34 ABSTRACTS OF CHEN ICAL PAPERS.Organic C h e m i s t r y .Exchange of Chlorine, Bromine, and Iodine between Organicand Inorganic Compounds. By R. BRIX (Awnalen, 225, 146-170).-These experiments were made to ascertain the iufluenceexerted by the nature of the element contained in any inorganichaloid compound on the exchange of halogens with a n orgauic haloiOHGAICIC CHEJIISTRT. 35derivative. The organic compounds employed were ethyl iodidtl,isobiityl chloride, benzyl chloride, and ethyl monochloracet ate, theinorganic compounds were selevted from tlhe lialogen compoundsof the alkaline earths, of the heavy metals, and of arsenic, antiinon!-,and bismuth. The mixtures were heat,ed i n vessels provided witha reflux apparatus, except when otherwise mentioned.Calcium chloride and ethyl iodide do not react at the boiling point'.Barium chloride and ethyl iodide react very slightly a t 14f~".Barium iodide and isobutyl chloride do not, react on boiling.Bariumiodide and ethyl monochloracetate exchange their halogens completelyat the temperature of the water-bath. Barium iodide and benzylchloride give a partial interchange. Cupric chloride and ethj-1 iodidedo not react when boiled together, but on heating with alcohol a t1.50-160" complete interchange is effected. Zinc iodide arid ethFlmonochloracetnte react readily and nearly completely at 90 -100".Zinc iodide and benzyl chloride react on mixing, the interchangebecoming complete a t 43-50". Zinc iodide and isobutyl chloride donot react when boiled together.Cadmium chloride and ethyl iodide d onot react when boiled together, but partial interchange is effected byheat#ing a t 130-140" in sealed tubes with alcohol. Cadmium broriiitlesueers partial interchange when boiled with either benzyl chloride ore1,hj-l monochloracetate, but does not react with ethyl iodide. Cad-mium iodide gives but a slight interchange with ethyl monochlor-acetate, reacts readily but not completely with beuzyl chloride, and doesnot react with isobutyl chloride except in sealed tubes a t 135", whendecomposition-products are formed. Tlialli uin chloride and ethyliodide do not reaet. Thallium iodide and ethyl mono2hloracet;tte givea partial reaction in presence of alcohol. Lead chloride and ethyliodide do not react, but in sealed tmbes a t 1.?0-160" in presence ofalcohol, nearly complete interchange is erected.Lend iodide andbenzyl chloride do not react unless heated a t 150-160" in presenceof alcohol, when a partial reaction occurs. Arsenious bromide re-acts completely with either benzyl chloride or ethyl monochloracetatea t 140-145" in presence of alcohol, ALnCiinonious bromide gives a,complete intrrchange with either ethyl iodide or ethjl monoelllor-acetate a t 140-145" in pi*esence of alcohol. Bismuth bromide andethyl iodide give a partial intuerchnge ah 150-160" in pyesence ( J €alcohol. Bismuth bromide and ethyl monochloracetate heated withalcohol a t 140" give decomposibion-products.Exchange of Chlorine, Bromine, and Iodine between Inor-ganic and Organic Compounds.By B. KOHNLEIN ( A n n d c ~ ,A. J. G.225, 171-1' 5).-This paper is essentially a continuation of Biix's(preceding Abstract), from which it differs in the use of a much laryernumber of metallic compounds ; in the employment, as far as possible,of the same temperature (145-150" for four hours) in all cases, so 8sto obtain comparable results; and in the avoidance of the use ofalcohol, which in many c'ctses vitiates the results.Lead iodide and isobutyl chloride react to a very slight extent ; withlead chloride and ethyl iodide, on the contrary, nearly complete inter-change occurs. Antimonious chlori l e and et!iyl iodide exchange theird 3ii ABSTRACTS OF CHEMICAL PAPERS.halogens completely. Antimonious bromide and ethyl m onochlor-ticketate react partially ; antimonious bromide and ethyl iodide reactcompletely. Antimonious iodide and isobutyl chloride react withdecomposition, butylene being formed.Arsenious chloride and ethyliodide undergo complete interchange. Arsenious bromide does notreact with isobntyl chloride ; it reacts partially with ethyl monochlor-acetate ; it does not react with ethyl iodide unless the temperature israised to 150-160", when complete interchange takes place ; it reactscompletely with isopropyl iodide. Arsenious iodide scarcely reactswith ethyl monochloracetate, and does riot react with isobutyl chloride.Phosphorous chloride and ethyl iodide do not react. Phosphorousiodide does not react with ethyl monochlorncetate in open vessels a t143", although complete decomposition occurs in sealed tubes at 1FiO" ;it dces not react with isobutyl chloride at 140°, but complete decomposi-tion occurs a t 160-170" ; it reacts with propyl chloride with decompo-sition a t 1,50".Stannous chloride, or stannic chloride, and propyliodide react nearly completely, whilst stannous iodide scarcely reactswith propyl chloride. Zinc chloride, or cadmium chloride, and propyliodide give a nearly complete reaction. Propyl iodide suffers decom-position if heated with titanium chloride. Yerrous iodide or chloridegives practically no reaction with the corresponding propyl compounds.Manganous iodide and propyl chloride exchange their halogens nearlycompletely ; manganous chloride and propyl iodide do not exchange,but the propyl compound suffers partial decomposition.Cobaltchloride and propgl iodide react slightly ; cobalt iodide and propylchloride scarcely react. Nickel chloride and propyl iodide, and nickeliodide and propyl chloride respectively are practically without actionon one another. Thallium chloride and propyl iodide react partially.Magnesium chloride and propyl iodide do not react. Calcium iodideand prop~-l chloride give a complete interchange. Strontium iodide2nd propyl iodide exchange partially, whilst strontium chloride andpropyl iodide do not react. Barium chloride and propyl iodide arewithout4 action on one another.The author draws the following conclusions as t'o these reactions :-K, Mg, Ca, Sr, Ba, Al, Mn, and Co unite by preference with chlorinerather than with bromine and iodine, and with bromine rather thanwith iodine (under some circumstances Sr, Ba, and Co gives light inter-changes in the opposite direction).Zn, Cd, T1, Bi, Fe, and Ni showno constant rule of interchange. Cu, Ag, Hg, Sn, Pb, As, and S bunite by preference with iodine rather than with bromine or chlorine,and with bromine rather than with chlorine. A. J. G.Action of Chlorine on Organic Compounds in Presence ofInorganic Chlorides. By A. G. PAGE ( A m d e n , 225, 196-211).-Some years ago Arouheim showed that the presence of molybdenumpentachloride greatly facilitated the chIorination of aromatic com-pounds, but, from some preliminary experiments, did not appear tohave the same effect on the chlmination of fatty bodies (this Journnl,1876, i, 309).The author has continued this investigation andextended it to the emplojment of other inorganic chlorides.Chlorine does not act on acetic chloride, even in presence of molybORGASIC ClIE-\IIST RT. s7dennm pentachloride. The chlorination of butyric chloride atid ofethylene chloride is actually hindered by the presence of molybtleiiuiiichloride. Molybdenum trichloride does not assist chlorination belowt,he temperature (70') at which it is converted into pentachloride.Of the numerous other chlorides experimented with, the following onlywere found to assist chlorination : Fe2C16, Al2CI6, TlCI, and TICI, ;the chlorinating action of MoC1, and SbCl, is already well known.As regards the action of these bodies in assisting chlorination, theauthor regards the view that a molecular compound is formed betweenthe metallic chloride and the substance being chlorinated, whichcompound is i n the second place decomposed by chlorine with forma-tion of hydrochloric acid and a chlorinated product, as being moreprobable than that which is based on an alternate reduction andchlorination of the inorganic chloride.Chlorine has no action on nitrobenzene, but in presence of ferricchloride a t ordinary temperatures it converts it into the dichloronitro-benzene [Cl : C1 : NO, = 1 : 4 : 3j, and a t 100" into the tetrachloro-nitrobenzene [Cl : C1 : NO, : C1 : C1 = 1 : 2 : 3 : 4 : 51, whilst athigher temperatures it converts it completely into perchlorobenzene.Whilst chlorine acting alone on alcohol converts it chiefly intochloral alcoholate ; in the presence of ferric chloride, it converts it intoa mixture of chloral and (very little) chloral hydrate. A.J. G.Anthemene, a Hydrocarbon obtained from Roman Chamo-mile. By L. NAUDIN (Bzdl. SOC. C'hiln., 41, 483--$88).--From theflowers of ch2momile (Ant11,emis nobilis), the author has obtained twowhite crystalline substances, one of which appears to be a hydro-carbon. The flowers are exhausted completely with light petroleum,the solution thus obhained is evaporated to one-ninth of its bulk, andthe liquid residue allowed to stand. I n a few days, groups of whitecrystals of the new substance separate out, and in the mother-liquidare substances previously described by Demarpy, Fittig, and Kopp.The crystals were purified by recrystallisation from ether and lightpetroleum, and were found to consist of two substances.9 s oneof them is twenty-four times as soluble in absolute cold alcohol asthe other, they were separated by dissolving in hot alcohol, boilingwith animal charcoal, and filtering. Anthemene crystallises out o! Lcooling, and the second substance melting a t 188-189", the investigil-tion of which has not yet been completed, remains in solution. Theprocess of separation was yepeated twelve times. The yield is verysmall, for from 1 kilo. of t,he flowers the author only obtainetl1.5 grams of anthemene and 4.5 grams of the second substance.Anthemene crystallises in sleiider microscopic needles melting at63-64", and boiling a t about 440" without much decomposition ;sp.gr. 0.942 a t 15". It is insoluble in water, but soluble in ether,petroleum, carbon bisulphide, and chloroform, and soluble in hotabsolute alcohol, but almost iiisoluble in cold (at 25", 1 litre dissolves0.333 gram). The vapour-density by V. Mepx's method in thevapour of sulphur was 127 (theor. 131). The results of analysis givethe percentage of carbon 83.80, and of hydrogen 14.40, showing a lossof 1-80. Scliiitzenberger, who repeated the analyses, obtained simila38 ABSTRACTS O F CHEMICAL PAPERS.rcsults, and the author cannot account for this loss, as the compoundappears to be pure and to contain no oxygen. It appears to be of theser:es CnHIZn, and to be a p-octadecene (C 85-82? H 1418).Diethoxymethane, and Preparation of Methylene Dichloride.R.y W.H. GREENE (Chem. News, 50, 75--76).-The author has madecliethoxymethane from sodium ethylate and methylene dichloride.S ,dium, in equal molecular proportion, is added gradually to a mixtureof methylene chloride with excess of absolute alcohol contained in aflask fitted with reflux condenser ; when all the sodium has been added,the mixture is heated for an hour, and then distilled. The product isfractioned, and all which passes over below 78' is shaken with calciumchloride solution, the uppep layer separated, dried, and rectified, whenpure diethoxymethane is obtained boiling a t 86-89'. It is an etherealliquid with penetrating mint-like odour, boiling at @go under 769 mm.pressure.I t is slightly soluble in water,and miscible in all proportions with alcohol and ether.The following is recommended as the most convenient process forpreparing methylene chloride. A mixture of zinc and chloroformwith much alcohol is treated with a small quantity of hydrochloricacid in a flask fitted with a condenser ; heat is developed and chloro-form aiid methylene chloride distil over. When the reaction subsides,more hydrochloric a'cid is added, and a gentle heat is applied untilnear the completion of the operation, which is stopped when thealcohol commences to come over in large quantities. The distillateis rectified, the portion coming over below 53" being retained, whilstthe rdsidue is again treated with zinc, $c.This operation is repeatedseverd times, and ul timntely, by numerous careful rectifications ofthe product boiling below 53", pure methylene. chloride boiling at40-41" is obtained.A. B.Its sp. gr. at 0" is 0.851.D. A. L.Mercury Fulminate. By A. EHRENBERG ( J . pr. Chew., 30,38-G8).-Cnrstanjen and the author have shown (Abstr., 1882, 816) thatwhen mercury fulminate is decomposed with aqueous hydrochloricacid, it yields its nit'rogen as hydroxylamine lipdrochloride. A furtherexamination of this reaction bas proved that both carbonic oxide andcarbonic anhydride are formed. The quantit'y of t,hese compoundsproduced is but small, more especially when the decomposition iseI"fectcd in absence of air ; and it appears that they owe their originto the decomposition of formic acid, which the autbor has shown isproduced by the action of aqueous hydrochloric acid on mercuryfulminate. Tlie reaction taking place may be represented as follows :-C2HgNz02 + 2HC1+ 4HzO = 2H.COOH + 2NH1.OH + HgCI,.I n the hope of realising the following decomposiiion, and thusobtaining fulminic acid, C,HgN,O, + 2HC1 = HgCl, + C,H,N2O,, bheauthor passed dry hydrochloric acid gas into perfectly dry ether con-taining mercury fulminate in suspension.Mercuric chloride is pro-duced, and the ether holds in solution a compound which undergoesspontaneous decomposition, most probably fulminic acid. If thisethereal solution is carefully added to aqueous ammonia, and thORGAINIC CHEMISTRY.39ethereal solution separated from the aqueous solution, the lattercontains a yellow solid which is sparingly soluble in cold water, butsoluble in hot water, from which it may be obtained in yellowishneedles. The analysis of this compound shows it to be C3H,N,02 ; itforms with silver nitrate a cornpound, (C9H4N,0,),AgN03, insoluble incold water, and with an ammoniacal solution of copper oxids thecompound (C3H4N,02)2CuO(NH3)2, which is obtained as a light bluegranular precipitate. From the ammoniwal solution from which theabove compound was obtained, the author has isolated an acid isomericwith fulminuric acid, to which the name Isofulminuric acid is given.It is easily soluble in water, from which it separates in ill-definedcrystals ; absolute alcohol dissolves it easily, and by cooling the hotsaturated solution it is obtained as a white powder. With silvernitrate, its aqueous solution gives a white amorphous precipitate ofC3H,N303Ag, but yields no precipitates with ammoniacal solutionsof copper oxide, lead acetate, or mercuric chloride.The silver,ammonium, and barium ealts of this acid are described.Together with this acid, there is formed a small quantity of a com-pound more easily soluble in ether than isofulminuric acid, which ismost probably the ammonium salt of amidofulminuric acid,C3H (NH,)N,Os.NH,.Its aqueous solution gives precipitates with silver nitrate, lead acetate,and copper sulphate, and a blood-red to brownish-red coloration withferric chloride.Thiocyanic acid reacts with merciiry fulminate in a manner ana-logous to aqueous hydrochloric acid, mercuric thiocyanate, ammoniumthiooyanate, and carbonic anhydride are produced.the productionof the ammonium salts arising from the instability of hydroxylaminethiocj anate. The reaction may be represented thus :-C2HgNZ02 + 4H.CNS + 2HzO = 2CO? + Hg(CNS), + 2NHd.CNS.The action of ammonium thiocyanate on mercury fulminate isanalogous to the action of the chlorides of the alkali metals, but ismore energetic ; it may be expressed as follows :-2(CJT,OzHg) + 2HzO + 2NHk.CNS = C,H,N,O,.NH, + Hg(CNS), + HgO + CO, + 2NH3.Mercury Fulminate. By L. SCHOLVIEN ( J . pr. Chem., 30, 91-Y2).