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ORGANIC CHEMISTRY 1590 r g anic Chemistry.Action of Chlorine on Trimethylene. By G. GUSTATSON (J. pr.Chem. [2], 42, 495--500).-Chlorine has hardly any action on tri-methylene in the dark, but explodes with it in direct sunlight.Chlorine was passed into a globe (74 litres) containing the trimethyl-ene (7 litres) and water; the globe was kept cool, and the oilallowed to collect in a separating funnel ground into the neck. Theoil consisted almost entirely of dichlorotrimethylenc.Dichlorotrimethylene, C3H4C12, is a colourless liquid of peculiarodour ; it boils a t 75" (746 mm.), and is nearly insoluble in water.Its chemical stability is great ; nitric acid decomposes it with diffi-culty; water at 180-190" has scarcely any action on it, and i160 hUSTftACTS OF CElEMlOAL PAPERS.can be distilled over sodium, which only acts on it a t 160-165",producing substances still under investigation.When dichlorotri-methylene and bromine (equal mols.) are sealed in a tube and exposedto sunlight for 4-5 summer days, or heated at 140-130" for 3-4hours, the dibromide, C3H4CI2Br2, is produced ; it is a heavy, colour-less liquid which boils almost without any decomposition a t 203-207"(770 mm.).Allylene dichloride is the only compound of the formula C,H,CI,which boils a t 75" ; that. dichlorotrimethylene is not identical withthis is shown by the fact that the dibromo-compound obtained fromallylene dichloride boils at 190" (Friedel and Silva ; 288", Piliner).Of the three possible formulae for this dichlorotrimethylene, theauthor favours CCl2<YH' * for the dibromide approximates in boil-in g point to a-epiciicliloi;hydrin dibromide, CH,Cl*C C1 Br*CH2Rr, andtherefore, probably, has a similar structure.Hexylene Dibromide obtained from Diallyl.By N. DEMYAA'OFF(J. Russ. Chenz. Soc., 22, 117--11&).-1n order to prepare hexyienedibromide, well cooled diallyl (b. p. 59--60") was saturated withhydrogen bromide, when a mixture of a solid with a liquid wasobtained. After washing with water, the two compounds were sepa-rated by filtration and suction. The liquid product was a hexylenedibromide boiling a t 2 12-220" with decomposition. The solidproduct, after recrystallisation from ether, was obtaimd in large,rhombic scales melting a t 38-39", and boiling almost without decom-position at 210".The author considers the liquid compound to beCH2Br-[ CH2],*CB2Br, and the solid as CHMeBr.CH,*CH,.CHMeBr,and that diallyl is a mixture of two (geometrical) isomerides.CH, 'A. G. B.B. B.Oxidation of Potassium Cyanide with Potassium Per-manganate. By J. VOLHAI~D (Anwdeja, 259, 3 7 7 4 8 0 ) .-Csrb-amide can be very conveniently prepared i n moderately large quanti-ties in the following iiianner :-A solution of potassium per-mnnganate (53 grams) in water (1 litre) is gradually added to Rsolution of pot.assium cyanide (59 grams) and potassium bydroxide(10 grams) in watw ( 1 0 c.c.), the temperature being kept below17"; but it is unnecessary to wait until the pink colour has dis-appeared before continuing the addition of the permanganate.Thesolution is then placed in cold water for seven to eight honrs until i tbecomes colourless, n;ised with a concentrated solution of ammoniumsulphate (70 grams), heated to boiling, and filtered ; the precipitateis washed with boiling water, the filtrate and washings evaporated todryness, and the carbamide extracted with 95 per cent. aIcohol. Tbuyield is 68 per cent. of the theoretical, but the product still containsa little ammonium chloride a n d traces of the sulphate, from which itcan most easily be freed b ~ - treating its aqueous solution with a, littleprecipitated barium carbonate, evaporating to dryness, and theiiextracting with absolute alcohol. F. S . KORGANIC CHEMISTRY. 161Combination of Mercuric Cyanide with Cadmium Salts.By R.VARET (Compt. rend., 111, 679-681).-Powdered mercuric:cyanide, 25 parts, 1s gradually added to a boiling concentrated solu-tion of cadmium iodide, 30 parts, and the liquid is filtered and allowedto evaporate over sulphuric acid. The compound HgCys,CdCy2,HgT2 + 7H20 separates ill transparent larnellae, which alter rapidly whenexposed to air, and dissolve in water and ammonia. It becomesanhydrous at llG", and at the same time decomposes with liberationof mercuric iodide. Dilute acids decompose it with liberation ofmercuric iodide and hydrocyanic acid, while mercuric cyanide andthe cadmium salt of the particular acid used remain in solution. Whenheated with a solution of cupric sulphate, cynnogcn is evolved, and ,zprecipitate of the composition CuzCy,,Hg12 is formed.These factsshow that all the cyanogen is not combined with the mercury, andthat the salt is not simply a compound of cadmium iodide withmercuric cyauide.Cadmium bromide (18 parts), added gradually to a boiling solutionof mercuric cyanide (25 parts), yields slender needlss of the corn-pound 2HgCy.,CdBr2 + 4kH20, which alters but little when exposedt o air, dissolves in water and in ammonia, and becomes anhydrous a t100". Dilute acids liberate hydrocyanic acid, but no mercuricbromide sublimes when the salt is gently heated; but when morestrongly heated, cynnogen and mercury are evolved and some mer-curic cyanide sublimes. It follows that the salt is a compound OFmercuric cyanide and cadmium bromide.If a solution containing 25 parts of mercuric cyanide and 30 partsof cadmium bromide is gently evaporated on a water-bath, the saltHgCy2,CdBr2,SH20 separates in small, very hard, granular crystalswhich alter but little when exposed to air, become anhydrous at lob",and are less soluble in water and in ammonia than the precedingcompound.I f a concentrated solution of 20 parts of cadmium chloride is addeddrop by drop to a saturated solution of 2.5 parts of mercuric cyanide,heated at 80°, and the liquid is slowly concentrated after addition ofsufficient warm water to dissolve the white precipitate which forms,the compound HgCy2,CdCI2 + 2H20 separates in small, granularcrystals. It is soluble in water and in ammonia, is decomposed bydilute acids, and becomes anhydrous at 110".C. H. B.Action of Alcoholic Potassium Cyanide on Halogen Deriva-tives of Amylene. By C. HELL and M. WILDERMANN (Bey., 23,3210-3215). --It is well known that whereas the primary dibom-ides of normal olefines are readily converted into the correspondingclinitriles, the dcrivatives of the iso-compounds only give very smallyields on trsatment with alcoholic potassium cyanide. Thus iso-amylene bromide forms, besides t h e dinitriles, large quantities ofbrornamylene and of humous substances. The authors find that thereaction takes placc! more readily if isoamylene chloride is employedin place of the bromide, and the mixture is heated in a sealed tube a t180". The nitrile formed gave on hydrolysis a crystalline acidseemingly identical with the trimethylsuccinic acid obtained b162 ABSTRAOTS OF CEEMICAL PAPERS.Schad (Inaug.Diss., Beme, 1886), and an oily acid which could notbe obtained crystalline. The yield of both these acids was betterthan that given by the bromide.It was also found that addition of hydrochloric acid to the mixtureof isoamylene chloride and alcoholic potassium cyanide causes a greatincrease in the quantity of humous substance formed, whence it wouldappear that the formation of the latter is due to the action of hydro-chloric acid on the hydrocyanic