is prepared a9 follows :-a-Met<hyl-tropidine is heated at 140-15d" in a reflux apparatus; on now re-moving the source of heat, the temperature rises to 190" ; the liquidis maintainell at this f o r boiut: miiiutes, a i d is then distilled, lie360 ARHTRACTS OP CHEJIICAL PAPERS.s v a l l quantities of di- and tri-methylamine pnss over, and at 200' afew drops of tropylen; whilst 13 methyltropidine passes over at204-205" (757 mm.), and a small quaritityof a base boiling at a veryhigh temperature remains behind as a thick, brown oil. It is acolourless, highly refractive oil, having a characteristic odour, and asp. gr. 0.922 at 15". When 13-methyltropidine is dissolved in hydro-chloric acid and the solution heated, tropylen separates as an oil andis driyen over with a current of steam ; whilst dimethylamine hydro-chloride remains behind. The fact that Ladenburg obtained tropylenand dimethylamine by heating tropidine methiodide with potash is,therefore, explained as follows :--a-Methgltropidine is initiallyformed, and this changes into the @-compound, which then decom-poses into fopylen and dimethylamine. When P-methyltropidineand met,hyl iodide are mixed in molecular proportion in methylalcoholic solution, tetramethylammonium iodide separates : thequicker if heat is applied ; whilst after removing the iodine fromthe solution by silver chloride, platinic chloride precipitates a pZatino-chloride, ( C,H,Me)2,H2Pt,(>16, as a bright-yellow, aniorphous precipitate,zind on evaporating the filtrate, an oily compound at first separates,R nd, later, lustrous crystals of the platinochloride, C,H1Me,,H,PtCl6.The author finds, contrary to TAadenburg's statement, that tropylenforms a crjstalline compound with potassium hydrogen sulphite, andit, must therefore be an aldehyde or a ketone ; since it gives an acidof the composition of adipic acid on oxidation, it is probably tetra-hydrobenzaldehyde, and in concordance with the above formulce, theA5-derivative. Ecgonine arid anhydroecgonine must, in conformitywith the above-given formula for tropine and tropidine, be repre-sented as follows:-,CHZ- CH2, CHZ- CH2,CH-CH(OH)-CH(COOH)-C ; CHLCH:C(COOH)-CH.'CH,--- NMe' 'C'H,----NMe/Ecgonine. Anh y droecgonine.The formation of dihydrobenzaldehyde from dibromanhydroec-gonine (Eichengrun arid Einhorn, Abstr., 1891, 65), then, admits ofsimple explanation. The dihydrobenzaldehyde must be the A3' 5-de-ri vative. A. R. L.A Violet from Codejlne. By P. CAZENEUYE (Conzpt. rend., 113,747--749).-10 grnms of codei'ne is heated with 10 grams of para-nitrosodimethylaniline i n presence of a litre of ethyl alcohol of 9 3 Ofor 300 hours. When tho liquid cools, i t deposits tetramethyldiamido-azobenzene. The alcohol is distilled off and the residue boiled withwater; after cooling, the liquid is filtered and agitated with amylalcohol, which dissolves out the violet colouring matter, whilst abeautiful blue colouring matter remains i n the water. When theamyl alcohol is evaporated, the violet, compound separates in amorph-ous, lustrous flakes, somewhat soluble in water, but especially solublei n ltlcohols and in ether, forming dichroic solutions. When theaqueous solution is poured on to strong sulphuric acid, it gives, likethe safranines, a green zone, changing to blue, and then to violetORGANIC CEEMISTRY. 361which indicates the presence of poly-acid combinations. The morph-ine violet gives a similar reaction.Codeine violet dyes silk, wool, and gun-cotton directly, but thecoloar alters somewhat when exposed to light.When the amyl alcohol solution of the compound is mixed withalcohol and ether, and treated with platinic chloride, a platino-chloride is obtained with a pder colour than the platinochloride ofthe analogous morphine compound.Nkfe$C6Hd*n: C17H18MeNOd, H2Pt CI,,NMe,*C6 H4*N :C17H,,MeNOd.It has the compositionand hence codeine violet has the composit’ionThe yield is small, but better results were not obtained by vary-Heating in a sealed ing the proportions uf tlhe reacting substances.tube gave a smaller yield (compare Abstr., 1891, 1220).C. H. B.An Alkaloid from Javan Coca Leaves. By F. GIESEL (Chem.Centr., 1891, ii, 488, from Pharrn. Zeit., 36, 419--420).