-A solution containing sodium fulminate is formed by treatingmercury fulminate suspended in water with sodium amalgam.Whenthis solution is decomposed with dilute sulphuric acid and shaken upwith ether, the ethereal solution is found to contain two acids of thecomposition HCNO. The less soluble of these crystallises from etherin colourless needles melting at 85" ; it is soluble in lukewarm watei,but is decomposed by boiling water. It forms a red insoluble silversalt, a dark yellow mercuric salt, and light yellow lead salt. Itssolutions yield a deep red coloration with ferric chloride. Decom-posed by hydrochloric acid, it yields hydroxylamine. The moresoluble isomeride may be crystnllised from hot water, jields noP. P. B40 ABSTRACTS OF CHENICAL PAPERS.coloration with ferric chloride, and forms no insoluble metallicsalts.The aqueous solution of sodium fulminate gives a precipitate clfsilver fulminate with silver nitrate, which when treated with metallic:chlorides and aniline hydrochloride forms double salts.It is decom-posed by ethyl iodide, and with potassium sulphide yields an easilyexplosive compound.Mercury fulminate and thiocarbamide yield carbonic anhydride,mercuric sulphide, carbamide, a compound thiocarbamide and mer-curic thiocyeuate. P. P. B.Rhodanic Acid. By M. NENCKI and BOURQUIN (Ber., 17, 2277-2282).-10 grams of rhodanic acid, C3H3NSz0, dissolved in 50 C.C. of90 per cent. alcohol, were mixed with 30 grams of strong sulphuricacid and heated on a water-bath ; 15 grams of benzaldehyde werethen added gradually. On cooling, or on the addition of water,BenzyZidene-~hod~iiic acid, C,oH7NSz0, crystallises out.When purifiedthis acid forms yellow needles, melting a t 200" (uncorr.). It givescrystalline salts with the alkalis, very easily soluble in alcohol andwater, less so in concentrated alkalis. It forms a yellowish-greensilver salt, CloH6AgNSz0, and an amorphous lead salt. The reactiontakes place according to the equationC3HJYS,O + C,H,.COH= CJT7NS20 + HZO.Acetaldehyde or its ammonia-compound similarly yields ethylidene-rhodanic acid, C,H,NS,O. This substance forms small yellow needles,melting a t 147-148". It is very sparingly soluble in water, easily inalcohol. Both of these com-pounds are decomposed when heated with alkalis, the aldehydesbeing reformed and the rhodanic acid further decomposed.Salicy 1-aldehyde and parahydroxybenzaldehyde also form similar condensa-t.ion-compounds, but these have not been investigated.When heated with water a t 200' in closed tubes, rhodanic acidis split up into carbonic anhydride, sulphuretted hydrogen, andammonium thioglycollate. When warmed with alkalis, it is readilydecomposed, potassium thiocyanate and a crystalliiie potassium (orsodium) salt sparingly soluble in alcohol being the products. Theacid or' which this is the salt appears to have the composition of ananhydride of thioglycollic acid, and to be of the formula(SH. CH2. CO),O.This acid is now undergoing investigation.As this formation of thiocyanic acid by the action of alkalis takesplace a t so low a temperature, there can be little doubt that the thio-It gives a yellow amorphous lead suZt.Ljanic group is already present in rhodanic acid.The formulaS 1 C<:$zF>CO, proposed by Liebermann, is therefore very im-probable, and that originally proposed by Nencki, SH.CH,.CO.S.CN,is in all probability the correct one.Circular Polarisation of Dextrose. By R. TOLLENS (Bey., 17,22%--2238).-1n continuation of his investigations with cane- sugarL. T. TOItGANIC CHEMISTRY. 41(Abstr., 1884,1285), the aut'hor has now examined very dilute soIutionsof dextrose. He finds that here, as in the case of cane-sugar, no increaseof rotation takes place, but that the same formula may be employecifor calcnlaiing the rotation whatever the degree of concentration ofthe solution.The dextrose employed was very carefully purified bythe method recommended by Soxhlet, and was purer than that pre-viously used. The author has therefore slightly amended his oldi'orrnuke, which now become-A (for anbydrous dextrose) [ a ] D = 52.50" + 0.018796P +B (for dextrose hjdrate) [%ID = 47.73" + 0.015534P +The following table gives a comparison between the results actually0-00051tXGP2.0.0003883P2.found with a Landolt-Laurent polarimeter and those calculated :-Weight of sugar in Rotation for [~ID.1.49 78 5 2*4( I 7 52.53d0 - 0.125"1.7933 52.289 52,537 - 0.2482.7533 52.370 52.556 - 0.1867.6042 52.691 52.673 + 0.01810.0992 52.738 52.742 + 0.00410,2567 5 2- 63 ti 52.747 - 0.11117.5982 52.991 52391 - 0~000100 grains solution.7--- -7 P. Found. Calculnt ed. Difference.L. T. T.Non-identity of Arabinose and Galactose. By E. 0. v. LIYP-MANN (Ber., 17, 2238-2240).-The author confirms Scheibler'sresults as to the non-identity of these two compounds. Galactoseforms large, hard, well-formed prisms melting a t 148" ; arabinoselong, fragile needles melting a t 160'. Arabinose has a sweetertaste than galactose. The rotation of arabinose in a 10 per cent.solution is [@ID = +105*4", [ a ] j = +lB" of galactose, +81*5" and + 92" respectively. Arabinose shows no birotation, galactose does ;a fresh solution having given [a],, = 134.5". Fermentation is easilyset up in solutions of galactose by means of yeast, but arabiriosecannot be fermented.When oxidised with nitric acid, arabinoseyields only oxnlic acid, while galactose forms mucic acid. Thereducing power of arabinose for E'ehling's solution is also greater thanthat, of galactose.With regard to the existence of the four arabinoses described byC. O'Sullivan (Trans., 1884, 41, et q.), the author calls attention tothe existence of unstable intermediate products (such as cerasinose,which is gradually converted, even in the crystalline form, into arabin-ose) analogous to these compounds, and suggests that the variousarabinoses may actually exist, and not be mere mixtures of arabinoseInfluence of Temperature and Concentration of Hydrochlo-By I?,with galactose as Scheiblei- believes. L. T. 1'.ric Acid on the Rdte of Inversion of Saccharose.(11)42 ABSTRACTS OF CHEIIICAL PAPERS.UKECH (Bey., 17, 2165-2178). The author refers to his previousexperiments (Abstr., 1883, 174), t,he results of which he now repre-sents byv means of ciirves and tables. A. K. M.'' Hydrate of Carbon '* from Cast Iron. By ZABOUDSKT (BdZ.ROC. Chim., 41,424-4%3).-A very pure specimen OF Swedish specularcast iron, free even from traces of graphite, phosphorus, or sulphur,but containing 0.23 per cent. of silicon and 4.1 per cent. of combinedcarbon, when treated with a mixture of copper sulphate and sodiumchloride yielded 5.72-5-79 per cent. of a *' hydrate of carbon," whichcontained C 71.6 ; H,O 86.9 ; siliceous ash 1.25 per cent,. These resultsapproximate to the formula C,,H,O,. Treatment of the steel withother reagents, silver nitrate, mercuric chloride, atmospheric air, andby Weyl's method, gave rise to the formation of an analogous sub-stance.The hydrate is not changed when heated in a closed tube to15C)", and although it gradually loses weight when further heated, at325" losing carbon a s well as water, it retains hydrogen and oxygeneven after being heated in a ba6h of metallic antimony. Heated in acurrent of hjdrogen, the compound lost considerabl7 in weight, butafter prolonged action the residue still contained hydrogen to theextent of nearly 3 per cent. The compound is insoluble in water,alcohol, ether, sulptiuric and hydrochloric acids. It is completelydissolved by warm nitric acid, forming a substance which probablyhas the formula C,,H,,(NO,) O1,.This body dissolves easily inalcohol and in nitric acid. It is insoluble in ether, but is dissolvedby alkalis, forming a, dark brown solution, from which hydrochloricacid precipitates the original compound apparently unchanged. Thisnitro-compound gives an odour of hydrogen cjanide when heated.Chlorine, bromine, and iodine also act on the hydrate of carbon ; theiodo-derivative probably has the formula C6aH2,10,5. W. R. D.Angelic and Tiglic Acids. By F. BEILSTEIN and E. WIEGAND(Bey., 17, 2261-2263) .-The authors have examined the productsproduced by the oxidation of these acids with potassium permanganate,in the hope of learning something of their respective constitutions.Aldehyde and acetic acid were formed in both cases ; the only differ-ence being that with angelic acid a very small quantity of a non-volatile acid yielding an amorphous barium salt was formed.The acids were prepared by Kopp's process from roman oil of chamo-mile (Abstr., 1879, 454), and their ethers were also made.Ethyl angelate is an aromatic liquid boiling a t 141.5" and having asp.gr. of 0.9347 at 0".3:tlzyZ tiglate boils at 152" and has a sp. gr. of 0.9425 at 0".Halogen-derivatives of Ethyl Levulinate. By M. CONRAD and31. GU'I'HZEIT (Bey., 17, 2285-2237).-With reference to the com-munication of Hell and Kebrer (Abstr., 1884, 1297), on the action ofbromine on levulinic acid, the authors publish this account of somesimilar work carried out simultaneously and independently by them-selves.Bth y 1 monobromoleculinate, CsHllBrOs, was obtained by graduallyL.T. TORGANIC CHEMISTRT. 43adding 16 grams of bromine to 14.4 grams of ethyl levulinatetLlutcd with 2.5 C.C. of ether, the whole being kept cool by means ofice. T t boils with partial decomposition at 240", and has a sp. gr. of1.430 at 1.5" compared with H,O at the same temperature. It entersinto reaction with ethgl sodomalonate, forming a colourless oil of thefor mu In ( C: 0 0 E t) ,C H. CIH,O. C: 00 E t, boiling at 280--285", a11 d havingthe sp. gr. 1.097 at 15". Ethyl monobromolevulinate absorbs morebromine and, as end-product, the authors obtained a mixture of thed i- and t ri- bromo- derivatives. E t h y 1 monoc hlorolevuli n ate, preparedi n R similar manner, is a colourless oil insoluble in water.It boils at225--230°, and has the sp. gr. 1.196 at 15". L. T. T.Adipic Acid, By W. DIETFRLE and C. BELL (Bey., 17, 2221-22&3).-1n continuation of the researches of Gantter and Hell 00suberic arid azelaic acids, t'he authors have investigated adipic acid,the third of the higher dibasic 2cids obtained in the oxidation of fats.The adipic acid was prep:ired from the mother-liquors obtained inthe preparation of suberic acid from castor-oil and other fats.Adipic acid is much less solublc in ether than suberio acid, butmuch more soluble in water. Tlre two acids can be therefore easilyseparated by successive crystallisations from these two solveuts. Theadipic acid thus obtained is still slightly yellow, and is purified bycrystallisation from strong aitric acid or by conversion into its salts.Adipic acid melts at 148-149", aiid solidifies to a crystalline fibrousmass.At 15", 1VO parts of water dissolve 1.44 parts of acid; 100parts of ether, 0.633 part of acid. Adipic acid has a very greattendency to form supersaturated solutions. It is not t-olat'ile insteam, but can be distilled alone withont decomposition. It is onlyattacked by bromine above 15U0, but i! about 0.3 per cent. amorphousphosphorus is added, broniiriation takes place at the temperature ofthe water- ba th.The potassium salt. K,C,H,O,, forms deliquescent crystals ; thesodium salt, mother-3f-pearl-liLe scales contaiuirrg +HzC), and easilysoluble in water. l'he ammonium salt is much more stable than thecorresponding salts of ;Juberic and azelaic acids, and may be evapo-rated without decomposition.I t crystallises in scales, and at 14", 100parts of water dissolve 39-97 of the salt : at, loo", it loses half its ammo-nia, the acid salt beiiig formed, and at 120-150", the rest of theammonia escapes and the puve ;reid is left. The bt-crium salt is lesssoluble in hot tharl in cold water, 100 parts of water dissolving 12-04!parts of salt at, 1jo, and only 7.47 at 100". The strontium salt formsprismatic prisms containing +H20 : 100 parts of water dissolve 13.61])arts of the anhydrous salt, at 14", and 2.r2 at 100". The cnlciumsaltc.rystallises with 1H20 : 100 parts of water dissolve 4.02 parts of theanhydrous salts at 13", 4.09 at li'", and 1.20 at 100".The mngnesiurn. d t crystallises with 4H,O : 100 parts of water dissolve 25.01 parts at15", and 21.71 at 100". The aluminium and ferric salts form volu-minous and a1 most insoluble precipitates. The 7nanJanese snlf mica-c'eous crystals containing 2H20, or, i f deposited at, high temperatures,IH,O : 100 parts of water dissolve 12.63 parts of the anhydrous salta t 18", and 2.71 at 100". The nic7ceZ salt yields apple-green scale44 ABSTRACTS OF CHEMICAL PAPERS.containing 4H20, and only loses the last. molecule completely a t 140" :100 parts of water dissolve 0.65 part of anhydrous salt a t 15", 4.07parts a t 100". The cobalt salt forms pale red prisms containing 4H02,which it loses a t 110": the anhydrous salt is of an intense bluish-violet colour: 100 parts of water dissolve 1.56 parts a t 15", 3.09 a t100".The zinc salt crptallises with 2H20 : 100 parts of water dis-solve 0.261 part a t 10" and 0.217 at 100". The copper salt forms itvoluminons bluish-green precipitate : when this is quickly pressedand dried, it, contains 1 mol. H20, but if allowed to remain undeywater takes up another mol. H20 and then forms small deep bluecrystals: 100 parts of water dissolve 0.024 part of the anhydroussalt a t 15", 0.089 a t 17", and 0.063 a t 100". The lead salt forms ananhydrous white precipitate : 100 parts of water dissolve 0.0206 partat l2*5", 0.0217 at 16", and 0-0217 at 100". The wereuric salt formsa n anhydrous crystalline precipitate : 100 parts of water dissolve0.0287 part at 11", 0.0125 at 1OU".The silver salt is stable towardslight, and forms sninll glittering scales : 100 parts of water dissolve0.0166 part a t 14";and 0.0491 a t 100".The sa?ts OP the heavier metals were mostly prepared by doubledecomposition. Precipitation often takes place very slowly in thecold, but is accelerated by stirring or heating the solution. The saltsof adipic acid resemble those of suberic acid in many respects, butthey are all more soluble than the latter. IJ. T. T.Normal Butylmalonic Acid : a New Isomeric Pimelic Acid.By C. HELL and G. LUMPP (Ber., 17, 2217-22PO).