acid ; this was confirmed by addinghydrochloric acid to an alcoholic solution of potassium cyanide whichhad previously been boiled for some time without undergoing altera-tion, when, after 8 few minutes, a copious separation of humus tookplace.Hence all those substances which readily lose hydrogenchloride or bromide by the action of potassinm cyanide will givelarge quantities of humus, owing to the action of the acid thus set freeon the hydrocyanic acid, azulmic and hydrazulmic acids being formed.When isoamylene bromide is heated with bromine, it is convertedinto a ti-ibrmzopentane, the most probable formula of which isCMe,Br*CMeBr,. This is readily acted on by alcoholic potassiumcyanide without formation of humus or of bromamylene in any quan-tity. The nitrile formed is almost insoluble i n water and ether, butdissolves readily in alcohol. The hydrolysis is best performed byheating it in it sealed tube at 13G-130" with concentrated hydro-chloric acid, arid extracting the product with ether.After removingthe latter by evaporation, a yellowish, syrupy acid remains whicligradually deposits a small quantity of needles ; these after repeatedcrystallisation from water, melted at 96-97', and evolved carbonicanhydride at 130-140" ; the quantity of the substance was too small,however, to allow of its being obtained in a pure condition. Thosyrupy acid, after purification by successive conversion into the calcium,barium, and silver salts, was obtaiued as a pale-yellow syrup which didnot crystallise, even when kept for some time ; it has the composition ofa trimethylsuccinic or dimethylglutaric acid, but its exact constitutionhas not yet been determined.It only evolves minimal quantities ofcarbonic anhydride on heating, due to the presence of traces of theabove crystalline acid. H. G. C.Derivatives of Melidoacetic Acid. By R. KRUGER (J. pr.Chem. [el, 42, 473494; compare this Journal, 1875, 1181).-Mel-idoacetic acid is best, obtaiued as follows :-lo grams of sodium isdissolved in alcohol, the solution cooled and mixed with a solutionof cyanamide (20 grams) in alcohol (40 c.c.); au equal volume ofether is then added, and the resulting precipitate is heated with a,mixture of cyanamide (10 grams) dissolved in alcohol (20 c.c.) andethyl chloracetate (30 grams) for 6 to 8 hours in a reflux apparatus.The whole is then dissolved in dilate soda, filtered, and the mel-idoacetic acid precipitated by acetic acid ; it is purified by dissolvingit in dilute hydrochloric acid and passing hydrogen chloride intothe cooled solution, when its hydrochloride separates in large needleswhich are recrystallised and decomposed by adding ammonia to theaqueous solution.The potassium, sodium, calcium, and barium saltswere obtainedORGANIC CHEMISTRY. 163Ammelidoacetic acid, C,N,( OH),*NH*C H2*COOH, is obtained byheating melidoacetic acid with excess of barium oxide and water in areflux apparatus until no more ammonia is evolved, and crystallisingthe portion which remains undissolved from hot hydrochloric acid.It crystallises in rhombic or monocl inic tables, and dissolves freelyin hot water, but not in alcohol. The copper salt, (C5HSN40&Cu + 6Hz0, crystallisss in dark-blue, rhombic tables ; tho silver salt is awhite precipitate of uncertain composition : the basic lead salt,C5H4N40aPb, crgetallises in tranRparent crystals which are i tisolublein water: the barium salt, C,oH34N,,0uBa3 + 8H20, crystnllises inlong, rhombic tables, soluble in much hot water ; the stwntium salt,CloHloN,OsSr + 4H20, forms rhombic or monoclinic tables; thecalcium saZt, which was obtained like the last two salts, namely, byadding calcium hydroxide to a solution of the acid, precipitating theexcess of calcium with carbonic anhydride, filtering, and crystallising,forms crystals which are similar to the strontium salt, but have anuncertain composition ; the calcium saZt, ClnHloN,O,Ca + 4820, ob-taiiied by mixing the calculated qnsritities of calcium oxide and am-melidoacetic acid and crystsllising, forms glistening, quadratic prisms ;the sodium, potassium, and artemo?lium salts (each with 2 mols.H20)are of normal composition, and easily soluble in water.Cyanuracetic acid, C,N3( OH)2*0*CH,*C00H7 is obtained whenmelidoacetic acid is heated i n a sealed tube with strong hydrochloricacid at 180" for several hours until it has all dissolved ; wheu the tubeis opened the liquid froths u p from the escape of gas, and after a timethe new acid crystallises out, together with ammonium chloride, fromwhich it is separated by its solubilit,y in absolute adcohol. It crys-tallises (with 1 mol. H,O) i n prisms and needles, and dissolves veryfreely i n water.There are three series of salts: the ccrpper salt,CloH,N,OloCu + 28,O; the silver salt, CaH,N,0,Ag3 + H,O; thebarium salt, C,H,N305Ba + 2Hz0, and the potassium salt, C5H4N306K + HzO, are here described ; the ethyl salt, C,H,N,O,Et, crystallises insilky needles which melt at 208" and solidify at 195".Cyanuracetic acid is synthetically obtained by heating disodiumcyanurate with sodium chloracetate in aqueous solution.TWO New Butyl Nitrates. By G. BERTOM (Gazzetta, 20,372--376).-Of the four theoretically possible butyl nitrates, onlyone, the isoprimary salt, has hitherto been prepared (Wurtz, Contpt.rerd., 1854).The normal primary nitrate, CH2Pi**N03, is prepared by addingquantities of 10 C.C. of pure normal butyl alcohol, drop by drop, to astrongly cooled mixture of 2 vols.of sulphuric acid (sp. gr.. = 1-85)and 1 vol. of nitric acid (sp. gr. = 1.4), and proceeding a s in themanufacture of nitroglycerol. It is a colourless liquid, with a pleasantethereal odour ar.d a sweet taste, which becomes pungent after a time.If boils at 136", and its sp. gr. at 0" is 1.048. It dissolves in alcohol,ether, acetic acid, carbon bisulphide, &c., but not in water. Withacids, it behaves like other ethereal nitrates. I t burns with an olive-green flame, and explodes with violence when heated in a sealed tubeto a higher temperature than its boiling point.A. G. B164 ABSTRACTS OF OHEMKCAL PAPERS.Secondary butyl nitrate, CHE tMe-NO,j, is prepared like the preced-ing compound, the temperature being carefully kept below 0" duringthe whole of the reaction.I t is a colourless, mobile liquid, with apleasant, penetrating odour, boils at 124", arid has a sp. gr. of 1.0382.It dissolves i n most organic solvents, but, not in water. It is morereadily decomposed than its isomer ides by aulphuric or hydrosulphnricacid. Its vspour explodes when superheated. S. B. A. A.Action of Hydrogen Chloride and Bromide on Ethyl Ally1Ether. By S.. N. K I J N E ~ (J. Russ. Chem. Soc., 22, 27-32).-The author has made attempts to convert ethyl ally1 ether into ethylpropyl ether by acting on it with hydrogen bromide, but the resultwas quite different when ethyl ally1 ether, saturated with hydrogcnbromide a t - 15", was heated in a sealed tube at 30-40" for 10 hours ;it was found to be deconlposed with formation of allyl bromide andethyl bromide, this reaction taking place to some extent even at-15".Hydrogen chloride and allyl ethyl etlier in like manneryield ally1 and ethyl chlorides, but the reactinn requires more timeaud a higher temperature. This result accords with the fact that thereaction takes place with development of heat. This is evident fromthe thermochemical data, and the reaction will be more energetic withthe gaseous acids than with the aqueous solution, as more heat isdeveloped by the action in the first case than i n the second.Tetraanethylene Glycol. By P. J. DEKKERS (Rec. Tyav. C/h17,.,9, 92-102 ; see also Abstr., 1889, 950).