-From 20kilos. of a smnll-leaved Javan coca, the author obtained 1 kilo. ofcinnamylcocaine, whilst about three times this amount, besides somecocaine, remained uncrystallisable. Prom the mother liquors analkalo’id was separated as hydrobromide, which resembled dextro-cocaine.The hydrochloride is more readily soluble i n water, and lesssoluble in alcohol, than is the hydrochloride of dextrococaine. Thesalts of the new alkaloid are precipitated crystalline from quitedilute solutions by potassium dichromate, which is not the casewith the salts of cocsi’ne or dextrococayne ; moreover, the polarisedray is not perceptibly deyiated.Concentrated hydrochloric acid splits it u p into benzoic acid andecgonine hydrochloride, without the formation of an intermediateproduct, as in the case of dextrococayne.The alkaloid could not be detected in the leaves of Americantruxillo ; a t the same time, an alkaloid, somewhat resembling Hesse’shygrine, but different from it., was obtained from them. It differsfrom Hesse’s hygrine in its solubility in solutions of the alkalis,and is destroyed by potassium permanganate ; whilst Hesse’s remainsunchanged. It occurs in the leaves in quanbities up to 0.2 per cent,and is 8 constituent of the plant, and not a product of decomposition.The hydrobromide melted at 49’.J. W. L.Cyanmethaemoglobin ‘and Detection of Hydrogen Cyanide.By R. KOBERT (Chem. Centr., 1891, ii, 501, from Apoth. Zeit., 6, 386).-Researches carried out by the author indicate that hydrogmcyanide forms with methEmoglobin a red compound cyan0m.t-hmnznglohin, which differs from oxyhmmoglobin and its modificativrisin that its spectrum is n o t characterised specially by any band.The remarkably bright-red colour of the blood, after poisoniiig withhydrogen cyanide, in places where the formation of methsemoglobi362 ABSTRACTS OF CHEMICAL PAPERS.has taken place, is caused by the formation of the cjanogen corn-pound.Blood which contains the cyanogen compmnd may be detectedilius:-l C.C. of the blood is dilutecl with 99 C.C. of water and n 1 percent. solution OF potassium ferricyanide is added drop by drop. I fcyanogen is absent, the colour of the solution passes from red toyellow, owing to the formation of methremoglobin, and it shows thecorresponding spectrum. In the presence of cyariogen, the colouronly becomes brighter red, and shows no absorption band. Hvdrogencyanide may be deteched by means of this test. Healthy blood isemployed, and, after diluting with water (1 C.C. of blood to 99 C.C. ofwater), it is shaken with a small crystal of potassium ferricyanideuntil the red colour has just changed to yellow, and it little of theliquid undei*.investigation is poured on to the surface. The presenceof hydrogen cyanide causes a bright-red coloration to form. Thesolutions must, nob be alkaline, b u t stionld be just acid.If blood contains cyanogen, a 1 per cent,. solution retains its colourfor some time ; whereas healthy blood becomes darker at the end ofa few hour6 or days, and shows the spectrum of hremoglobin.J. W. L.Transformations of Albumins. By G. PATEIN (Cornpi. rend.Snc. Bid., 1891, 207--212).--Brom experiments on egg-.albumin andserum-albumin, it is shown that the action of acetic acid and alkalisproduces changes in the albumin which render it 110 longer coagulableby heat or precipitable by certain reagents. The same sometimesoccurs in the albumin which passes into the urine in cases of disease.W. D. H