-To prepare thisacid, normal caproic acid is heated with bromine at 130", the mono-bromocaproic acid obtained is converted into the ethyl salt, and thisis boiled for one and a half to two days with a dilute alcoholic sol-u-tion of pure potassium o r sodium cyanide, the nitrile thus formed beingsaponified by boiling witah aqueous potash.Bufy ZmaZoriir, acid,C,81204, crystallises from water in thick prisms, melts a t 101*5", andis readily soluble in water, alcohol, and ether. On warming it or itssalts with concentrated sulphuric acid, they assume a red to violetcoloration. When butylmalonic acid is heated, it readily splits upinto carbonic anhydride and caproic acid, the decomposition beginninga t st little below 140", and being complete a t 150" ; the readiness withwhich this acid is decomposed distinguishes it from the pimelic acidobtained from fats, which may be distilled without decornposition.The barium salt, C7HIU04Ba, crystallises in white anhydrous scales ;solubility at 24", 2.98 parts salt in 100 parts water, and apparentlyless solnble in hot than in cold water.The Zead salt, C7HJI4Pb, isprecipitated in lustrous white crystalline scales, 100 parts of waterdissolving a t 20" only 0.0112 part salt. The si2ver salt, C,H,,O4Ag2,forms a voluminons pulverulent precipitate, 0.1 19 part dissolving in100 parts water at 23". The cqper. salt, C,H,,O,Cu, forms blue scalescontaining 1 rnol. H,O.Occurrence of Pimelic Acid amongst the Oxidation-productsof Castor-oil. By F. GAKTTER and C. HELL (Ber., 17, 2212--2217).-Arppe showed that the so-called pimelic acid obtained by the actiouA. K. MORGASIC CXEMISTE1T. 45of nitric acid on oleic acid and fatty bodies was a mixture of adipicaud suberic acids.The author has obtained it, however, in consider-able quantity by the oxidation of castor-oil by nitric acid. The moresparingly soluble acids are first separated, and the syrupy mother-1 iquor is largely diluted with water, nen tralised with chalk, filtered,and concentrated. The calcium salt obtained is decomposed with acid,when a partly oily and partly crystalline product separates, and maybe purified by alternate treatment with ether and water. Pimelicacid, which may also be obtained by the oxidation of earth-nut oil,crystallises from water in clusters of large flat plates, which melt a t105*5-106", and solidify t o a crystalline mass, which suddenly falls topieces with the slightest touch.The blxrium salt, C7Hl,04Ba,H,0,crystallises in white indistinct scales ; the Zeud salt, C,H,,O,Pb, andt,he silrer salt, C7Hl0O4Ag2, form white pulverulent precipitates ; andthe coyper saZt, CjH-loOICu, a green precipitate. The pimelic acidappears to be distinct from all the acids of the composition CjH1,O6hit,herto described ; its properties approximate most to those of Banerand Schuler's isopimelic acid (from amyleno bromide), but a moreextended comparison of the two is necessary to decide the question ofidentity. A. K. &I.Chelidonic Acid. By J. U. LERCH (Xonatsh. Chem., 5, 367-$l$)--The author refers to his previous work, and claims prioritybefore Haitiiiger and Lieben (see next Abstract).The ethyl salts were prepared by the usual methods; the diethy;!saZt, CjEf,O,Et,, melts a t 62"; the wtouetliyl salt, also formed bydecomposition of the preceding, melts a t 182-184"; its lead andsilver salts, C7H,0GEtAg, are cyystalline.The diethyl salt, dissolvedin alcohol, gives with ammonia a yellow solution, and then whitecrystals, probably the amide of chelidonic acid, C,H,O,(NH,),. Theyellow solution obtained by adding excess of potash to chelidonicacid is gradually decomposed, even at ordinary temperatures, intooxalic acid and acetone ; the acid is also decomposed by bromine andchlorine, oxalic acid and substituted acetones being formed. Potashgradually added to water containing calcium chelidonate in suspen-sion converts the whole into a stiff yellow jelly, without the forinationof oxalic acid and acetone ; it is a potassium calcium salt of che&hydronic acid (xanthochelidonic acid of Haitinger and Lieben), and ismore applicable for further preparation work than the easily decom-posable potassium salt.The free acid can only be prepared withgreat difficulty ; the gelatinous potassium calcium salt is treated withsulphuric acid, and fractionally extracted from ether ; from the secondand following ethereal extracts it is obtained as a pale yellow amorphousmass. By neutralising the gelatinous potassium-calcium salt wit13acetic acid, the calcium salt, C7H20,Ca2, is obtained as a citron-yellowprecipitate. Chelihydronic acid neutralised with ammonia givesa red solution, from which a crystalline arnmouiurn salt may beobtained.This red solution gives, with silver nitrate, a yellowprecipitate, CJl307AgS + 4N20, which by boiling is converted into abrown precipitate, C;H207Ag+ If in the above the chelihydronicacid be replaced by the gelatinous calcium potaasium salt, silve46 ABSTRACTS OF CHEMICAL PAPERS.precipitates having the same colour are obtained; but they aredouble salts, viz., yellow, (C7H307Ag),Ca + 4H20, and brown,(C7H307Ag3)2Ca, whilht lead and barium solutions also produceyellow precipitates of tlie composition (C7H207)4Pb5Ca3 + 6H,O andC7H,O7BaCa ; the calcium potassium salt precipitated from its solu-tion by alcohol has the composition (C7H2O7),Ca,R2 + 2H20. Cheli-hydronic acid has therefore the composition C7H6O7, and containsthree or four hydrogen-atoms that may be replaced by metals.Chelidonic acid evaporated with ammonia gives the ammonium saltof chelidammic acid, whose salts are also formed by the action ofammonia on the clielidonates. Hydrochloric acid added to a solution ofthe ammonium salt produces a precipitate of tlie formula CI,H,,N30,, ;this is a compound of the free acid with its ammonium salt, C7H,N0, + C7H,N0,.NH4 ; i t seems to be monoclinic, and dissolves in 1576 partsof cold water.By boiling this substance with potash, and then acidify-i n g , the cornpourid C7H7NO6 separates; this is a hydrate of the freeacid, C,H5N0, + H,O ; i t crystdlises in rhombic prihms, and dissolr-esi n 637 parts of cold water. Ethyl chelidnnzniate, C,H,N05Et, + H,O,melts a t 80- -81", and becomes anhydrous in a vacuuxn.Although theacid coutains only two acid hydroxyl-groups, i t forms three classes ofsalts ; the following are described :-C7H2N0,Pb(NH,) ; (C,H,XO,),Pb,;+ 3H20 ; C,H,NO,Ags ; C7HANOSC& + 2H20 ; (C7H2N05)2Ca, ;C,H,N05Ca (NTIJ + 2H20.When chelidammic acid is treated -with the halogens, i t yields hi-substitution-products. Bro,nocheZidummic acid, C7H,Br2N0, + 2H20,forms large efflorescent crystals ; its silver salt is C7HBr,N05Sg,.ChZorocheZiJammic mid, C7H3C12N05 + H 8 , forms long fibrous cr-j-stals ;i t s silver and lead salts are C7Cl,N0,Ag, and (C7C12N05),Pb3. Iodo-chelidanimic acid is obtained by dissolving chelidammic acid in analkali, saturating with iodine, and then acidifying; its formula isChelidammic acid at 250" loses carbonic anhydride, and there remainsa crystalline mass of chelmnide ( h y d r o z ~ p y r i d t n e ) , C,H,NO, melting at95-96', and therefore different from the hydroxypyridines of Ost,of Fischer and Korner, and of Konig and Geigy, which melt at 14b",123.5", and 107".When crystallised from water: it has the formulaC5H5NO + H,O. Heated with zinc-dust, i t yields pyridine. Thedouble salts ( C5H5NO)?,H2P~C16 + H,O ; C5HJV0,N03H,AgN0, ;C,H,N 0,HgC12 ; and the hydrochloride, C5H5N0,HCI, are described.Chelidonic acid is also acted on by aniline, producing a crystallinebody. Aniline chelidonate when heated evolves carbonic anhydride,and leaves a crystalline residue which after recrystnllisation from wateim,has the cornposition CIIHSNO + 2H20 ; this anilide, bowever, does notform eitlier single or double salts.Following is a discussion of the constitution of these bodies ; thefollowing forniuk are aclvocat ed :-C7H3N0,Pb; C7H:,NOjPbAg; (C7H,N05)2Pb$a+ 3H20; CTH2NO5PbKc7 H 312N 0 5 .0 Chelidonic acid, C00H.CH : CChelihydronic acid, COOH.CH : CCH.C(COOH)<Cd>.CH.C(OH)(COOH),ORGANlC CHEJIISTRY.47Chelidammic acid, C00H.CH : C : CH.C(COOH)/ Ii'C.OHH. R.Chelidonic Acid. Bg HAITINGER and A. LIEBEN (Nonatsh.Chem., 5, 339-3GG).-Reference is made to all previous work on thesubject. Lietzenmayer's method for isolating the acid was used.The free acid suspended i n alcohol and hydrochloric acid gas passedthrough, the solution evaporated and the residue dissolved in alcoholdeposits monethyl chelidonate, the diethyl salt remaining in solution.The diethyl saZt, C7H,06Et2, forms crystals melting at 62.7".Thenzon~thyl salt, C7H,0,Et, is crystalline, melts a t 223--224O, and itsalcoholic solution has an acid reaction. Chelidonic acid is dibasic,and not tribasic.It has been previously shown t h a t when chelidonic acid is heatedwith x l k a h or, much better, alkaline earths, it yields acetone andosalic acid. This has been rigorously confirmed, and it is alsoshown that the reaction proceeds exactly according to the equationC7H,06 + 3H,O = 2C,04H2 + C3H60.When chelidonic acid is treated with potash solution, a transientyellow coloration is produced with each addition, until two molecularproportions of the potassium salt have been addtd, i.p., until the neutralsalt of the bibasic chelidonic acid has been formed.Further addition ofpotash produces a permanent yellow coloration, hiit the solution doesnot remain alkaline until more than three molecular proportionsof potassium hydroxide hare been added. This pellnw soluiion con-tains the potassium salt of a new acid, zccnfhocheZidorric arid. If thissolution is acidified with acetic acid, it gives a yelluw precipitate,C,H,Pb2O5 + H20, with lead acetate ; tetrabasic calcium and silversalts could not be prepared. BJ acidifying a solution of chelidonicacid in excess of caustic potash with nitric acid, a light yellowcrjstalline deposit of an acid potassium salt, CiH5EOi, was obtained.The free acid cannot be isolated from its salts, since by the additionof an acid i t is at o ~ c e partly converted into chelidonic acid, and stiilmore so on standing.If chelidonic acid is treated with hydriodic acid, it yields pimelicacid (probably the normal acid).When it is heated with zinc andacetic acid, and the zinc removed by sulphuretted hydrogen, a n acid,hydrochelidork acid, C7H1,,O5, is obtained. This is colourless, crys-ta,iline, melts a t 142", and can be distilled unchanged. The zinc salt,CiH,OjZn + 2H20, is hut slightly soluble in cold water, and crys-tallises in small monoclinic tables,a: b : c = 1.0292: 1 :1*737; ,8 = 89" 7.5'; O P . 032m. m$2.also - Pa. Pm .322.The calcium salt, C7H,05Ca -+ H20, is indistinctly crystalline.Thesilver salt is C7H805Ag2 ; the copper, lead, and mercurous salts arealso mentioned.An alkaline solution of hydrochelidonic acid was treated mithpotassium permanganate, and oxalic and succinic acids obtained, i48 ABSTRACTS OF CHEMICAL PAPERS.accordance with the equation C,H,,05 + 60 = C204H2 + C,H,O, +COZ + H2O.Hydrocheliclonic acid heated with a saturated solution of hydriodicacid a t 200-210" is in greatest part reduced topirnclic acid, C,Kl2O4,which is obtained by simple evaporation ; it melts a t 1029- 103*9",and forms monoclinic crystals,a : b : c = 3.691 : 1 : 2.058 ; p = 103" 33' ; mPm . OP . mP . P .It is probably the normal acid. During the reduction, a smallquantity of a hydrocarbon is also formed.An alkaline solution of sodium xanthochelidonate was reduced withsodium amalgam, and the new sodium salt precipitated from theconcentrated solution by alcohol.The silver salt was found to havethe formula Ag,C7Hlo07, hence hydroxa,nthoclzelidonic acid must havethe composition C7H12a ; it is a syrupy liquid. Heated with hydriodicacid, it also acts like hydrochelidonic acid and chelidonic acid,I f chelidonic acid is heated a t 240" it loses 2 mols. CO,, and gives asdistillate a body melting at 32.5", and boiling a t 215". With aqueousammonia it gives hydroxypjridine (Mormtsh. Chem., 1883, 339),and tliere is no doubt that it is identical wit>h Ost's pyroconiene( J . pr. Chem., 29, 63), thus showing a connection between chelidonicand meconic acids.Chelidonic acid is certainly dibasic ; the pimelic acid referred to isprobably the normal acid, and by boiling with an alkali chelidonicacid jields oxalic acid and acetone.These and other facts are explained11;- the constitutional formulae :-CO0H.C-0-C.CO0HI-IC I1 . C 0. CH II COOH.CH<~~>CH(CEI,),.COOHChelidonic acid. Hydrochelidonic acid.CO[CH: C(OH).COOH], 0 H . C H[ Cl H,. C H ( OH). C 0 OH]H. B.Xanthochelidonic acid. Hydroxant.hochelidonic acid.Nitrogenous Derivatives of Meconic Acid. By H. OST (J. pr.Ch~m. [2], 29, 57--69).