-Tetramethylene glycol isthe only dihydroxy-derivative of normal butane which has not beenpyeparcid up to the present time.Tbe author endeavoured to obtain itsclibeneoate by the action of sodium on chlorethyl benzoate, C2HI*Cf.0Bz,but only obtained a inixtnre of sodium chloride, sodium benzoate,and ethylene benzoate. The action of' sodium and silver nitrite ona solution of tetrsmethylenediamine sulphate or oxalate also gavenegative results, although with the former salt a liquid was obtainedwhich was possibly tetrarnethylene oxide.The following method was then adopted with more satisfactoryresults. Tetramethylenediamine, when mixed with methyl carbonatein the cold, gradua.lly deposits white cr-ystals of methyl tetramethylene-dianzidoformnte, C,H,( NH*COOMe)?, which, after recrystallisation fromwater, melt at 128".When the latter is treated with five times. itsweight of cold abwlute nitric acid, it yields m e t h y l tetramethylenedi-r,iti.nmic?ofoo,mate, C',He[ N( N02)*COOMej2, which separates from alco.ho1in crystals melting at 61-62". To convert this into the nitrainiue, itis warmed with ammonia, the solufion. precipitated with acetic acid,the precipitate washed with cold water, and recrystallised from thehot li qnid. The t ef ra met hy Zenedihtitrarnine, C,Hz, ( N He thusobtained forms hard crystals melting at 163", which are fairly solublein hot water. When it. is wnrmcd on the water-bath with verydilute sulphiiric acid, a, volatile liquid distils over, and a gns is formedwhich is partially absorbed by hydrobromic acid with formation oftetramethylene bromide, and by bromine with formation of butinetetrabromide.The unabsorbed gas consists of nitrous oxide. WhenB. BORGANIC CEEMISTRT. 165the residual liquid in the flask is distilled under reduced pressure ityields tetramethy Zene gZycoZ, C,H8 (OH),, as a thick, colourless liquidwhich boils at 20.3-205" under 752 nim., and at 152-153" under120 mm. pressure, and yields succinic acid on oxidation. Whenshaken with benzoic chloride and soda solution, it yields the dibenzoate,C4H8(OBz)2, melting at 81-82".As mentioned above, a volatile liquid distils over when tetra-methylenenitramine is warmed with dilute sulphuric acid. Thisseparates into two layers, the upper one consisting of a liquid boilingat 67", and the lower of an aqueous solution of a liquid boiling a t$3-888".These have not been closely examined, but the formerprohably is tetramethylene oxide.By K. ZULKOWSE~ (Be).., 23, 3295--3297).-Starch dis-solves in hot gly.cerol, znd is converted into the soluble modification ;by further heating and treatment with alcohol, erythrodextrin andachroodexti-in are obtained free from sugar ; from the alcoholicfiltrate, two soluble carbohydrates may be separated by treatmentwith barium hydroxide, absolute alcohol, and anhydrous ether ; thesecond of these remains dissolved in the ether-alcohol; and may beprecipitated by means of barium hydroxide.From the extzeme difficulty experienced in removing the glycerol,the author suggests that it may take part in ihe reaction.a- and /%Ampin.By A. TESTERRERG (Bey., 23, 3186-3190;see also Abstr., 1&8i, 733). The elemi resin employed in theseresearches, after trituration with alcohol, showed, under the micro-scope, numerous crystals of amyrin, together with a few isodiametriccrystals of elemic acid. The total amount of a- and p-amprin is20-25 per cent., a large portion of the residue being of a n alcoholicnakure, as it is acted on by acetic anhydride. The empirical formulaof both a- and /3-emyrin was found, from analysis and determinationof the hydrolysis equivalent of their acetates, to be C30H600. Thecompounds we extremely similar, and form slender, elastic, silkyneedles which are readily soluble in benzene, ether, acetic acid, andhot alcohol.sparingly in cold alcohol and light petroleum, The ratioof their solubility in alcohol at 19-19.5" is 3 : 5.12. a-Amgrinmelts at 181-181-5, and rotates the plane of polarisation to the right,[a]== +91.59", whilst p-am-pin melts a t 193-194", and rotatesthe plane of polarised light more strongly to the right, [aID =99.81".Both compounds, unlike cholesterin and lactucerol, crystallise fromaqueous alcohol without water of cry stallisation. They are prohablysecondary alcohols, as they give acetyl and benzoyl derivatives, andon oxidation yield a- and p-amyron, which are probably ketones,Phosphorus pentachloride converts them into dextrorotatory hydro-carbons, C30H.18, which may be termed amyrilenes. Phosphorus pent-oxide, on the other hand, yields with a-smyrin a laevorotatoryam yrilene.a- and P-Amyrin acetates, C30H&Ac, are formed in the separationof the amyrins (Zoc.cit.), but are only obtained pure by repeatedH. G. C.Starch.J. B. T166 ABSTRACTS OF OHEMICAL PAPERS.crystallisation from light petroleum or benzene. Both are sparinglysoluble in alcohol and ether, readily in light petroleum, and moreeasily in benzene and chloroform. The a-compound ciytallises inlarge plates, melts at 221": and has a sp. rot. power [aID = +77".The &compound forms long, prismatic cryskals melting at 2X0, andhaving a sp. rot. power [ a ] ~ = 78.6". Both are oxidised by chromicacid to oxyamyrin acetates, C36H1702A~.The a- and p-anzyrin benzoates are obtained by heating a- andR-amyrin with benzoic chloride at 130".The a-compound is crystal-lised from alcoholic ether, and is sparingly soluble in alcohol, morereadily in ether, and very easily in light petroleum and benzene. Thep-compound, after recrys tallisation from light petroleum, is almostinsoluble in cold alcohol, sparingly soluble in ether and cold lightpetroleum, readily in the hot liquid and in benzene.When a- and /3-amprin acetates are dissolved in chloroform orcarbon bisulphide, and bromine added, either alone or diluted withacetic acid, the sdutions are coloured brownish-yellow, and hydrogenbromide is evolved. The crystalline masses which remain afterspontaneous evaporation are reorystallised from benzene ( a ) or lightpetroleum (p). and the finely-powdered bromacetates treated withalcoholic potash.Brom-a-artzyrin, Cm.€14~Br.0H, melts a t 177-178", is sparinglysoluble in cold acetic acid and alcohol, readily in benzene, and almostinsoluble in light petroleuni ; it is dextrorotatoyy, and has a sp.rot.power [a]= = + 72.8". Its acetate, CwHaBr*OAc, crystallises frombenzene in six-sided plates or flat prisms, containin'g benzene of crystal-lisation, which is evolved when the crystals are allowed to remain inthe air. It has not, however, been obtained quite pure, but appears tomelt at about 268'; the bromine is not removed by alcoholic potash,ammonia, or aniline.Brcim-/3'-arny~in conld not be obtained crystalline, the warm solu-tions in alcohol, benzene, and light petroieum solidifying to jellies.It is very soluble in hot acetic acid and benzene, less readily inalcohol and light petroleum. After drying at 98", i t melts at1 8 2 - 1 8 6 O .The acetate forms prismatic crystals, readily soluble inchloroform and benzene, sparingly in lighf petroleum, which, afterrecrystallisation from the latter, melt at 238". As it is fairly solublein hot light petroleum, i t me,y be thus easily separated from thebrom-a-acetate, and can, therefore, be prepared directly from themixture of amyrins.Isopropylarnines. By H. MALBOT and A. MALBOT (Con2pt. Yeftd.,111, 630-652) .--The act ion of isopropyl iodide on an equivalent,quantity of highly concentrated aqueous ammonia, at the ordinarytemperature, is very slow, bnt is complet.e, the product consistingentirely of isopropylamine hydriodide.At loo", the action is stillslow, and requires about four days before it is complete. The chiefproduct is isopropylamine hydriodide, but a small quantity of thediamine is also formed. Ammonium iodide is formed in quantitylarger than that corresponding with the quantity of diamine, a resultdue to the liberation of some propylene. At 120-130", and atH. G. CORGANIC CHEMISTRY. 167140-155", the chief product is still the monamine, mixed with asmall quantity of diamine, the proportion of the latter being practic-ally the same in both cases. The quantity of propyleue liberated is,however, considerably greater at the ' higher temperature. Thequantity of diisopropyhmine hydriodide does not exceed a certainvalue, because it reacts with the wonamine, with elimination ofpropylene.Isopropyl chloride reacts with aqueous ammonia at 140°, and themonamine is mixed with some dianiine, but the change is far fromcomplete.because the aaines are present partly in the free state. Inthis respect isopropyl chloride differs from isopropyl iodide, and morenearly resembles orthopropyl, isobutyl, and isoamyl chlorides, whichyield the free amines. There is, however, this difference, that whilsti t is easy to obtain tripropyl-, triisobutyl-, and triiso-amylamines, diiso-propylamine is the final term in the action of ammonia on the haloidsalts of isopropyl.Propylnitramine and Isopropylnitramine and their Deriva-tives. By J. C. A. SIMON THOMAS (Rec.Trav. Chim., 9, 69-91).-Yropylnitramine and isopropylnitramine are readily obtained in asimilar manner to methylnitrarnine (Franchimont and Klobbie, Abstr.,1888, 492). The propylamine and isopropylarnine required for theirpreparation were obtained by HoogewerE and van Dorp's method(Abstr., 1887, 245 ; 1888, 1194), and converted into the correspondingamidoformates by the action of methyl chloroformate in 25 per cenf.aqueous solution, extraction with ether, and fractionation. MethylpropyZantidoformate, NHPrWOOMe, is a coloni-less liquid, which has:i faint penetrating odour, and boils at 180" under 755 mm. pressure.Its sp. gr, is 0.992 a t 15".NHPrB-COOMe,is likewise a colourless liquid, having a faint penetrating odour,which boils at 165.5" under 760 mm.pressure, aud has a sp. gr. of0.981 at 15". Both compounds are readily converted into the nitro-derivatives by gradually adding them to cooled absolute nitric acid,with continuous shaking. In the case of the isopropyl compound,cooling with ice and very gradual addition of the timidoformate, isnecessary, as otherwise oxidation readily takes place. The acid solu-tion is then, in both cases, poured on to soda crystals covered with alittle water, the yellowish liquid which separates taken up withether, the ether distilled off, and the residual liquid dried over sulph-uric acid. Methyl propy lnitramidoformate, N02*NPra.COOMe, is thusobtained as an almost colourless liquid, which has a sweetish odour,and does not solidify at -20".It has a sp. gr. of 1.187 at 15", andevolves gas when heated at 139". Methyl isol-'ro~ylnif1.amidoforrltate,NO,.NPrWOOMe, has a sp. gr. OE 1.1585 at 15", and commences t odecompose at 120".To convert these compqunds illto the nitramines, dry ammonia gasis passed into their ethereal solutious. The ammonium salt of propyl-nitramine is precipitated as a crystalline mass, which is collected,washed with ether, decomposed by sulphuric acid, and the propyl-C. H. B.&!ethyl isopropylaiiiidoformate168 ABSTRACTS OF OEEMICAL PAPERS.nitramine extracted with ether. After evaporating off the ether anddrying the residue over sulphnriu acid, propyZnitrami?ze, N H P I ~ ~ N O ~ ,is obtained as a colourless, inodorous liquid, which cannot be distilledwithout decomposition at the ordinary pressui'e, but boils at 128-129"under 44) mm.pressure. Itl has a sp. gr. of 1.102 at l5", decomposesat 142", and solidifies between -21' and --23", anci is not colouredon exposure t o light. Its aqueous solution has an alkaline reaction,and gives a precipitate with many salts of the heavy metals. Thepotassium salt, NPFK*NOZ, obtained by acting on the nitramine withthe theoretical quantity of alcoholic potash, forms small, nacreous,hygroscopic plates, and the silver salt, NPPA~NO,, crys tallises insmall, slender needles, which blacken in the light.Isopopylnitmmine, NHPrs-NO2, is obtained in the same manner asthe normal compound, but must be further purified by dissolving itin potassium carbonate solution, extracting the lattcr with ether, andacidifying the residual solution with sulphuric acid.It is a colourlesscompound which melts at -4': distils at 90-91" under 10 mm.pressure, commences to decompose at 150°, and has a sp. gr. of 1.098a t 15". It is scarcely soluble in water, but mixes with alcohol andether in every proportion. The potassium salt, NPrpK*NO,, formslong, slender, very hygroscopic needles, and the silver salt,NP@Ag*NO,, crystallises in thiu plates.When the potassium salts of these nitramines are treated withan alkyl bromide, or the silver salts with an alkyl iodide in alcoholicsolution, dialkylnitramines are obtained. The following have beenprepared in this manner :-Dipropy Znitramine, NPF2*.N02, a colourlessliquid boiling at 76-79' under 10 mm.pressure; di-isopropyl-nitramine, NPrSz*N02, boiling at 55-57' under 10 mm. presmre;p o p ylisoprop y lnitramine, NPPP~S-NO~, boiling a.t 65-68" under thesame pressure ; and benxyZpropyZnitra?nine, N02.N Pia.C H2Ph, meltingat 8-10', and boiling at 200-205" under 40 mm. pressure. Thefirst three compounds do not solidify in a mixture of solid carbonicanhydride and ether. Thc silver and potassium salts of propylnitr-amine, unlike the corresponding methyl derivatives, do not yield apicryl compound on treatment with picric chloride, the latter beingsimply converted into silver or potassium picrate. Ethyl and iso-propylnitramine behave in a similar manner.When the silver salts of the nitramines are warmed with acetic orbenzoic chloride, a simple reaction does not take place.Some silverchloride is precipitated, and nitrous oxide is evolved. It appearsprobable that the acetyl or benzoyl compound is first formed, andthen splits up into prop91 acetate or benzoate and nitrous oxide :-CH,*CO*NPP+NO2 = CH,*COOPP + NZO.The author has succeeded i n isolahg propyl benzoate from $he pro-duct of the reaction with benzoic chloride.The molecular weights of picrylmethylnitramine (Abstr., 1886,455) and of isopropylnitramine have been deteimined by Raoult'smethod, the results agreeing with the formule above ascribed tothem. H. G. CORGAX'IC CHEMISTRY. 