-1n previous papers (Abstr., 1879, 708, and1883, 791), the author has described those nitrogenous compoundswhich are readily obtainable from meconic acid, as substitutedproducts of a hypothetical pyridoue :-Pyridone, C5HSNO.Pyromecazonic acid, C,H,NO(OH),.Comenamic acid, C5H3NO(OH) (COOH).The author now shows that pyridone is hydroxypyridine, thatpyromecazonic acid is a trihydroxypyvridine, and comenamic acid adihydroxypyridinecarboxylic acid.BJthyl dkcetylcomenamale, C5HzN( O?G),.COOEt, was prepared byboiling ethyl comenamate with excess of acetic anhydride and thenevaporating- The diacetyl-compound melts at 38', whilst thORQANIC CHEMISTRY.49monacetyl-derivative, which is formed when the above mixture is onlywarmed, melts a t 152". Both compounds are decomposed by water oralcohol in the cold, with liberation of acetic acid.The ethyl dibenxoyZcomennmate, which is ohtained by boiling ethylconienamate with benzoic chloride, melts a t 102", and is more stablethan the acetpl-compounds.Since the existence of these diacetyl- and dibenzoy 1-compoundsdoes not conclusively prove that comenamic acid contains twohydroxyl and not one hydroxyl and one imido-group, the isolation ofpyridone was next proceeded with and accomplished by means of thea c ~ d C6H2C1202, to which the author gives the nnme of dichlorocomanicacid, comanic acid, C5H302.COOH, being comenic acid in which thehydroxyl is replaced by hvdrogen.Dichlomconzanic acid, C,HCl,O,.COOH, is prepared by heatingcomenic acid with 4 mols.of phosphorus pentacliloride and oxy-chloride, using a reflux condenser, until no more hydrochloric acid isevolved; on then distilling to 150" an oil remains behind whichyields the acid when decomposed with warm water.When purified,by crystallisation from alcohol, the acid forms voliiminous needlesmelting a t 217". A small quantit,y of monochlorocomanic acid isformed a t the same time; this crystallises in needles, and melts a t247".Coma& acid, C5H,02.COOIT, is obtained by boiIing the dichlor-iiiated acid for several hours with rather more than the theoreticalproportion of aqueous hydriodic acid (b. p. 1 2 i 0 ) ; the iodine is thendriven off in a current of steam, and on evaporating the solution theacid crystallises out in small nodules. The pure acid forms smalloblique prisms melting at 250" with violent evolution of gas. It givesno coloration with ferric chloride. The barium, silver, and ethylsalts are described ; the latter melts a t 103", and is not acted on byacctic anbydride or chloride.This shows that comanic acid is nota hydroxy acid, although barium hydroxide precipitates a basic salt,which, however, is derived from another acid into which comanicacid is readily converted by strong bases, and which gives a darkbrown-red coloration with ferric chloride. On heating it with excessof barium hydroxide, the precipitate formed is rapidly converted intobarium oxdate: acetone being formed also ; in this respect, comanicresembles chelidonic acid (Abstr., 1883, 8'70). When comanic acidis heated, carbonic anhydride is evolved, arid it is converted intorocomane, C5H402, a neutral body soluble in water, melting a t :go, and boiling a t 210-215".On gently heating comanic acid withstrong ammoilia, i t is readily converted into P-hydroxypicolinicacid, C,H,N( OH).COOH, which has already been described (Abstr.,1883, 791). Since this acid can also be obtained from pentachloro-picoline, there is no doubt that i t is hydroxypyridinecarboxSlicacid. I n a similar manner, although less readily, ammonia acts oncornenic acid, jielding comenamic acid, C,H,N( OH),.COOH, and onhydroxjcoinenic acid, yielding hjdroxycomenarriic acid,C,HN(OH),.COOH ;this proves that cornenamic acid is a dihydroxy-, and hydroxF-VOL. X L ~ X l : . 50 ABSTRACTS O F CHEJIICAL PAPERS.comenamic acid a trihydroxy-pyridinecarboxylic acid ; both theseacids, moreover, belong to the a-pyridinecarboxylic series.Hydroxypyridine, C5H4N.0H, is obtained from p-hydroxypicolinicacid by heating it above its melting point, carbonic anhydride beingevolved.It crystallises in small grains melting a t 148", is easilysoluble in water and alcohol. has a neutral reaction, combines withacids, and forms a platinocbloride crystallising in large rectangularprisms. This hydroxypyridine is identical with t,hat obtained byLieben and Haitinger (Abstr., 1883, 870). The following is a list ofthe nitrogenous derivatives of meconic acid :-E y drmjpyridines.C,H,N 0 H, h y drox yp yri dine.C5HtE,N(OH)?, dihydroxypyridine, pyrocomenamic acid.C,H,N (0 H) 3, trihy drox ypyridine, pyromecazonic acid.C5H2N02.0H, hydroxypyridinequinone, pyromecazone.C,HN(OH),, tetrahydroxypyridine (?), hydroxypyromecazonic acid.C,H,NMe(OH)a, dihydroxypicoline, methyldihydroxypyridonc(Abstr., this vol., p.$40).H ~ d r o x ~ p ~ r i d i e ~ ~ ~ o x y l ~ c Acids.C5K3N( OH).COOH, /3-hydroxypicolir1ic acid (and the isomeric a- andC5H,N(OH),.COOH, dihydroxypieolinie acid, comenamic acid.C,HN(OH),.COOH, trihydroxypicolinic acid, hydroxycomeriamicC,HNO,(OH).COOH, hydroxypicolinic acid quinone, azonecar-yacids).acid.hoxylic acid. P. F. F.Beta'ine in Cotton Seed. Bey H. RLTTHATJSEN and F. WEGEB ( J .pr. Cllem., 30, 32-37) .-The authors have succeeded in obtainingbetn'ine from the cotton seed, by trcatment of the mothcr-liquors fromwhich melitose had been separated (J. pr. Chew,., 29, 351). Theauthors have not, as yet determined in what form the betaine occursin t h e cotton seed.P. P. B.Seleniocarbarnide. By A. VERNEUIL (BUZZ. Xw. CIiem., 41, 599).-This compouud may be prepared by the action of hydrogenselenide on cyanamide. The latter dissolved in ether absorbs thegas completely in the cold, and after a short time crystals are depositedand finally the liquid becomes solid. The react,ion is facilitated bythe presence of a small quantity of ammonia. The compoundpurified by two crystallisations from boiling water forms whitecrystals which assnme a rose tint when exposed to light. Selenio-carbamide is very soluble in hot water, less so in cold, which dissolves10 7 per cent. at 19". Absolute alcohoI dissolves 28 per cert. a t 18",and ether 0.56 per cent. a t the same temperature, When rapidlyheated, the compouud melts without any apparent decomposition, butif slowly heated it melts at about 200" with decomposition.W.R. D.The Thiophene Group. By R. NAHXSEN ( B e y . , 17, 2197-219s).-The author has prepared larger quantities of dithiertSl (Abstr.ORGANIC CHEMISTRY. 511884, 1132), and has submitted it to a more thorough examinationthan was previously possible. It crystallises from hot alcohol 01'glacial acetic acid in silky scales, melts at 83", and boils at, 266".I t s solution in concentrated sulphuric acid is reddish-brown intrnnsmitt'ed and deep-green by reflected light, and in pouring thesolution into water dithienyl separates unchanged. Dith ienyl-sdpholzic acid. C8H5S2.S0,3H, is obtained by heating dithienyl with20 times its weight of sulphuric acid.(C,H,S,.SO,),Ba,is obtained as a ci-ystalline mass and is hygroscopic ; the potassi?lmsn7t is deliquescent arid yields dithienyl when distilled with ammoniumchloride. Perbroinodithienyl, CeBr& is prepared by beating a solu-tion of ditbienyl in glacial acetic acid with an excess of bromine.It, is very sparingly soluble in hot alcohol and i n cold benzene,~eadily in boiling benzene, from which it crjstdlises in small needlesmelting a t 235" (uncorr.).The bariutn saltA. K. 3f.p-Thiophenic Acid. By R. NAHNSEN (Ber;, 17, 2192-2196).-A thiophenic acid was prepared by Meyer and Kreis from thio-phenesulphonic acid by Merz's method (Abstr., 1884, 46). I n theliopes of obtaining larger quantities of this acid, tlie author submitteda mixture of iodotliiophene and ethyl chlorocarbonate to the action ofsodium amalgam. The reaction takes place much more readily thanin the case of Wurtz's synthesis of benzoic acid.The product issteam-distilled, the distillate extracted with ether, and the oilobtained is boiled for five hours with concentrated aqueous potash : thesolution is diluted, separatJed from the uiiattacked iodothiophene,supersaturated with sulphuric acid, and extracted with ether. Thethiophenic acid, C*H,S.COOH, obtained is, however, isomeric miththat obtained by Meyer and Kreis, and melts constantly a t 129". Theacid prepared from the sulphonate is assumed to be all a-derivative, inwhich case the new acid would be /j-thiophenic acid, thus:CH- CH CH- CH>S.I 1s.C(CO0H) : CH/ IC'H : C(CO0H)a-Thioplienic acid. a-Thiophenic acid.B-Thiophenic acid closely resembles benzoic acid. It crystallises incolourless needles, can be sublimed, and distils at, 260" ; it yields ablue solution when heated with sulphuric acid and isatin. It giveswhite precipitates with silver nitrate, lead acetate, and mercurousnitrate, and a very bulky yellow precipitate with ferric chloride;ivliilst copper, cadmium, zinc, ferrous, cobal t, nickel, mercuric,barium, calcium, and magnesium salts produce no precipitate. Thesilver salt, C,H,S.COOAg, foiwms lustrous transparent scales 01-l~eedles somewhat soluble i n hot, sparingly in cold water; the c u l c i u p ~s(11t, (C,H,S COO)LCa,3H,0, is readily soluble in water, and separatesin clusters of lanceolate crjstals ; the barizlm s d t ,(C4R$3.COO)2Ba,2H20,€ 52 ABSTRACTS OF CHEXICAL PAYERS.forms small lustrous crystals readily soluble in water. The chloride,C,H,S.COCl, is a colourless liquid boiling a t 190" (uncorr.), and hasthe same penetrating odour as benzoic chloride ; the ethyl salt,is a colourless, strongly refracting liquid, boils a t 218" ( o r r .) , andhas an odour closely resembling that of ethyl benzoate. P-Thiophen-amide, C4B3S.CON H,, forms dense prisms melting a t 180" (uncorr.).When /iI-thiophcnic acid is nit'rated and the product crystallised fromwater, dense yellow prisms, CIH2S(NOr).COOH, first crystallise out,,and afterwards long needles.A. K. M.Action of Chlorine on Boiling Benzene. By R. SCHUPPHAUS(Ber., 17, 2256--2260).--Meunier (Abstr., 1884, 733) has describeda compound obtained in the preparation of benzene hexachloride, andhas ascribed the formula xC6H6Cl6 to it. The author also discoveredthis substance independently about two years ago. Meunier noticedthe presence of this substance a f t e r sublimation of his crude product,and it has been thought it might have been formed a t the high tem-perature of sublimation. The author obtained it, however, amongstthe first crude crystals deposifed after the action of the chlorine onthe benzene. From the results of his analysis, and the general cha-racter of the compound, the autlior believes the formula of this com-pound to be C,,H&l,,, and not zC6H6C16) and that it is thus diphsqtyZdodecachloride.The crystals are brittle and become highly elect,rified when powderedin a mortar. Contrary to the statements of Mennier, the crystals arestrongly double refracting.By J.MEC'NIER (Bull.SOC. Chim., 41, 5 3 0 4 3 2 ) .-The rapour-density of this compound,the preparation and properties of which have previously beendescribed (Abstr., 1884, 733), has been defermined, and found to be9.365 and 9.207 a t 260" (theor. 10.03). The vapour-density ofordinary benzene hexachloride a t 22W was found to be 10.139. Thisdifference is probably due to partial decomposition of the isomeride a tthe temperature of the determination- The formula of this isomerideis therefore C6H6C16, and its melting point is about 3310°, that of ordi-nary benzene hexachloride being 157".By E.XLTING ( B ~ l l . BOC. Chin$.,41, 502--504).-Since the oil obtained its a bye-product in the pre-paration of paranitrobenzyl chloride (Abstr., 18%, 1005) consistscliiefly of orthonitrobenzyl chloride, it may, perhaps, serve as a meansof preparing orthonitrobenzaldehyde, the starting point in Baeyer'ssynthetical preparation of indigo, but the author has not j e t succeededin preparing the aldehyde from the oil.Decomposition of Benzonitrile by Fuming Sulphuric Acid.By F. GUMPERT ( J . pr. (%ern., 30, 87-90).-1n preparing cyaphewi~teaccording to Pinner and Klein's method (Abstr., 1878, t64), theThey belong to the regular system.L. T. T.Isomeride of Benzene Hexachloride.A. B.Orthonitrobenzyl Chloride.A.BORGANIC CHEMISTRY. 53author did not obtain this compound, but dibenzamide, NHBz,, identi-cal with that prepared by Barth and Senhofer (Bey., 9, 975), and byFischer and Troschke (Abstr., 1881, 51). Dibenzamide melts a t 148".When heated with alkalis, i t is converted into benzoic acid and ammo-nia; heated with alcoholic ammonia in sealed tubes, it is convertedinto benzamide. The compound' described by Pinner and Klein asdibenzimide oxide is formed along with the above compound ; whentreated with dilute hydrochloric acid it is converted into dibenzamide,and the author regards it as benzimidobenzamide, NHBz.CPh : NH.P. P. B.Acetonequinol. By S. HABERMANN (.iWonntsh. Chem., 5, 329-331).-Quinol dissolves easily in acetone and, on cooling, very fine crystalsof acetonequinol, C3He0,C6H602, separate out.When exposed to theair, they soon become opaque, and then consist only of quinol. I n com-position and easy decomposition, it resembles quinhydrone, and itsexistence is an argument in favour of the formnla for quinone,recently advocated by Kekule (AnnaZen, 223,170), showing two car-bonyl-groups. H. B.By W. H. GREENE (Chm. News,50, 76).-A mixture of methylene chloride (30 grams), phenol(30 grams), sodium hydroxide (40 grams), and water (50 grams), isheated in a sealed tube a t 100" for six hours; the contents of thetube are then neutralised with hydrochloric acid, extracted withether, and the ether distilled 08. The residue is repeatedly treatedwith boiling water, the aqueous solution is concentrated, the drops ofphenol which separate are removed, and the strong solution then leftto crystallise over sulphuric acid ; the product, when recrystallisedfrom boiling water, is pure saZigenin.Compounds of Glucoses and Sucroses with Phenylhydrazine.By E. FISCHER (Ber., 17, 579--584).-When an aqueous solution ofphenylhydrazine hydrochloride, to which sodium acetate has beenadded, is heated on the water-bath with the aqueous solution of asugar, combination takes place and an insoluble compound is formed.I n many cases, the production of these compounds may be used as ameans of detecting the presence of a sugar and of identifying thesame.They may, as a rule, be easily purified by crystallisationfrom alcohol. Of the sugars experimented with, inosite and trebaloseare the only two which have not the property of unitirrg with phenyl-liydrazine.PhenyZgZucosazone, C,sH2,N404, is the name given by the author tothe compound formed when dextrose or 1e-i-dose is treated with phenyl-hydrazine in the manner described. This compound is insoluble inwater, but soluble in boiling alcohol, from which it is precipitated bywater in slender yellow needles melting at 204-205".It is not actedon by aqueous solutions of caustic alkalis, but is decomposed by stronghydrochloric or sulphnric acids, with the production of dark red solu-tions. This compound is formed even when dilute solutions of dex-trose are employed, and it would appear that its production may beused as a means of detecting grape-sugar in urine.New Synthesis of Saligenin.D. A.L54 ABSTRACTS OF CHEAlICXL PAPERS.Phenylgalactosnzone, ClsHa2N404, is tlie product of the combinationof phenylhydrazine and galactose ; in properties, it resembles phenyl-glucosazone, differing from it in melting a t a lower temperature,namely, 182 O .Sorbin also unites with phenylhydrazine, forming a compoundwhich is easily soluble in hot alcohol, and may be precipitated from thesolution by water, in the form of fine yellow needles melting a t 164".When cane-sugar is warmed with the solution of phenylhydrazinehydrochloride, it is first inverted, and subsequently phenylglucosazoneis produced. Milk-sugar and maltose both unite with phcnylhydrazine,forming pheny lactosnzone and y h e y lmcdtosazone respectively.Thesecompounds have tlie same composition, viz., CZ4HJV4O9, are svluble inhot water, and crystallise in yellow needles ; the former melts a t 200",the latter a t 190- 191". P. P. B.Action of Potassium Cyanate on MetanitramidobenzoicAcid. By P. GRIESS (Ber., 17, 2184--2187).-Five: isomeric nramido-iiitrobenzoic acids have been described, in three of which the groupsNO, and NH.C0.NH2 occupy the ortho-position to one another, aridin the remaining two, the para-position. With the object of obtain-i n g an acid containing these groups in the meta-position, the authorhas submitted metanitramidobenzoic acid (Abstr., 1884, 314) to theaction of potassiuni cyanate.The nitramidobenzoic acid is graduallyadded to a cold aqueous solution of crude potassium cyanate, themixture heated for some hours at 50-60", and then tyeated with ailexcess of acetic acid. The product is allowed to stand for severalhours, a large excess of hydrochloric acid is added, and the precipitateseparated and washed, The product consists of two acids : urarnido-nitrobewoic acid, NH~.CO.NH.C~H~(PO~).COOH [I : 3 : 51, and di-urarnidonitrobe~~zoie acid, (NH~.CO)~N.C~H~(NO~).COOH [l : 3 : 51,which may be separated either by treatment with boiling wateror by means of the barium salts. Uramidonitrobenzoic acid,C,H7N3O5,H2O, is moderately soluble in boiling water, from which itcrystallises in bright yellow needles ; is much more readily soluble inhot alcohol, but very sparingly in ether ; it has a strong bitter taste.When heated, it detonates, producing a yellow smoke and leaving alarge carbonaceous residue.The barii~m salf,[NHz.CO.NH.C&&(NOZ) .C00]2Ba,5H,07forms yellow nodules, readily soluble in hot, moderately in cold water.On dissolving uramic3onitroberlzoic acid in nitric acid (sp. gr. 1.5), itis converted into uramidodinitrobenzoic acid,N Hz. C 0. N ( NOz) . C, H3 (N 0 2 ) . C 0 OH.Diuramidonitrobenzoic acid crystallises from alcohol w i t h 2 mols. H,O.It forms almcst white microscopic needles or scales generally unitedin tufts, is very sparinglv soluble even in boiling water, andsparingly also in hot aIcotol and in ether. It has a st,rong bitkertaste, and also resenibles the last acid in its behaviour when heated.By the action of tin and hydrochloric acid, it is converted into a newamido-acid, crjstallising from boiling water in slender white needlesORGIhNlC CHEMISTRY. 55The harium salt, [ (NH,.CO),N.C,H3(NO,).COO],Ba,7~H2O, is verysparingly soluble even in boiling water, and crystallises from it insmall yellow nodules when the solution is rapidly cooled, and in needlesby slow crptallisation ; it is insoluble in alcohol.Action of Hydrochloric Acid and of Chlorine on Aceto-benzoic Anhydride.By W. H. GBEEKE (Chew,. News, 50, 61-62).-It has been stated (Loir, Abstr., 1880, 31) that acetobenzoicanhydride prepared from beiizoic chloride and sodium acetate, differsfrom the anhydride prepared from acetic chloride and sodium benzoatein its reactions with hydrochloric acid and with chlorine.The authorshows that this is not the case, but that scetobenzoic anhydride, which-ever way prepared, behaves always in the same manner with hydro-chloric acid and chlorine. When dry hydrochloric acid is passed intot tie anhydride a t ordinary temperatures, acetic chloride and benzoicacid are the principal products, whiist a t higher temperatures, 130" tolW0, acetic and benzoic chlorides, and acetic and benzoic acids, areproduced in about equivalent proportions. With chlorine a t about 150",the products are acetic and benzoic chlorides, chloracetic and (1 : 2)uhlorobenzoic acids, whilst at lower temperatures the reaction yieldschiefly acetic chloride and chlorobenzoic acid.A.K. &I.D. A. L.Action of Phenol and Sulphuric Acid on Hippuric Acid.By J. ZEHENTER (Monatsh. Chern., 5, 33.2-338) .- Experimentswere made to obtain condensation-products of phenol with glycocolland alanine, but with negative results. But by heating hippuric acidwith phenol and sulpliuric acid a t 140", the nascent glycocoll does unitecompletely with the phenol. The product of the reaction is dissolvedin water, the berizoic acid removed by ether, and then neutraliseciwhile hot with lead carbonate. The solution of the lead salt is decom-posed with sulphuretted hydrogen, and the filtrate evaporated finallyin a vacuum and allowed to crysfallise. The substance, C,H,O,NS +H,O, melts a t 153-185", and is an acid forming salts, It is probablysulplio~heny Tgl~cocoZI, its formation being expressed by the equationXH2.CHz.COOH + C6H5.0H + H,S04 = C8H905NS + 2Hz0.Thesilver salt, C8H80,NSAg + 3H2U, the barium salt, (C,H,05NS)2Ba +H20, and also the copper and potassium salts are described.When the free acid is heated t o 200", it gives a distillate of phenol.Treated wihh aqua regia, a, yellow crystalline substance is formed.Wo satisfactory clue to the constitution of the acid is obtained byfusing it with alkalis. Phenol and hippuric acid do not act on eachother if heated with water under pressure.By. 0.WIDMANN (Ber., 17, 2282--2284).-As Einhorn and Hess have justpublished a communication containing some work on this subject, theauthor now gives a preliminary note of the results of a research whichhe has been carrying on of late.He has at present prepared andexamined the following compounds :-H. 13.Nitrocumenylacrylic Acids and their Derivatives5F ABSTRACTS OF CHEMICAL PAPERS.A. From orthonitrocumenylacrylic acid-Ethyl orthonitroc umenylacrylate ........Orthonitrocnmenylacrylic acid dibroniide. . m.p.Acetamidocumenylacrylic acid .......... ,,Cumostyril (isopropylcarbostyril) ........ ,,Orthoxycumenylacrylic acid ............ , .Orthamidocumenylacrylic acid .......... ,?Hydrocumostyril ...................... 5 ,B. From cumenylnitroacrylic acid-Cumen ylamidoacrylic acid .............. , ,C. From metanitrocumenylncrylic acid-Metanitrocumenylacrylic acid. ..........., ,Metanitrocumenylacrylic acid dibromide . . 9 ,Ethyl metanitrocumenylacrylate ........ 7 7Metamidocumenylacrylic acid ........... ,,Acetamidocumenylacrylic acid .......... 7Metamidocumenylpropionic acid ........ 7 7Acet'amidocumenylpropionic acid ........ 9Liquid.171"16522016 7-- 16813.5176154-15514158-59184I65240168L. T. T.103-105Compounds of Phenols with Ethyl Acetoacetate. 111. ByH. V. PECHYANN and J. B. COHEN ( B e y . 17, 2187-2191). I n continu-ation of their experiments on the substituted coumarins (Abstr., 1884,66, 1331) the authors give further evidence of the general applicationof the reaction for their formation. A comparison of the coumarinsobtained from ethyl acetoacetate with the ordinary coumarins shows astriking analogy in the properties and especially in the colour reactionsof those members of both series which are derived from the samephenol.The coumarin obtained from paracresol and ethyl acetoacetate (Zoc.cit.) may (in accordance with Baeyer's notation, Abstr., 1884, 998) benamed b-5-dimethylcoumarin ; it melts a t 148".p-Methyldaphnetin, C6H2( OH),< '?de :'">GO [l : 2 : 3 : 43, ob-tained from pyrog,zllol and ethyl acetoacetate (Zoc.cit.), closelyresembles daphnetin ; after boiling with bisuiphite, both compoundsyield an intense blue coloration with ferric chloride and a reddish-yellow reaction with ammonia and potassium ferricyanide. The actionof sulphuric acid on orcinol and ethyl acet'oacet'ate hss been examinedby Wittenberg ( J .pr. Chwn. [2], 26, 69), but his results disagreewith the authors'. The product is termed /3-6-dimethylumbelliferolie,C o H , M e ( O H ) < ~ ~ ~ > C O [CMe : 0 OH : Me -= 1 : 2 : 4 : 61.It melts at 248-250", crystallises in needles, dissolves readily in alcoholand glacial acetic acid, sparingly in benzme and chloroform, and isalmost insoluble in water. It yjelds yellow solutions with concen-trated sulphuric acid and with dilute alkalis. The solution obtainedby boiling i t with bisulphite yields (like homo-umbelliferone) a redcoloration. The ace$-derivative, CIJHl,Or, crystallises in white needlasORGANIC CHEJIISTRT. 57melting at 195", dissolves readily in alcohol, glacial acetic a d ,benzene, and chloroform, sparingly in ether, and is insoluble inwater.4- 6-Dihydroxy-P-~~zet?~ ylcoumnrin,C6H2( OH)2<-O-- CMe:CH>CO [CXe: 0 : OH: OH =1: 2 : 4 :6],from phloroglucol and ethyl acetoacetate is isomeric with /3-methyl-daphnetin. I t crystallises in colourless needles, melts ati 282-5284',dissolves readily in alcohol and glacial acetic: acid, sparingly in water,benzene, and chloroform, is almost insoluble in ether, and is readilydissolved by dilute alkalis. Its aqueous solution gives no reactionwith ferric chloride, and yields a yellow precipitate with lead acetate.It yields no colour reaction with bisulphite. The ncetyl-derivative,CI4Hl2O6, crystallises from alcohol in white glistening needles, melts at138-140°, is insoluble in water, sparingly soluble in ether, readily inalcohol, glacial acetic acid, and chloroform. /'3-Methylcounzarifi of>CO, from P-naphthol and ethyl aceto- naphthalene, C1OH6<acetate, forms white glistening needles, melting at 161-162" ; it dis-solves in alcohol, benzene, and chloroform, but is nearly insoluble inwater and ether.Sulphuric acid dissolves it with green fluorescence.Reduction of Phthalic Anhydride by Zinc and GlacialAcetic Acid. Bg J. WISLICENUS (Bey., 17, 2178--2183).--Whenphthalic anhydride (200 grams) is dissolved in glacial acetic acid(1 kilo.), heated on a water-bath, and zinc-dust (about 300 grams)added in small quantities a t a time, the latter at first dissolves rapidly,with considerable evolution of heat but without generating hydrogen ;when the reaction becomes sluggish, heat is applied, and hydrogen isthen seen to escape.The hot filtered solution deposits needles ofdiphthnZyZ, C16H804, on cooling ; this melts above 32U" and can be sub-limed in a current of carbonic anhydride. @n diluting the moiher-liquor with water, a flocculent precipitate is obtained, containinghyclrodiphthalyl, C16H1004, and hyc~rod~~hthalluctorlic acid, C16H1204,separable by means of sodium carbonate solution. Hydrvdiphthallyl,CO <yf:>CH.CH<Cf:>CO, crystnllises from boiling alcohol inslender colourless needles, melting between 228" and 229" ; it dissolvesextremely readily in boiling glacial acetic acid. Hydrodiphthal-lactonic acid, cO<yf:> CH. CH,. C6H4. COOH, dissolves very readilyin hot, sparingly in cold alcohol, and crystallises in short thick four-sided, vitreous prisms, melting a t 198.5" ; the potassium salt is readilysoluble, the silver salt, C1,H1,O4Ag, forms a white very stable pre-cipitate. On boiling the acid with excess of potash, two molecules ofthe latter become neutralised, and on then acidifying with hydro-chloric acid, ~ i ~ d r o h ~ i d r o x ~ ~ i p h t ~ a l y ~ ~ c acid,COOH.C6H,.CH2.CH( OH) .C6K4.COOH,is obtained, crjstallising in colourless prisms ; this melts a t 170" wirhseparation of water, then solidifies and melts again at 198.5". When hy-drodiphthallactonic acid is boiled with hydriodic acid and phosphorus,CMe CHA. K. M5 8 ABSTRACTS OF CIIEMICAL PAPERS.the acid, Cl6HI40.i, obtained by Or-aebe from diphthalyl, is formed, andis named by the author dib(!nayEdiorthocnrbo~~l~c acid,COOH.CcH4.CH,.CH,.C6H,.COOH.The dilnteci mother-liquor from the diphthalyl and diphthallactonicacid contains phthulicle which can be separated by extraction withether; i t crgstallises from warm ether and alcohol in densc stronglyrefracting prisms, and from boiling water in needles ; i t melts at 73",arid is volatile without decomposition, its boiling point being 281.5" a t:t pressure of 750 mm. (286.5" cow.). The residual solution freedfrom phthalide still cont ains zinc salts of acetic, phthalic, and hydro-diphthallactonic acids.The formation of diphthalyl from phthalic anhydride and zinc takesplace thus: 4C80,0, i 2Zn = 2C8H404Zn + C16H,04, this beingproved by heating fused plithalic anhydride at 130-140" with zinc-dust (free from oxide), wheu a mixture of zinc phthalate anddiphthalyl is obtained. A.K. M.Isatin. (Preliminary Note.) By H. KOLBE (J. pr. Chern., 30,S4--87).-Isatin is converted by chromic acid, dissolved in glacialacetic acid, into an acid which the author styles iscntoic acid, and whichhe regards as ~~itrogen-~eiza~~lcarboxylic acid, c6 { $} CO.COOH.It is sparingly soluble in cold water and alcohol, but easily in hotivater, from which it crystallises in yellow rhonibic tables. Thissitme acid is obtained by oxidising indigo with chromic acid.IVhen isatoic acid is heated above its melting point, or when itsayneons solution is boiled, it is decomposed, water and carbonic anhp-dride being formed.When boiled with baryta-water, a new acid isproduced, which is easily soluble in water, and seems t o be formedwhen isatoic a.cid is heated with sulphuric acid. In attempting toprepare th5 ethyl salt of this acid, a liquid was obtained, probablyC6H4N.COOEt, and an acid, which is probablyc { Ei} c { gHH} COOH. P. P. B.Formation of Dibenzyl from Ethylene Dichloride andBenzene in Presence of Aluminium Chloride. By W. H. GREENE(Chem. News, 50, 61).-By a,pplying Friedel and Crafts' reaction to amixture of benzene and ethylene dichloride, the author has obtaineddibenzyl (boiling point, according to present determination, 279" at'767 mm.), in nearly tbeoretical quantities, along with oily condensa-tion-products, which can neither be completely distilled, even a t 200"in a V~CUUIII, nor fractioned, nor solidified in a freezing mixture.D.A. L.Trichlorocamphor. By P. CAZENEUVE (Cornpi. rend., 99, 609-Gill).