189Amylamines. Bp A. BE KG (Conapt. rend., 111, 606-608). -Amy1chloride and saturated aqueous ammonia are mixed in equivalent pro-portions, and sufficient alcohol of 93" is added to completely dissolvethe mixture.The liquid is heated a t 110-120" for eight or ninehours, poured off from the crystals of ammonium chloride (mixedwith a small quantity of diamylamine hydrochloride), acidified withhydrochloric acid, and distilled, to remove alcohol and unaltered amylchloride. The residual liquid, when allowed to cool, deposits nacreousplates of diamylamine hydrochloride, which can be almost completelyseparated by successive concentrations. If recrystallised from boilingwater after treatment with animal charcoal, it is obtained in per-fectly pure, lar,ge plates, with a niicaceous lustre.The mot,her liquor from the diamylrtmine hydrochloride is evapo-rated to dryness and made alkaline with potash or soda; the liberatedbase consists of almost pure amylamine mixed with ft very smallquantity of the di- and tri-amine, tbe proportions i n which the threebases are obtained from the original product being monamine 6 parts,diamine 9 parts, tzinrnine 4 to 1 part.The same result is obtainedwith only half the quantity of alcohol. Alcoholic ammonia yieldssimilar results, but the diamine is formed in still larger proportiontj.Pure aruylarnine is cbtained by the method of Duvillier andBuisine. A dilute aqueous solution is mixed with a suitable quantityof ethyl oxalate, a rise OE temperature being avoided; diarnyloxamideie precipitated, and is almost completely insoluble i n water. Themother 1 iquw, when concentFated, yields amylamiue amyloxamate,C,H,,*NH*CO*COC\H,NH2*C5H,1, very soln hle in hot water, but muchless soluble in cold water, and easily decomposed by aqneons potash,which bas very little action on diamyloxamide.With calciumchloride, nmylamine amyloxamate yields a precipitate of calciumamyloxamate, which crystallises readily from hot water in small,brilliant, hydrated lamellaDiethylenediarnine. By A. W. v. HOFMANN (Ber., 23, 3297-3303) .-Ljiethylenediamine puri6ed by treatment with sodium meltsat 104", boils at 145-149, and solidifies on cooling, forming a hard,white, crystalliire mass, which is extremely soluble in water, andici deposited from absolute alc ~hol in large, transparent crgstals.The benzoyl derivative is deposited from alcohol in rhombic crystalswhich melt at 191". A technical product termed "spermin," " piper-szidin," or '* piperazin '' is fouiid to be identical with diethvlenedi-amine (compare Sieber, Abstr., 1890, 476).Action of Zinc and Ethyl Chloracetate on Ketones andAldehydes.By S. ~ F O R M A T S K T (J. Russ. Chem. SOC., 22, 44-64),-Acetone, when treated with ethyl chloracetate and zinc, gives a pro-duct which, on decomposition with water vields the P-dimethylethyl-ciielactic acid (hydroxgvaleric acid), 0H*CMe2*CH2*C00H, of M. andA. Ssytzeff. Methyl propyl ketone, under similar conditions, yieldsp:inrt hy Zpropy Zethytenelactic acid, 0 H*CMePr*CH,*C 00 H. This, ondistilllttion with dilute sulphuric acid, yields methyZpropyZacryZic acid,CMePr:CH*COOH.Diethgl ketone, when similarly treated, yieldsC. H. B.J. B. T.VOL. LX. 170 ABSTRACTS OF CHEbIICAL PAPERS.Shinokoff's p-diethylethylenelactic acid, OH*CEt,*CH?*COOH. By dis-tillation with dilute sulphuric acid, this acid loses the elements of water,and P-diethylacrylic acid, CEt,:CH*COOH, is obtained. The abovereaction when applied to hutyrone gives rise to Shinokoff's P-dipropyl-ethylenelactic acid, OH*CPr,*CH,*COOH, which, on losing the elementsof water, is converted into Albitzky's dipropylacrylic acid. This acidjields a dibromide melting a t l02-104", whereas the dibromide pre-pared by the author from Albitzky's original acid melts at 80-82".This difference is prob<ibly due to geometrical isomerism, as thecompounds contain an asymmetrical carhon atom.The above re-action may be represented by the general scheme, RR,CO +CH,Cl*COOEt + Zn = CRR,(OZnCl)*CH,*C~OOEt, atid this with8H,O gives RR,:C(OH)*CH,.COOH. Analogous results obtained withaldehydes will be communicated i n a future paper. B. B.Action of Phosphorus Trichloride on Organic Acids andWater. By C. H. BOTHAMLET and G. R. THo&ii'soN (Clwn. NWS,62, 191).-Thorpe showed (Trans., 1880, 186) that the equationSCH,*COOH + 2PC1, = 3CII,*COCl + Y,O., + SHCl representedthe action of phosphorus trichloride on acetic acid. The authorsagree that this does represent the fundamental change (which i ssimilar for other monobasic organic acids), and therefore true withincertain narrow limits, but with excess o€ either reagent varioussecondary reactions take place, which increase with other acids of theseries, as the molecular weights become greater and the volatility ofthe products less.With benzoic acid and phosphorus trichloride,secondary changes take place to tt very considerable extent. In fact,this reaction cannot be regarded, as it hitherto has been, as a goodmethod for preparing acid chlorides. Even the action of phosphornsIIA trichloride on water, which is as follows, PCI, + 3H,O = H3PO, + 3HC1, as long as the water is in considerable excess, is disturbedby various secondary reactions as soon as the phosphorus chloride isi n excess! giving rise to the formation of yellow phosphorus oxide andother oxides, including the soluble form of the oxide P40, which be-comes insoluble at i0" ; the yellow oxide was also produced in the othereases given above.Various conditions affect these changes, especiallytemperature. L). A. L.Paracrylic and Hydracrylic Acids. By E. K L r m N K o (J. RUS.Chew. BOG., 22, 100-102) .-The aiithor's method of preparing par-acrylic acid by the action o€ silver oxide on &iodopropionic acid yieldslarger quantities ot the pure acid with difficulty only. The author'simproved method consists in evaporating hydracrylic mid with hydro-chloric acid on the water-bath. On treating paracrylic acid with anexcess of bromine, it yields bromopropionic acid. When paracrylicacid is heated with water at lOOOfor six hours,it is converted into an acidC3H603, having the composition of IiFdracrylic acid.By the action ofphosphorus pentachloride on hydracrylic acid, a chloride is produced,which with alcohol yields ethyl /3-chloropropionate.p-Chlorocrotonic Acids. By W. ATJTENRIETH (AnnuZen, 259,358-362) .-The sodium salt of P-chlorocrotoiiic acid, unlike the freeB. bORGANIC CHEMISTRS. 171acid, does not undergo intramolecu?ar change whsn it is heated at170-180" for 12 hours, but is almost completely decomposed i n t oallylene, sodium chloride, and carbonic anhydride ; the sodium salt of@-chlorisocrotonic acid is comple telp decomposed under the same con-ditions yielding the same products as the isorneride.Preparation and Properties of Ethyl Sodacetoacetate andEthyl Sodethylacetoacetate. Bg H. ELION (Be~.,23,3123-:3124).-It has been previously shown (Rec.Trav. Chim , 3, 231) that an-hydrous ethyl sodacetoacetate and an hydrous ethyl sode t by lacetoace t-ate are readily soluble in ether, but that both compounds forma hydrate which is insoluble iu ether. In preparing the anhydrouscompounds by the author's method (Zoc;. c i t . ) , they are obtainedin etheretil solution ; this solution can be most suitably employed forcarrying out reactions in which the presence of water or alcohol is tobe avoided, and the anhydroas compounds cat1 be readily obtained in asolid state by evsporating tha et'her at, a low temperatore. Otto andRiissing's statement (AbRtr., 1890,1137) that a n hydrous ethyl sodaceto-acetate can be obtained by keeping the hydrate over sulphur c acidis contrary to the author's experience, and Michael's assumption(Abstr., 1888, 1054) that pure anhydrous ethjl sodacetoacetate existsin two forms, one of which is soluble, the other insolnble in ether, isquite unwarranted.F. S. K.Cyanacetoacetates an d their Chlorimido-derivatives. B,yA. BALLEH. and A. HELD (Coiiipf. rend., 111, 64i--65u).