-Monochlorocamphor (melting a t 83-84") is heated on a water-bath and saturated with chlorine gas. The product is washedrepeatedly with water in order to remove hydrochloric acid, then dis-solved in alcohol, and the solution placed in a rnixtuie of ice anORGASIC CIIEXISTRII'. 59salt, when it separates into two layers, the lower of which is a mole-cular combination of the trichlorocainphor with alcohol, solidifyingbelow 0". This compound is decomposed by waler, ihe product com-pressed in order co expel a liquid substance, which is in all proba-bility a more highly chlorinated derivative, and then purified byrepeated solution in alcohol and precipitation by water.The trichloro-camphor thus obtained has the composition CloH,,C1,O, and formswhite microscopic crystals, which have w r y little odour, and resembleterebenthene derivatives. It is insoluble in water, but dissolveseasily in cold alcohol, ether, chloroform, carbon hisulphide, and theother solvents for camphor, It melts and solidifies at + 5 4 O , liquefiesin the vapours of ether and chloroform, like the mono- and di-deriva-tires, and in alcoholic solution has a dextrorotatory power [a] = + 64".When boiled, it decomposes with evolution of hydrochloric acid andformation of a carbonaceous residue.Prom its appearance, solubilities, and crystalline form, this deriva-tive seems to belong to the /3-series of chlorocamphors.C.H. B.Camphoronic Acid. By J. KACHLER and F. V. SPITZER (Monatsli.Clienz., 5, 415-416) .-The formula C9H,,05,H,0 has been previouslygiven to this acid (A7waZen7 159, 286), which Kissling (Inuuq. Diss.,Wurtzburg, 1878) believes to be an anhydride, the true acid beingC9H1406. The authcrs are studying the action of aqua regia a'ndpotassium permangsnate OII the acid.Kinoin in Malabar Kino. By C. ETTI ( B e y . , 17, 2241-2244).-Kremler (Vienna yl~ul.mnceutisclie Post, 16, 117) and A. Bergholz(Inauy. Dissert., Dorpat, 1884) deny the presence of kino'in in Malabarkino, and state that they have found protocatechuic acid therein.The authoi' proves the methods employed by these investiptors to bevery faulty, and fully sustains the comectness of his own earlierinvestigations on this subject (Abstr., 1879, 159).Substances contained in Saffron. By R.KAYSER (L'er., 17,'2228--8234~).--I(ouillon, Vogel, Qnadrat, Rochleder and &layer, andWeiss have a t various times worked at this subject, but the infoima-tion at present available is unsatisfactory. The author has thereforecarefully investigated a sample of saffron from Crocus eZectus, Qutin.Essential Oil of Safron.-This was obtained from saffron by steam-distillation in a current of carbonic anhydride. It is an almostcolourless mobile liquid, with an intmse odour of saffron. Whenexposed to the air, it becomes oxidised and turns brown and syrupy.Aiialysis showed its composition to be C,,H,,, so that it belongs to theclass of terpenes.Crocin.-Saffron was first freed from fatty matters, &c., by etherand then extracted with water at the ordinary temperature.Theaqueous solution was shaken up with bone-charcoal. which absorbednearly all the colouring matter. The charcoal was filtcrcd of, and thecrocin extracted from i t by washing with pure water. This solutionwas evaporated to dryness, and the residue treated with 90 per cent.alcohol. On evapordting the alcoholic solution, a yellowish-brownH. B.L. T. T60 ABSTRACTS OF CIIE31ICAL PAPERS.brittle mass is left, which yields zt yellow powder. Crocin is easilysoluble in water and dilute alcohol, less so in absolute alcohol, andalmost insoluble in ether.Strong sulphuric acid dissolves it to adeep blue solution, which turns first violet, then cherry-red, andlastly brown. Nitric acid (sp. gr. 1.4) gives a similarly colourad sola-tion, b u t the colour immediately changes to brown. Hydrochloricacid yields a yellow solution. Load acetate, and lime- and baryta-water give no precipitate, but, on heating, they decompose crocin intocrocetin and a sugar. Alkalis cause the same decomposition in thecold. Crocin is thus a glucoside, and analysis shows its cornpositionto be CalH7,02,.Crocetin is best obtained by the action of hydrochloric acid oncrocin. It is precipihted in the form of yellow flocks, which whendried yield a red powder. It is almost insoluble in pure water, butis rendered soluble by the addition of a small quantity of an alkali.Acids reprecipitate it from such solutions in orange flocks.It iseasily soluble in alcohol. An alcoholic solution gives bright red preci-pitates with lead acelate, and with lime- or baryta-water ; the com-pounds so formed, however, are not definite, but vary in composition.Snlphuric and hydrochloric acids behave with it as with crocin. Itscomposition is C,4H,60,. The decomposition appears to take placeaccording to the equation ~ C J ~ H ~ O O ~ S f 7H20 = C:,J€&, + 9C6H&.0rocose.-The sugar mentioned above yields rhombic crystals. Itsfiolution has a, sweet taste and strong dextrorotatory action. Itsreducing power for Fehling’s solution is only half that of dextrose.The quantities of crocetin and crocose obtained by the decompositionagree very closely with those required by the above equation.Picl.ocroci.n.-Su~~un-bitter.-l’his substance crystallises out in theether-extracting apparatus if the extraction be continued for a longtime.It forms colourless prismatic needles, very sparingly solublein ether. It dissolves easily in water and alcohol, less so in chloro-form. It has a, characteristic bitter taste, which is very persistent.It melts a t 75” to a colourless liquid. Its formula is C38H6S017. Leadacetate, lime-water, and baryta-water give no precipitate in the cold,but decompobition takes place on warming, crocose and the terpenedescribed above being formed, Picrocrocin is thus a glucoside likecrocin, and the decomposition may be expressed by the equation-C.>EIHFI~OI~ HzO = 3C6H1206 + ~CIOHI,.L. T. T.C arboxylic Acids from Synthetically Prepared PyridineBases. By R. MICHAEL (AmaZe.n, 225, 121--146).-Hantzsch hasrecently described the synthesis cjf a ppridiDe-derivative, ethyl hydro-collidinecarboxylate, by the action of ethyl acetoacetate on aldeliyde-ammonia, the formation from it of collidinedicarboxylic acid, andfurther, the limited oxidation of this latter substance by which it isconverted into lutidinetricarboxylic acid, pisoliaetetracarboxylic acid,and pyridinepentacarboxylic acid (Abstr., 1883, 82). The presentpaper deals with the formation of a collidinemonocarboxylic acid andits oxidation into a series of acids each containing a COOH-group lehsthan those above mentionedORQANIC CHEBIISTRP.61ColIidinemoriocni.boaylic acid is formed by heating collidinedicarbo-xylic acid, but in such small quantity that a more satisfactory methodfor its preparation had to be found.Hydrogen ethyl coZZidined i c a r b o q Zate, C5NMe3 (C 0 OE t) . C 0 0 H, isprepared by heating the diethyl salt with the quantity of alcoholicpotash necessary to saponify o d y one COOEt-group ; any undecom-posed diethyl salt m7as then removed by shaking with ether, the solu-tion of the potassium ethyl salt evaporated to dryness with the equiva-lent amount of hydrochloric acid, and the hydrogen etliyl salt sepa-rated from potassium chloride by solution in absolute alcohol. Itcrystallises (+ ;?H,O) from water in rosettes of long prisms or in thickwell-formed prisms, apparently of the monoclinic system ; from alcoholin stellate groups of needles.It melts, when anhydrous, at 157", isreadily soluble in alcohol and water, sparingly soluble in ether. Thefollowing salts were prepared from it. The acld silver salt,AgEtC,,H,NO, + HEtCioH,NO* + H20,forms small monoclinic prisms, and is not blackened by exposure tolight. The zinc salt, (EtC,,K,NO,),Zn + 5H20, crystallises in rosettesof colourless prisms, sparingly soluble in cold, readily in hot water.The cadmium salt, ( EtC,oH,N04),Cd + 4H20, crystallises in striatedprisms, and is readily soluble in hot water. The copper salf,(EtC,,H,NO,),Cu, forms an indigo-blue powder consisting of micro-scopic plates. It is anhydrous and insoluble in water.The caZciurnsaEt, (EtC1,H,NO,),Ca + 3H20, forms crusts of fine needles, and isreadily soluble in water and alcohol. The baritm salt,(EtC&gN0,)2Ba + 3H20,is sparingly soluble in water, insoluble in alcohol. It can also beobtained with only 1 mol. H20. The potassizcnz salt crystallises with1 mol. H,O in fibrous masses. The niclcel salt crystallises in pale greenprisms, the mezerc~~roi~s salt in thick tables. The hydrogen ethyl salt,like the free acid, combines with acids : the hydrochlode,C,NMe,(COOEt) .COOH,HCl,prepared by the action of hydrochloric acid on an ethereal solution ofthe salt, crystallises in thick transparent cube-like forms, melts a t1%" with decomposition, is very readily soluble in water, readilysoluble in alcohol.The platirudiloride,[ C5NMe3( C OOE t) . C 0 0 HI,, HzPt CI,,crystallises in red rhombic (?) tables, or with 2 mob, R,O in large,broad prisms, is sparingly soluble in cold alcohol, readily soluble inwater ; i t melts with decomposition a t 219".Ethyl collidi.nemonocarboxylate, C5NHMe3.COOEt, was obtained illvery small quantity by Hantzsch (Zoc. cz't.) by heating ethyl hydro-collidinemonocarboxylate with hydrochloric acid ; it is readily obtainedby heating hydrogen ethyl collidinedicarboxylnte, when it passes overbetween 230" and 260°, and can be purified by continued fractiona-tion. The yield is 56--.58 per cent. of the theoretical. It is a colour-less oil, distils at 256", has a sp.gr. = 1.0315 a t l5", and is readilG2 ABSTRACTS 01'' CHEMICAL PAPEHS.soluble in ether, alcohol, benzene, chloraform, and dilute acids. Crys-talline compounds with acids could not be obtained. The platinochlo-Tide, (C,NH~~e,.COOEt),,H~PtCl~, crystallises in thick reddish-yellowprisms, and melts a t 193"; i t is sparirlgly soluble in alcohol, readilysol iible in water.C,NHMe,.COOEt,MeI,formed by the union of its components at ordinary temperatures,crystallises in silky needles, melts a t 128", is readily soluble in alcoholand water, insoluble in ether.CoZZidinemonocarbox~Zic &7, C5NHMe3.COOH + 2H20, is preparedfrom the ethyl salt by saponification with alcoholic potash, and evapo-ration to dryness of t'he potassium salt formed with the equivalentamount of hydrochloric acid. It crystallises in short tetragonal (3)prisms o r in cube-like forms, and melts at l l O o , or, when anh-j-drous,a t 155".It is extraordinarily soluble in water and alcohol. It haseither a, very faint acid reaction or none at all, and unites with acidsand bases. The potassium salt, C5NHMeJ.COOK, is obtained as ayellowish powder, but can be crystallised from alcohol, when it formstufts of needles. It is very readily soluble in water and deliquesceson exposure t o the air. The calcium salt, (C9HloN0,),Ca + H,O,forms a crystalline powder soluble in water.ELhy I co Zlidiitecarhozy 1 ate met hiodide,The hydrochloride,C5NHMe3.COOH,HC1,crystallises in wart-like groups of needles or prisms, and is readilysoluble in water or alcohol.(C5NHMe3.COOH)2,H',PtC16 + H20,ciytallises in thick yellowish-red tables, melts at 198" with decompo-sition, is readily soluble in water, sparingly soluble in alcohol.Lu,tidinedicai.bo~,~lic acid, C5NHMe2(COOH)2 + l$H,O, is preparedhy heating on the water-bath a mixture of an aqueous solution ofpotassium collidinecarboxylate with the amount of potassium per-manganate necessary to oxidise one methyl-group, filtering off theinanganic oxide separated, neutralising with nitric acid, and precipi-tating with lead nitrate, the lead salt being then suspended in waterand decomposed with hydrogen salphide.It crystallises in colourless,lustrous pyisms, melts, when anhydrous, at 245", is sparingly solublein cold, more readily in hot water, and nearly insoluble in alcoholor ether.With silver nitrate, a solution of the ammonium salt givesa gelatinous precipitate, becoming crystalline on boiling ; with leadnitrate a, thick white precipitate, or from dilute solutions, after a time,rhonibic tables separate, which on being boiled become transformed intofihort prisms. The calcium salt, (15NHMez(C00)2C;. forms indis-tinctly crystalline crusts readily soluble in water. The magnesiuinFalt, C,NH&fe3( COO),Mg + 3H,O, resembles the calciuni sait. ThehydrochZoride crystallism in slender needles. The pZatl'nochloridP,[C,NHbIe,( COOH),],,H,PtCI, + 6H20, crjstallises in golden rhombictables or in reddish-yellow prisms, does not melt at 290", and isreadily soluble in water and alcohol.PicrJZinetl.icarbozyZic acid, C,NHMe(COOH), + 2H20, is obtainedThe platirtochlorideORGAXIC CHEJIISTRP.63in a manner similar to the abo-re, but with use of sufficient potassiumpermanganate to oxidise two of the methyl-groups in the potassiunzcollidineearboxj-late ; it is separated from any 1 utidinedicarboxglic acidformed a t the same time by repeated crystallisation from water, inwhich it is the more readily soluble of the two. I t crystallises inflocculent groups of slender needles, on heating becomes yellow below2C)O0, brcwn or black a t 210-22507 and melts with much frothing a t238'. A solution of the ammonium salt gives a gelatinous precipitatewith silver nitrate ; witb barium chloride a voluminous precipitate ;with lead and mercnry salts heavy white precipitates; and mit,hferrous salts a yellow coloration not altered by acetic acid.Thesilver saZt, C5NHMe( COOAg),, i s not crgstallinc. The bariwn salt,[C,NHMe(COO)3],Ba3, forms a hard sand-j- powder. Picolinetricar-boxylic acid does not combine with mineral acids nor yield a platino-chloride. A picolinetricarboxylic acid was obtained by Besthorn andFisher (Abstr., 1883,600) by the oxidation of flavenol, but it is doubt-ful whether it is identical with the acid abore described; the differencein the colour-reaction with ferrous salts and i i i the solubilities of thebarium and calcium salts seem to indicate tbat it is not.Pyridinetetl.acar7)ox?/Zic acid, C5NH( COOH), + 2H20, is preparedfrom potassium collidinecarboxylate by oxidation with a quantity ofpotassium permanganate slightly less than that necessary for theoxidation of the three methyl-groups. Its preparation is somewhatdifficult, the oxidation readily proceeding further with formation ofoxalic acid and carbonic anhydride.The solution, after filtering offthe manganic oxide, is neutralised with nitric acid, evaporated, andmixed with cupric sulphate, when cupric ~.'yridinetetracarboxSl,zte isprecipitated, whilst cupric lutidinedicarboxylate and picolinetricar-boxylate remain in solution. The free acid is obtained by decomposingthe copper salt with hydrogen sulphide ; it is still far from pnre, tbeanalytical numbers bcing very unsatisfactory. It crystsllises inslender needles, melts with decomposition a t 188", and is sparinglysoluble in alcohol and water.A solution of the ammonium salt giveswith cadmium sulphate a pulveriilerit precipitd e insoluble in hotwater, with silver nitrate it gelatinous precipitate blackened by expo-sure to light. A solution of the acid gives with copper sdts anamorphous bluish-green precipitate ; with ferric chloride a yellowishflocculent precipitate ; and with ferrous salts a brownish-red colora-tion, turning to dark cherry-red on addition of acetic acid.A. J. G.Brucine. By 9. RANSSEEN ( B e y . , 17, 2266--2267).-On heatingbrucine with hydrochloric acid, methyl chloride is given off and a sub-stance formed which crystallises in yellowish needles melting at 284".This when freshly precipitated dissolves readily in alkalis, and is re-precipitated by carbonic anhydride.With ferric chloride, it gives abluish-violet, with potassium dichromate and snlphuric acid a blood-red colour, and with nitric acid a brownish-yellow precipitate. Itforms a platinochloride crystallieing in bronze-coloured flakes. Boththe free base and its platinochloride, on analysis, yield numbers agree-ing with the loss of one methyl-group from brucine. If this com-pound is treated with potassium hydroxide and metllJl iodide, brucinG4 ABSTRACTS OF CHEMICAL PAPERS.methiodide, melting at 270", is formed identical with that obtaineddirectly from brucine. It is thus probable that brucine contains butone methoxy -group.Alkaloids from the Bark of Remijia, Purdieana.By 0.HESSE ( A n n u l e n , 225, 211-262) .-A preliminary notice of some ofthe results contained in this paper has already appeared (Abstr.,1883, 601). A description is given of the structure and properties ofthe bark. The alkalo'ids of this bark have been previously examinedby Arnaud, who found about 0.2 per cent. of cinchonamine, and0.8-1.0 per cent. of cinchonine. The author confirms the presenceof these bases, but finds that several other alkaloi'ds are present, andthat the amount of cinchonine is only 0.1-0.2 per cent. Theseparation of the alkaloids is effected as follows : the finely dividedbark is extracted with hot alcohol, the solution evaporated, and theresidue after treatment with excess of caustic soda, extracted withether.The ethereal solution is treated with excess of dilute sulphuricacid, and shaken, when the sulpbates of concusconine, chairamine,conchairamine, chairamidine and conchairamidine are precipitated,(A) whilst the sulphates of cinchonine and cinchonamine with smallquantities of the other bases remain in solution (B). By addition ofvery dilute nitric to the solution (B) cinchonamine is precipitated asnitrate and cinchonine is left in solut>ion. The precipitate A is di-gested with dilute soda, and the separated nlkalo'ids, after washing, aredried in the air, dissolved in hot alcohol, and sulphuric acid diluted withalcohol, added in the proportion of 1 part H2SOJ to 8 parts of thealkaloids. Nearly the whole of the concusconine separates as sulphate,a fnrther very small quantity separating on cooling.On adding con-centrated hydrochloric acid to the cold alcoholic filtrate, c7zairamineseparates as hydrochloride. The mother-liquor from this is heated,and small quantities of ammonium thiocyanate added as long as acrystalline precipitate is formed of conchuircrrnitie thiocyanate.After cooling and filtering, the liquid is again treated with am-monium thiocyanate, when a dark-coloured pit eh-like mass separates ;the filtrate from this is treaked with ammonia, and the resultingprecipitate shaken up with brnzene. The benzene solution is shakenwith dilute acetic acid, and the solution of the acetates so obtainedmixed with a saturated aqueous solution of ammonium sulphate,when %I precipitate of chairamidine aid conchairamidine siilphates isobtained.These are separated by dissolving them in boiling water andcooling, when the whole gelatinises ; on standing, crystals appear,the crystallisation being complete after some days ; on now heating to40°, the chaii*a?~iidl:ne sulphate dissolves, whilst conchairamidinesulphate is left. The process must be repeated several times on thesolution to obtain a pure product.Cinchonamine and its salts have been to some extent described byArnaud (Ahstr., 1884, 87)) whose results the author in generalConfirms, although differing in some details. Cinchonamine, ClsH2eNa0,crystallises in brilliant colourless needles, melts when anhydrous a t184-185" (194", Amaud), is readily soluble in hot alcohol, ether,chloroform, carbon bisulphide, and benzene, sparingly soluble i nL.T. TORGANIC CHEMlSTRP. 65light petroleum and water. I t s adcoholic solution has a strong bittertaste, and an alkaline reaction, and is dext'rorotary : [m]D = + 121.1"at p. = 2 and t . = 15". It dissolves in concentrated sulphuric acidwith reddish-yellow colour, which slowly darkens ; in nitric acidwith an intense yellow. It is soluble in concentrated hydrochloricacid, but it is decomposed when heated with it in sealed tubes at150". It,gields two series of salts, normal and monacid. Theh@oc7~ lorzde, C19H24N20,HC1, crystallises in anhydrous colourlessplates, readily soluble in alcohol, very sparingly soluble in water(according to Arnnud it contains 1 mol. H,O). The plntinochloride,( ClgH,,N20),,H,PtC1,, is obtained as a yellow flocculent precipitate,apparently becoming crystalline after a time. The hydwbrornide,C19H2aN20,HBr, crystallises in long flat needles, sparingly soluble incold water.The 2, ydrioditle, CIYH24N20rHI, forms long colourlessflat needles. The thiocynnatn, CI9HZ4N,O,CNSH, forms colourlessplates or short prisms, and is very sparingly soluble in coldwater. The nitrate, C19€€21N20,HNOJ, forms short colourlessprisms, melts a t about 195", is sparingly soluble in cold water,readily in boiling water and hot alcohol. The normal suZp7iafe,(C,9H,,N,0)2H,S04, crystallises in colourless prisms, is readilysoluble in hot or cold water, very sparingly soluble in cold alcohol.Its aqueous solution is dextrorotary : [ a ] D = + 36.7" a t p.= 2 andt. = 15 ; [O]D = f 39.8"atp. = 6 ; and [OC]D = -l- 39.6" a t p. = 2 and2 mol. H2S04. The arcid sulphnte, C19H2iN20,Hk30J, crystallisesin anhydrous prisms and shows the rotary power = + 34.9" atp. = 2.4 and t. = 15" and [ 1 ] D = + 37.4" a t p . = 6. The th;osuZplm,ts,C19H24N20,S203H2, forms anhydrous prisms sparingly soluble in water.Acet?lZainchonantine, CI9H2,AcN,O, prepared by heating cinchonaminewith acetic anhydride for some hours a t 85", is amorphous, sinterstogether a t 65", and melts a t 89-90", is readily soluble in ether,alcohol, chloroform, and acetic acid. DinitrociiLchonamine,c 19H22 (PU'O,) 2x20,is best prepared by dissolving cinchonamine in nitric acid of sp. gr.1.06, and pouring the intensely yellow solution into an excess of verydilute ammonia.It forms yellow flocks, melts a t 118", is readilysoluble i n ether, chloroform, alcohol, and acetic acid. A solution inhydrochloric acid gives with platinic chloride a yellow flocculentprecipitate of thephtiizoch Zoride, [ C,,H,,(N0,),N,0]2,H[,PtCl~ + 3H20.Cinchonninine rnethiodide, C19H,,N,0,MeI + HzO, prepared byadding methyl iodide to a solution of cinchonamine in methylalcohol, crystallises in hard colourless prisms, readily soluble inalcohol, sparingly soluble in water. The chloride. C19H,4N,0,MeCl~ isamorphous. The pZntinoc7doride7 ( CI,H,,N,OMeC1),PtCI4, is obtainedas a yellow crystalline precipitate. The h?ydroxide, obtained by theaction of silver oxide on an aqueous solution of the chloride, formsan aniorphous mass, readily soluble in water and alcohol, sparinglysoluble in chloroform and ether.It has an intemely bittev taste,and is a powerful base, eagerly absorbing carbonic anhydride fromthe air.VOL. XLVIIT. 66 ABSTRACTS OF CHEMICAL PAPERS.Methylcinchonnmine, C,,H,,MeN,O, is prepared by boiling cinchon-amine methiodide, chloride, or hydroxide, with caustic soda. Itforms an amorphous white powder, melts a t 139", is readily solublein alcohol, ether, and chloroform, insoluble in water. The chloride isamorphous, the p7ntinuchZoride7 (C,,H2,MeN2O),,H2PtC1, + 4H20, isobtained as a reddish-yellow flocculent precipitate.Cifichortaniine ethiodide, C19H24N20, EtI, forms a colourless varnish,readily soluble in alcohol, nearly insoluble in water.The eldorideforms colourless prisms, readily soluble in alcohol and hot water.The plahnochloride, (Cl,Hz4N20,EtCI),,PtC14 + 2Hz0, forms orange-colouretl crystals. The sdphate, (C,,H,,N,OE t),SO,, is colourless andamorphous. The hydroxide resembles the corresponding methylcompound.Ethz~7ci~~echoizanziize, ( C19H2,EtN20)3 + H20, forms a white powder,melts at. 75-i8", or when anhydrous at 140", aild is readily soluble inether and alcohol. The platinochlnride, (C,,H,,EtN,O),,H,PtCl, +3Hz0, forms a reddish-yellow flocculent precipitate.Conczwonhie, C,7H26N,04 + H,O.-This alkaloid is obtained as thenormal siilphate as already described, and is obtained in the free stateby decomposition of the snlphate with dilute soda, and recrystal-lisation from alcohol to which a little ammonia has been added.It forms colourless or pale-yellow compact prisms.It is readilysoluble in ether, chloroform, and benzene, sparingly soluble in boilingalcohol, insoluble in water. It is optically dextrorotary, giving forC,,H2,N204 + H20, p. = 2, t. = 15" ; in 97 vol. per cent. alcohol= 40.8" The hydrate melts at 144", becomes anhydrous, and thenmelts again a t 206-208"; a t 140-150" it becomes dark-browncoloured, being in small part converted in to amorphous concusconine.(This amorphous concusconine is readily separated by conversion ofthe fused mass into the normal sulphates, treatment with alcohol inwhich the sulphate of the a!morphouu base is readily soluble, andprecipitation with ammonia, when it separates in dark-brown, amor-phous, readily fusible flocks.) Concusconine dissolves readily inacetic anhydride apparently withoiit formation of an acetyl-derivative ;from t h i s it seems that no hydroxyl-groups are present.Nitricacid converts it into a dark-green mass ; addition of nitric acid to itssolution in acetic o r hydrochloric acids gives the dark-green colorationcharacteristic of this group of alkalo'ids. Concentrated sulphuricacid dissolves concuscoiiine with bluish-green colour, becomingolive-green on beating. With chromic acid and sulphuric acid, itgives a coloration at first dark reddish-brown, then intensely dark-green. Although concusconine is tasteless, its solutions in acidshave a bitter taste.The platino-nhloridp, ( ~ , , H , 6 N , ~ 4 ) , . ~ 2 P t c ~ 6 + 5H20, is obtained as a voluminousyellow flocculent precipitat'e.The salts are as a rule gelatinous.The nornzaZ sulphate,forms small white prisms nearly insoluble in water and alcohol in thecold, sparingly soluble on heating. The acid sulphnts is a gelatinousmass readily soluble in hot water. By mixing an alcoholic solutionwith methyl iodide, and allowing it to stand 21 hours, there iORGANIC CHEMISTRY. 67obtained a mixture of two iodides in about equal quantities ; they canbe separated by the difference of their solubilities in hot alcohol.The less soluble a-compound forms microscopic hexagonal prisms ofthe formula C23H,fiN201,MeI, very sparingly soluble in hot alcohol,moderately poluble i n boiling water.By trextmdnt with silverchloride, i t is converted into the chlorid~, C2,H,,N,0,,hfeCI, crystallisingin microscopic needles, readily soluble in water and alcohol. ThepZa,tiuiochloride, ((=,,H,,M~N,OIC1),,PtClI + 4 H 2 0 , forms a yellowish-red flocculent, prccipitate, and is insoluble in water. The aurochlorideforms a dirty gellow flocculent precipitate, from which gold soonseparates. The sulplmte, (C2,H,,MeN,0J)2S04, formed by the action ofsilver sulphate on the iodide, is amorphous arid very readily soluble inwater and alcohol. I t s rotarg power in aqueous solution at p. = 3.764and t. = 15" is [%ID = + 73". The hydroxide, C2,H,,N,04Xe.0H +5H20, obtained by the action of baryta-water on the sulphate, cr.ystal-lises in colourless cubes, melts at 203", is rea3ily soluble in alcohol andboiling water, insoluble i n ether.The iodide of the /3-co)npoud,C27H26N101MeI, is gelatinous and dries in air to a horcy mass ; is some-whak soluble in boiling water, readily soluble in alcohol. The chlorideis amorphous. The platinochloride, ( C,,Hz,N,O,MeCl)?,PtCZ1 + 5H,O,is a reddish-yellow flocculent precipitate. The sulphate,( C23H2GN204Me)2S0i,is a brown amorphous mass, and has no action on polaiised light.The hydroxide, Cn3H,,NZO4Me.OH + 2$H,O, forms a brown amor-phous mass, readily soluble in cold water and alcohol.Chairamine, C,,H,,N20, + H,O, crystallises in white needles orthick colourless prisms, and melts at 140", or when anhydronq, at233.It is readily soluble i n ether and chloroForm, 1 part of t h ebase dissolves in 540 parts o€ 97 per cent. alcohol. The alcoholicsolution is strongly dextrorotary ([a]? = about looo). Dissolved insulphuric acid containing molybdic acid, the solution a t first colour-less becomes after a tiqie an intense dark-green. The hyrZroclJoride,C22HJY?0,,HCl + H,O, crystallises in colourless needles, sparinglysoluble in boiling water and alcohol, insolulde i n dilute hydrochloricacid. The pZci,tinochlo.ride, (C,2H2,N,04),,H,PtCIs + 2H20, formsyellow needles insoluble i n water and alcohol. The ??orrrrci/ suI/iJL,ite,(C22H26N204)2,H2SO~ + 8H,O, forms concentric gi-oups of colourlessneedles, sparingly soluble in cold water or alcohol. The fhicrcyanateforms white needles insoluble in water.Conchairlnmine, crysta!lises with both water and alcohol of crystal-lisatiori in thick colourless prisms of the formula C,,H,N,O, +H,O + CzH60, the compound showing three meltinq poiiits, namely,82-86" for the whole compound, 108-110" after expulsion of thealcohol, and about 120" for t h e anhydrous compound, the massresolidifying between each temperature.A small portion is convertedby the heating into amorphous conchairamine. Conchairailline isreadily soluble in hot alcohol, in ether, and chloroform, sparinglysoluble in cold alcohol. Its solution i n 97 per cent. :ilco+ol has arotary power [ a ] ~ = + 68.4" a t p. = 2 and t. = 15". The alcoholatedissolves in sulphuric acid containing molybdic acid, qivin? a brownf 68 ABSTRACTS OF CHEMICAL PAPERS.colorat.ion that soon becomes intensely dark-green.With potassiumchromate and sulphuric acid, i t gives a coloration at first reddish-brown, then dark-green, and reddish-yellow if boiled with excess,The hydrocldoride, C,,H,,N204,HC1 + 2H20, crystallises in colourlessplates, readily soluble in hot water and alcohol, spwingly solublein cold water, nearly insoluble in ether. The platinochloride,(C72H282O4)2,H2PtCI6 + 5&0,forms it dark-yellow flocculent precipitate. The hydroiodide, +crystallises in colourless needles, sparingly soluble in cold water.The tlLiocyanate crystallises in colourless needles, very sparinglysoluble in hot water. The sulphate, (C,,H26N204),,H2S0, + 9H20,crystallises in long lustrous prisms, soluble in boiling water.Then i t r a t e forms satiny plates o r needles very sparingly soluble in water.Conchnira.mine rnethiodide, C2,H2,N204,MeI, is obtained either in redcrystals containing 1 mol. H20, or in colourless crystals with 3H20.The ch7oride, C22&N204,MeC1 + 2H,O, crystallises in large colourlessrhombohedrons, readily soluble in water and alcohol. The pZnti?