-Ethyl *I-cjan-acetoacetate, boiling at 135-138" under a pressure of 40-45 mm.,is mixed with its own volunie of absolute alcohol, and the mixture isadded to about double the quantity of absolute alcohol saturated withhydrogen chloride and cooled to 0". Heat is developed, amrrioniumchloride separates, and the liquid contains a ch lorinc! derivativeaild ethyl acetodicarboxylate. IE ammonium chloride does notseparate, the liquid is evaporated in a vacuum, mixed wikh fine sand,and extracted with ether. The! ethereal solution yields slender, whiteneedles of the hydrochloride of the irriido-eth 'r of ethyl acetodicarb-oxylate COOEt*CHZ,*CO*CH2*C(OEt):NH,HCI, which is decomposed bywater with forma tion of ethyl acetodicarboxylate, CC!*(CH,*COOEt),.If ethyl y-cyanacetoacetate is dissolved in two or three times itsweight of methyl alcohol, and hydrogen chloride is passed into thecooled liquid, crystals are obtained which me1 t with decornpositionat 122", and consist of the methyl-imido-ether of etbyl acetodicarb-oxylate plus one molecule of hydrogen chloride.When treated withsilver nitrate, half the chlorine is precipitated, but the remainder canonly be removed by boiling with potash.When boiled with diluteand slightly aciditied alcohol, the compound yields ammoniumchloride and an oily chlorinated product.Methyl y-cyanucetoacetde, obtained in the same way as the ethyleom pound, is a somewhat thick, colourless liquid, which rapidlybecomes pellow. It boils a t 21f-218" under normal pressure, andat 127-128' under a pressure of 20-30 mm. ; it does not solidifyeven a t a very low temperatnre. When treated with hydrogen cltlorideiii presence of methyl alcohol, it yields confused white prisms whichF. s. K.n 172 ABSTRACTS OF CHEMlaAL PAPERS.melt with deccmposition at 144", and consist of the hydrochloride ofthe imido-ether of me thy1 acetodicarboxyiate plus one molecule ofhydrogen chloride.It dissolves in water and in alcohol, and withpotash, acidified alcohol, and silver nitrate i t behaves like the uorre-sponding ethyl compound.It is necessary to assumo that under the conditions of experimentthe alkgl cyarincetoacetate undergoes molecular change, and behavesas an unsat-urated compound. the chloro-derivatives having the con-stitution COOMe*CH2*CH(OH)*CHCI.C(OMe):NH,HC1 orC 0 OMe*CHC 1-C H (OH) *C H& ( OMe) : N H, H C 1.C. H. B.Mesitene Lactone and Isodehydracetic Acid. By R. -4NSCH ik,P. BENDIX, and W. K E R P (Anrcaten, 259, 148--186).--The authorshave repented a number of experiments mqae by Hantzsch (Annaten,222, 1) i n his invostigation of the condensation products of cbthylmetoacetate ; they have proved that the formulse assigned by Hmtzscht o mesitene lactoue and isodehydracetic: acid are correct.arid that theoriginal condensntim product (m. p. 61-62"> is a mixture of twohubstances and nob a compound of the composition C,,H,,O,, as wassupposed by Hantzsch ; they also obtained results at4 variance withthose of Hantzsch in studyirip the action of rimrnonia wnd alkalis onethyl isodehydracetate, as will be described below.When the crude condensation product of ethyl a2etoacetate is re-peatedly extracted with cold chloroform or benzene and the extractmixed with light petroleum, isodehydracetic acid (m. p. 155") is pre-cipitated in a pure condition, and its ethyl salt unci mesitene lactoneremain i n solution. The acid can be more easily isolated by dis-solving the condensation product in t-i mixtnre of ether and chloroformand shaking the solution, with conventrated potassium carbonate ; onacidifying the alkaline solution, the acid is precipitated in a purecondition, and the ethereal chloroform solution, on evaporation, yieldsthe ethyl s d t and mesitene lactone, tlie last-named compound beiriginvariably produced when ethyl acetoacetate is treated with concen-trated sulphuric acid.Ethyl isodehydrace trtte and mesitene lactone can be separated fromone another by fractional distillation under a prcssure of about12 to 14 mm.; the mesitene lactone passes over at 12€!-130", theethyl salt at 166".Methyl isodehydmcetate, CsHlnOQ, prepared by treating the potassiumsalt with methyl iodide, cr-ptallises from ether in long, colourlessneedles, melts a t 67-67*5", and boils a t 167" under a pressure of14 mm.; it can also be obtained, together with isodehydracetic acidand small quantities of inesitene lactone, by treating methyl aceto-acetate with concentrated sulphuric acid.When a mixture of pure ethyl isodehydracetate and the free acidis crystallised from dilute alcohol, a substance is obtained which isidentical in a,ppearance with, and has the same melting point. (59-60,")as, the originill condensation product.Attempts to prepare the homomesaconic acid described bv Hantzschwere unsuccessful ; when ebhyl isodehydracetate is hydrolysed witORQANIC CHEMISTRY. 173potasb, i t gives vnrying quantities of two new acids, melting a t 2'21'and 149" respectively, together with oily by-products. These twoacids were prepared by warming the pure ethyl salt ( 5 grams) 011the water-bath, qnickly adding a solution of potash (13 grams) inboiling water (4.5 grams), clncl then warming the mixture for 10minutes; 5 0 grams of the e t h j l s a l t yield 13 grams of the highermelting and 2.5 gmnis of the ioHve1- melting compound.The acid melting at 221" has the composition C5HI;O?, but its mole-cular formnla is probably ClnH1?OJ ; i t is almost insoluble in ether,benzene, chloroform, and cold water, and only moderately easilysoluble in boiling water, from which i t crystallises in transparent,,prismatic needles melting a t 221" with decomposir ion.The potmsiuinsalt, ClnHln04K2, is a vitreous, very hygroscopic coin pound.Thebavium salt, C,,,HloOdBrt + 4H30, crystallises from cold water inFpherical aggreg.ates and is tiioderately easily soluhle (19.1 parts ofanhydrous salt in 100 parts at 20") in water. The copper salt,ClnH,,,04Cu + S+H20, is apple-green and almost insoluble in water.The silvw salt was not obtained in a pure condition. Tlie methill salt,C10ET'1004Me2, prepared by treating the silver salt with methyl iodide,crptallises from ether in colourless, transparent prisms, melts at 71',and is readily soluble in ether, alcohol, benzene, and chloroEorm, butis precipitated from the solutions on the addition of light petroleum.The acid melting at 149" has the composition C&l,,,O,; i t crysta.1-lises from boiling water, in which it is more sparingly soluble thanthe acid melting at 221", in colourless needles, and is readily solublein alcohol, ether, and chloroform; i t decomposes about 160".Thebnriwn salt, ( CsH903)LB;t + 2H20, crystallises ill microscopic needles,and is very sparingly soluble in water. 'the siEver salt, C,ll,O,Ag, ismoderately stable in the light.Mesitene lactam (pseudolutidostyril,) is formed in small quantitieewhen mesitene lactone is treated with aqueous or anhydrous ammoniaunder various conditions. It is best prepared by passing anhydrousammonia for 14 o r 15 hours into mesitene lactone (15 grams) heateda t 150 to 160"; the lactam (8.5 grams) thus produced is separatedfrom the unchanged 'lactone (4 5 grams) by fractional distillation.The compound obtained in this way is identical with Hantmch'spseudolutidostyril (Ahstr., 1884, 1045, and 1885, 397).Tile platino-chloride, C,1H,,N202,H,PtC1,, separates from alcohol in dark-orange,transparent cry8 ta 1s.When mesitene lactone is treated with alcoholic ammonia,, tl smallquantity of the lactam is obtaincd, together with ammonium carb-aruate and a liquid, unstabie compound, the nature of which was notdetermined.An hydrous ammonia converts ethyl isodeh ydracetate into the cov-responding lactam, which is identical with the substance (m. p. 137")obtained by Collie (Abstr., 1887, 501) by the condensation of ethyl13-amidocrotonate.A compound of the composition Cl,,Hle04N2 is precipitated as acolourless powder when anhydrous ammonia is passed into an alcoholicethereal solution of ethyl isodehjdraaetate, moisture being cwef nllyexcluded, It melts a t 104" with evolution of ammonia, being recon1 i 4 ABSTRAOTS OF CHEMIGAL PAPERS.vertcd into ethyl iaodehydracetate, and its constitution is probablyrepresented by the formula COOEt.C<,,e'-o>C(NH2)*ONH~ ;when its concentrated aqueous solution is treated with copperchloride, a dark-green, crystalline, copper compound of the compo-sition ( ClOHl4O4JS ),Cu + H20 is precipitated.Ethyl isodehydracetate can be prepared hF boiling ethgl sodaceto-acetate with a benzeue solation of ethyl chloriyocrotonate ; methylisodehydracetate can be obtained in like manner.The synthesis of ethyl isodeliydmcetate in this way shows that theacid has the constitution assigned to it, by Hantzsch ; it is probable,therefore, that the acid obtained by Collie (Zoc.c i t . ) from the lactam,Ci0Hl3NO3 (m. p. 137"), referred to above, has an analogous constitu-tion, COOH*C<CMe:NH>CO, that of the acid obtained by Colliefrom the isomeric lactam (m. p. 165") being probably represented bythe formula COOH-CH,.C< NB-co>CH.CMe'CHCMe'C'HF. S. I(. CH*CMeAction of Methylene Iodide and Chloride on Ethyl Malonatein the Presence of Sodium Ethoxide. By S. TANATAR (J. Buss.Chem. Soc., 22,32-%).-l'he experiments were undertaken with theview of obtaining an acid, CaHd04, isomeric or identical with fumaricor maleic acid. The proportion of the substances taken was calculatedfrom the equation C38,Et20, + 2Na + CHJ, + 15CzH,0.Sodiumwas dissolved in absolute alcohol and ethyl malonfite was added t40the solution. As on the addition of methylene diiodide, so much heatis developed that the solution will boil if care be not taken, it isadvisable, to add the iodide in small portions at a time; to com-plete the reaction, the mixture was heated for 12 honrs in a refluxapparatus. The alcohol was then removed by distillation, wateradded, and the oily product, which is partly soluble in water, ex-tracted with ether. After distilling off the ether, the residue, containingsome unchanged ethyl rnalonatt! and niethylene iodide, was saponifiedwith n 15 per cent. solution of potash, but part, of it remained a n -changed.k'rom a solution of the potassium salt thus obtained, theacid was liberated by acidifying with hydrochloric acid and extract-ing with ether; the iodine was thm removed from i t by treatmentwith molecular silver. The free acid forms a honey-like syrup, whichdoes not crystallise, but, on being kept in a desiccator for severalmonths, becomes converted into a hard, gum-like substance. It canbe further puritied by converting it into the lead or silver salt anddecomposing the latter with hydrogen sulphide. The calcium salt,C6H8CaO6, is less soluble in hot than in cold water. The free acid,C6H,,O,, is called, by the autbor, adipmalic acid. The silver salt isC,H&,05 ; the barium salt, C6H,BaOs + 'LH,O.That portion of the original product of the reaction which remainedunchanged on boiling with 15 per cent.potash was saponified byboiling with strong potash, the potasfiium salt converted into thelead salt, and this, on decomposition and saturation with lime, into asalt C8H,ca2o9. From the tiltrate, alcohol precipitates a calcium salORGAN10 CHEMISTRY. 175containing a little less calcium than the salt c6H8Ca?09, which showsthat a mixture of acids was obtained. From a second portion, iodinewas removed with silver nitrate, and tbe silver salt, CsH8Ag4O,o, wasobtained, so that probably the original acids were CRH,,Oo andCRHIZO1,,. Methylerie dichloride and ethyl Rodiomalonate, in likemanner, yielded the compound C,H,E&04, which, on hydrolysis andconversion of tho potassium salt, gave the silver salt C8H6Ag409.The free acid C,H,,3, crystallises in prisms which melt at 108-109".Reaction between Methylene Iodide and Ethyl MaJonate.By S .'~'ANATAR (J. R1~s.c. Cftem. Soc., 22, 39-44).-The acidC,H,,,O5 (see preceding paper), when heated with water a t 150",undergoes no change, but if heated with hydriodic acid at 150" ityields ethyl iodide and an acid, C4H60a tbus:-C6H1,,OL + HI =C2H5T + C4H,05. This acid, OH*CH2*CH(C0OH),, the author calls(?) " hydroxymethy Zmulonk acid," whereas the original adipomalic acid,CGH1005, is regarded as ethoxyisosuccinic acid, EtO*CH,*CH(COOH),.On heating the acid at 250", dccomposition takes place, carbonic an-bydride being liberated, and a yellow oil distilling over. This is aneutral ethei*eal salt, which on hydrolysis yields a potlaqs;um salt, whichis converted into the lead salt, C6H,PbOa.The free acid is a thicksyrup : the calcium salt is not thrown down on boiling its aqueoussolution, so that the acid CsH,oO5 is not identical but isomeric withethoxyisosuccinic acid, being probably dilactylic acid, as shown bythe properties of the calcium and lead salts.Succinamic Acid. By R.. SERVA and J. WIEDEMANN (Bey., 23,3284-328;) .-Succinamic acid, "H,*CO-CR2*CH2*COOH, preparedby treating succinimide with barium hydroxide, as described by'l'euchert (AnnuZen, 134, 139), is identical with the acid prepared byheating nitrosoglutaric acid (Wolff, A n t d e n , 260, 114). I t crys-tallises from hot acetone in long needles, melts at 156-157", and ismoderately easily soluble in water, but very sparingly soluble or in-yoluble in alcohol, benzene, and light petroleum ; i t is converted intoammonium succinate on prolonged boiling with water, and whenheated alone at d W 0 , it is transformed into succinimide.B.B.B. B.F. S. K.Synthesis of Asparagine. By A. PIIJTTI (Guzetta, 20, 402-(Abstr.,CHGOOEtCH*COOAn 406).-?Vhen silver y-oximidosuccinate, OHON< I1889, 381), is heated on the water-bath with an excess of a"? etherealsolution of ethyl iodide, the silver iodide removed, and the solutionremainsC*COOEtCH-COOEtevaporated at, 60- 70°, diethy1 nitdosuccinute, X< Ias a neutral. yellowish oil. which mav be distilled in a vacuumwith partial decGmpositioo. When this slbstclnce is shakcn with strongoraqueous ammonia, ethyl nitrilosucc&aamute, NebH.COOEtC.CONH2C*CoNH3, is formed ; this compound crptallises from alcdhol <hH*O*C*Et176 ABSTRACTS OF CHEMICAL PAPERY.or acetic acid in brilliant, rhombic plates, melts at 166-167', andyields a bromide, CoH,N20$3r, which melts with decomposition akabout 140'.On reducing an acetic acid solution of this amide with soiliumamalgam (5 per cent.Na), care being t&en to maintain the liquidacid, separating the bulk of the sodium acetate by crystallisa-tion, and allowing the mother liquor to remain in prolonged contwtwith coppcr acetate, a crystalline deposit of insoluble copper saltsis formed, which, on decomposition with hydrogen stilphide, yieldsn solution containing three asparagines.These rimy be obtainedperfectly pure by precipitating their concetitrated solution withalcohol and recrystallising from water. On leaving the mixture in avacuum, the inactive a-compound loses its water of crystallisationand falls to powder ; the /I-asparagines may then be separated by theirmicroscopic characters.The author regards ethyl nitrilosuccinamafe as a derivative of theCH-nucleus N< I , which he terms " etazole," and has prepared a longCH,series of derivatives of ni trilosuccinamic acid i n support of this view.S. B. A. A.Amic and Anilic Acids of Fumaric Acid and Malei'c Acid.By E. ANSCH~TZ (Awnalen, 259, 1~7--148.