~o-chloride has the coEplex formula (C20,H2,N20JMeC1),,PtCil +( C,,H,6N,01MeHCl,),PtC1, + 14H20 ; it crystallises in orange-colouredneedles, and is insoluble in cold water. The nitrate forms colourlesssatiny plates. The hydro.cide formed by the action of moist silveroxide on the chloride, forms an amorphous brown mass of bittertaste, readily soluble in water, insoluble in ether.Chairamidine, C2,H,,NZO4 + H20, fornis an amorphous whitepowder, melts a t 126-128", and is readily soluble in ether, alcohol,benzene, and chloroform, insoluble in water.Its alcoholic solutionRhows the rotary power [ a ] D = + '7.3" at p. = 3and t. = 15". Itdissolves in roncentrated sulphuric acid with yellowish colour, whichlater turns dark green. The platinochloride, ( C22H,N,04),,H,PtC16 +5H&, forms yellow amorphous flocks insoluble i n water. The normalsulphafe and liydrochloride are gelatinous, the acetate forms a slimymass.Conchairamidine, C2,Ho,,N20a + H,O, crystallises in white needles,melts at 114-115", and is very readily soluble in ether, chloroform,alcohol, benzene, and acetone. Its solution in alcohol (97 per cent.)is levorotary, [a]= = - 60" a t p.= 3 (anhFdrous) and t. = 15". Itdissolves in concentrated sulphuric acid with an intense dark-greencolour. With chromic: and sulphuric acids, it gives a solution at firstbrown, then dark-green. The hydrnchlo~ide, C,,H,,N,O,,HCl + 3Hz0,crystallises in long colourless needles. The pZatinochloride,( C,,H~~NZOI),,HZ?~CI~ + 5Hz0,forms a yellow flocculent precipitate. The normal sulphate,(C,,H,,N,Od),HzSOI + 14H20,crystallises in long colourless needles, sparingly soluble in cold water.The tli iocynnate is amorphous, readily soluble in alcohol, and spar-ingly soluble in cold waterORGANIC CHEMISTRY. 69The substance described under the name of concusconidine in theauthor's earlier communication (Zoc.cit.) has been found to be a,mixture of alkaloids. A. J. G.Preparation of Albumin. By W. MIHAILOFF (BUZZ. SOC. Chim.,41, 547--548).-The author describes a new method for obtainingpure albumin. White of egg, filtered through muslin, is treated withthree times the quantity of a saturated solution of ammoniumsulphate, and to this as much more solid ammonium sulphake isadded as will dissolve. The tillnuminoid substances (globulins, glo-bulinates, and albumin) are thus precipitated. The precipitate iswaslied wit,h a saturated solution of ammonium sulphate, and, havingbeen rendered slightly alkaline with ammonia, is dialpsed. The waterwhich replaces the excess of sulphate and the alkalis of the precipi-tated ai buminoids, leaves the whole of the globulins and globulinatesin the precipitate, and the pure albumin i s obtained in solution.Thissolution map be boiled without coagulation taking place, is almostneutral in its reaction (slightly acid): and gives no precipitate withbarium salts. By means of' ammonium sulphate, all albuminoids andtheir derivatives may be precipitated. A. B.Colouring Matter of the Blood. By M. NENCRI and N. SIERER(Ber,, 17, 2267-2276).-The authors find that tlie use of amyl alcoholas a solvent forms a very good method for obtaining hcemin fromblood. Freshly defibrinated blood is mixed with a solution of saltand allowed to stand for 2 4 4 0 hours in shallow dishes. It is thenmixed with double its volume of 99 per cent. alcohol, and stirred welluntil thoroughly coagulated.The coagulated mass is allowed to standanother 24 hours, and then filtered off and spread on blotting-paper.It should not be allowed to get too dry, and is usually dry enoughafter exposure to the air for about 24 hours, when it should still loseabout 60-65 per cent. of water if dried a t 110". This partly driedmass is then powdered i n a mortar, 400 grams n e introduced into itflask with 1600 grams of amyl alcohol, and the whole heated toboiling; 25 C.C. of pure hydrochloric acid of sp. gr. 1.12 are thenadded, and the whole boiled for 10 minutes and filtered. As it cools,the amyl alcohol deposits the hcemin as hydrochloride in thinglittering rhombic plates. These should be washed with alcohol andether, and dried a t 105". 1.5-3 grams of pure crystals are obtainedfrom 3 litres of blood.I n this way, haemin was prepared andanalysed from human blood, the blood of the ox, horse: and dog. Ineach case some of the crystals were converted into haematin by solu-tion in caustic soda and precipitation with hydrochloric acid. Allthese specimens of hEmatin from different sources mere also analysed.In all cases when tlie hiemin crystals were dissolved in alkali, amyl:ilcohol was liberated, and i t was found that when prepared as aboveIit~min alwap contains amyl alcohol of crystallisation, which it losesiieither by digestion with alcohol nor by drying a t 110". Thecrystals do not change in composition even when digested with diiutehydrochloric acid.The analyses of the samples from various sourcesgave numbers agreeing very closely, and leading t o tlie formuli70 ARSTRACTS OF CHEMICAL PAPERS.(C32H3,N4Fe03,HC1)2,C5H,,0 for haemin hydrochloride crystals, andCR2H3,N,Fe04 for haematin ; so that the latter is produced from heminby the addition of the constituents of water. The properties of thehaematin obtained as above agree with those ascribed to this compoundby Hoppe-Seyler. From the ease with which haemin forms doublecompounds with indifferent bodies such as amyl alcohol, t h e authorsthink it probable that its composition varies according to the methodof preparation ; and that the various hzenioglobins are possibly suchdouble compounds of haemin with albumins.Concentrated sulphuric acid deprives hematin of its iron, andHoppe-Seyler, who named the resulting compound haematoporphyrin,ascribed t o it the formula, C6sH,4N4012-a more highly hydrogeriisedformula than that which he ascribed to hzematin.The authors findthat the real formula of haematoporphyrin is CnHJ2N4O5, and that it isformed according t o the equation-C32H,,N404Fe + H2S04 + 0, = C'aH32N,05 + FeSO, + H,O.Haematoporphyrin is obtained much more easily by treating hemincrystals with conceiitrated sulphuric acid. Hydrocliloric acid isevolved, the crystals dissolve, and the solution deposits hEmatopor-phyrin. Haematolin, which is the product of tlie action of strongsulphuric acid on hEmatin out of contact with t h e air, is neithersolnble in acids nor in alkalis, and has not been further investigated.When subjected to the action of reducing agents, hmnin andhze-eiatin yield various reduction-products according to the nature of thereducing agent, the temperature employed, &c.With t i n and hydro-ch I o ric R ci cl , th e chief p rod uct i s heaah y d 1'0 h mnntop o r p h y r in , C ,H,,N,O,,which is formed from hemin crystals, according to the equationC3,H30N40,Fe,HC1 + 2H20 + HCI + H, = C32H3PN40j + FeCLIt is a brownish-red pigment, easily soluble in ;tlcohol, eparingly i ndilute hydrochloric acid, insoluble in water and alkalis. Whenboiled with alcoholic potash, i t is converted into a product easilysoluble in aqueous alkalis, and very closely resembling urobilin inproperties. The authors are now investigating this compound, whichalso appears t o be formed in stnall quantities during the redoction ofhaemin with tin and hydrochloric acid.By long-continued boilingwith tin arid liydrochloric acid, a soliltion of hmnin becomes qaitecolourless, volatile siibstaiices with odonrs resembling pyricline heirigformed. Attempts to obtain oxidation-products of hematin provedfruitless, nothirig bn t oxalic and carbonic acids being obtained.Leyer and Koller state ( B e y . , 7, 1064) that hRn1iitin is split up bydilute sulphuric acid into lucine and tyrosine. When fused withcaustic potash-towards which it is very stable--haematin gives offammonia and pyrroline, b u t no lucine is formed. Leyer and K611erwere probably dealing with impure hzematin.The colouring matter of the hlood is undoubtedly allied to thecolouring matter of the bile, and the conversion may be expressed bythe equationC,,H,,N,O,Fe + 2H,O = CJ2HEI:,.N106 + Fe.1-I mnat in.Uilir~binORGANIC CHEMTSTRY. 7 1Whether hasmatin is converted in the liver into bilirubin or bilirubiiiinto hsrnatin and hmmin is at present very doubt’ful, but the authorsare much inclined, from analogy with the formation of glycogen fromdextrose, &c., to think the latter more likely. L. T. T.Studies on Blood. By H. STRUVE (J. pr. Chem. [2], 29, 305-350).-The author contests the hitherto accepted riew of the com-position of blood-crystals, which according to Preyer are oxyhsmo-globin, of the formula C6,H,,N,5rFeS30,,,. The author finds thatthese crystals are rendered insoluble by treatment with alcohol, with-out changing their form, and that, they can then be further decolorisedby treatment with alcoholic ammonia, glacial acetic acid, strongsulphuric acid, or chlorine water, and therefore regards them ascrystals of a colourless albuminous subshnce accompanied by aniiuute quantity of one or more blood colouring matters. By extract-ing with ether, water, and alcohol respectively, the author hasobtained from the blood-corpuscles three distinct groups of com-pounds. The portion soluble in ether is, at ordinary temperatures, abrcJwn mass, which is generally soapy but sometimes crystalline. Whenheated, it melts and burns, emitting an odour of fat and acraldehyde ;the ash contains traces of phosphoric acid but no iron. Its solutiongives an absorption-band in the red, and it contains cholesterin,lecithin, cerebrin, and glycerides. The aqueous extract, on the otherhand, leaves on evaporation an amorphous mass of dark colour, readilysoluble in alcohol and water, but only slightly so in ether. Itssolution gives a strong absorption- band corresponding with Preyer’soxyhmmatin alkali; it gives no precipitate with lead acetate OYmercuric chloride in the cold, but the colouring matter is completelyprecipitated on boiling. Acids produce a precipitate even in the cold ;this is readily soluble in alkalis and alkaline carbonates withoutevolution of ammonia. It gives no hEmin-crystals ; the ash containsferric oxide, phosphoric acid, and silica. Elementary analyses of thecoloiiring matter point distinctly to its being a mixture of severalsubstances. The author regards the colouring matter as a feebleacid, which is probably combined in the blood with soda or someorganic base, and proposes to name it hcematic acid. The thirdgroup of SII bstsnces is obtained from the corpuwles by extractionwith alcoholic ammonia, and is represented by a single crystallinecolouring matter, which is quite insoluble in water, alcohol, ether,and dilute acids, sparingly soluble in dilute ammonia ; the ashconsists almost wholly of ferric oxide. The alkaline solutions of thecolouring matter exhibit the spec truin of Preyer’s oxyhaematin-alkali : on adding an acid, the colouring matter is precipitated quanti-tatively in an amorphous state ; this colouying matter yieldshmrintin-crystals. The elementary analysis corresponds with theempirical formula C,,&N8Fe,~lo, which agrees very closely withHoppe-Seyler’s formula for hematin, C68H70N8Fe2010. The author isof opinion that the hematin analysed by Hoppe-Seyler was impure,and that the carbon and hydrogen were coiisequently low. Owing toits behaviour with alkalis, the author regards this crystallinecolouring matter as a feeble acid, and proposes for it thc name o72 ABSTRACTS OF CIIEUICAL PAPERS.lrcrmic acid. The blood-crystals are thus to be considered as crystalsof a blood-albumin (globulin-crystals) free from iron, which arecoloured by a definite quantity of hematic and haemic acids. Thequantitative determiuation 9f these two acids is a t present impossible,but’ supposing the colouring matter to be entirely hEmic acid, and ifthe proportion of iron in the blood-crystals be -42 per cent., and inliemic acid 8*71 per cent., then the blood-crystals are composed ofglobulin-crystals 95.18 per cent., haemic acid 4.82 per cent. More-over, since tbe above empirical formulq both of the blood-crystals andof hemic acid, are calculated from the proportmion of iron they contain,the difference between the two must be the empirical formula ofthe globulin-crystals-ClsSHw9N50S058, taking Preyer’s formula,and C200H331Nj9SOS2, from Hufner’s formula.It is at present impossible to decide between the above formulae,but i t is especially interesting that the percentage compositionindicated by either of them corresponds in a remarkable mannerwith that given by Gorup-Besanez for the albuminoids in general.According to the author’s theory, all the spectroscopic phenomenaexhibited by solutions of blood are due exclusively to the colouring-matters, haematic and heemic acids ; he has not, however, succeededin attificially producing by means of mixtures of these two bodies, thebands a and p, which are characteristic of oxyhemoglobulin, andwhich are exhibited by all fresh solutions of blood. All the otherspectroscopic phenomena of blood solutions, e.g., the spectra ofhemoglobin, metahemoglobin, and haernochromogen, are to be re-garded as spectra of certain definite products of oxidation, reduction,or decomposition of hematic and hEmic acids. P. F. F