-~~aleZr,a?rtic acid,C4HbNO3, is obtained when anhydrous ammonia is passed into achloroform or benzene solution of maleic anhydride, and the gum-like ammonium salt which is gradually precipitated M armed withwater until the evolution of ammonia is at an end ; on acidifyingwith hydrochloric acid, the maleinamic acid is precipitated in crystals,the yield being about 70 per cent. of the thecretical.It crystalliaesfrom water in large, transpareut, anhydrous plates, melts atl152-153", and is readily soluble i n hot alcohol anu water, but onlysparingly i n hydrochloric acid, and almost iiisoliible in benzene, ether,and chloroform ; when treated with alcobolic potash, it is convertedinto fumaric acid, but with aqueous alkalis and barium hydroxide inthe cold, i t yields salts of maleic acid.Fnmaranilic chloride, C,,)H&lN02, is obtained when fumaricchloride is treated with aniline in ethereal solution, the quantity ofbase employed beiiig less ihan is theoretically necessary to con-vert the chloride into furnrtric acid dianilide; the diauilide aridaniline hydrochloride produced are separated by filtration, theethereal filtrate evaporated, and the residue recrystallised from ether.Fumarrtnilic chloride forms transparent, yellow, prismatic needles,and melts at 119-120" ; with alcohols, it yields crystalline etlierealsrtlts, and with amines, it gives amidcs.When treated with coldwater or dilute alkalis, i t is converted into an acid of the compositionC10H9N03, which melts at 230-231", and is quite different from thefumaranilic acid (m. p. Hi--187.5") previously obtained by theauthor and Wirtz (Abstr., 1887, 934) from maleinanil in likemanner ; tho acid melting at 187-187.5" is, therefore, in future tobe termed mnleinanilic acid, to distinguish it from the acid meltinga t 230-2;31", which is named fum;dl*ibniIic acidOROANlC CHEMISTRY.177Fumaranilic a d is only sparingly soluble in boiling water, butmore readily than maleinanilic acid, and when warmed with aIcoholicor aqueous potash, it is, like the letter, converted irito fumaricacid.Judging from their behaviour, the amido- and anilido-derivatives oEmaleic and fumaric acids have the constitutiori expressed by thefollowing formula :-CH-C(OH)*NH,Malei'namic acid (m. p. 152-153") 11 >O 'GH-COCH*CO.NH,Fumaramic acid (m. p. 217"j 11 .C:H*COOHCH-C (OH)*NHPhMale'inanilic acid (tn.p. 187-187.5)" 11 >O 'GH-COCH*CO*NHPh0C:H*COOHFumaranilic acid (m. p. 230-231") 11The article concludes with a short criticism of BischoE's paper ondynamical isomerism (compare Abstr., 1890, 723). F. S. K.Diglycollic Anhydride. By R. ANSCHUTZ (Annalen., 259,187-193).--DigZycolZic anhydride, O< cH,.co>O, is obtained when tinelydivided diglycollic acid is boiled w i t h acetic chloride, or when thoacid is distilled under a pi-essure of 11 to 12 mm. It separates fromwarm chloroform in long, spear-shaped ciytaJ,ls, melts at 97", andboils nt 220" (12 mm.) ; it is only sparingly soluble in ether, and isreadily reconverted into the acid by cold water.Diglycollanilic acid, CloHIIO,N, is gradually deposited in crystalswhen an ethereal solution of the anhjdride is tieattd with aniline;i t melts at 118".CH?.COF.S. K.Dilactylic Acid. By S. TANATAR and CH. TCHGLEVIEFF (J. Rum.Chem. Soc., 22, lOi-llO).-~t was shown by Friedel and Wurtzthat calcium lactate, when beated at 270-%0", loses 1 mol. H20,and becomes calcium dilactate, but neither the salt nor the acid wasinvestigated by them. The experiment was repeated by the authors,and from the calcium dilactate o5tained, the frue acid, CBHII0O5. wasseparated by decomposing it with oxalic acid. The syrupy liquidobtained was puritied by diktillrttion at 170", under a pressure of80-90 mm. The distillate, after remaining for some time in tbedesiccator, was converted into monoclinic, prismatic crystals meltingat 105-lOi", easily soluble in water, ether, chloroform, and aceticacid, but only slightly in benzene.It gives an acid potassium salt,CaHgOaK, and a silver salt, CsH80aAg.?, which, on treatment withmethyl iodide, gave the methyl salt, CeHSUaMe2, boiling at 260". Thl i 8 ABSTRACTS OF CHEMlCAL PAPERSzinc salt, CsK805Zn + 3H20, is amorphous. Hydriodic acid at 159"is without action on dilactylic acid.Synthesis of Citric Acid. By A. HALLER and A. HELD (Cumpt.vend., 111, 682--685).--Ethy! acetodicnrboxylate is prepared fromct.byl y-cyanacetoacetate in t h e manner previously described (thisvol., p. 171), aud the ethereal s3lution ot the crude product from10 grams of the cyanacetcacetate is converted into a cyslrihydrin bycooling i t i? a mixture of ice and salt, adding 5 to 6 grams of finely-powdered potassium cyanide,and then,drop by drop, concentratedhydro-chloric acid i n quanthy exactly equivalent to the cyanide.The mixtureis allowed to remain in a closed vessel in a cocl place for 24 hours, andis then filtered, and the ether distilled off. The cyanhydrin is boiledfor two or three hours with concentrated hydmhloric acid in anapparatus with a reflux condenser, the ammonium chloride isremovGd and the liquid, after being concentrated to expel excess of mid,is boiled with excess of potash. The liquid now contains potassiumcitrate and chloride with other products formed in the course of thererlctions. The citric avid is best separated by means of lead acetate,the precipitate8being deconiposed by hydrogen sulphide, and the citricacid extracted by means of ether.50 grams of ethyl y-cyanacetoaceta[e yield about 6.2 grams of purecitric acid, and a further quantity of about 4 to 5 grams remains inthe syrupy mother liquor.Action of Phosphorus Pentachloride on Citric and AconiticAcids.By E. KLIMENEO and BUCRSTAR (J. Russ. ChemSoc., 22,96-99).-Pebal, by acting with phosphorus pentachloride ou citric acid,obtained the solid hydrox~chlorocitric acid and two liquid chlor-anhydrides. Tbe authors have treated citric acid (1 part) with phos-phorus pentachloride (3 parts) without heating ; after some time, thesolid contents of the vessel became converted into a liquid, whichafter the addition of Rome more citric acid became partly solid.Itwas then extracted with dry carbon bisu!phide and Pebal's bydroxy-chlorocitrjc was left together with some citric acid ; this whetitreated with alcohol, yielded R liquid boiling between 283" and 285",identical with Malagutti's triethyl citrate, so that the solid chlorideohtained at the beginning of the reaction is CsH5C1,O1. The samechloride is contained in the liquid product of the reaction. On heat-ing citric acid with phosphorus pentachloride, the liquid product isfound to prevail, and this contains some aconitic chloride. Aconiticacid with phosphorus pentachloride gives the chloride C,H,03C13identical with the above bye-product, and this, on being treated withethyl alcohol, yields Mercadante's triethyl aconitate.The formulaCsH,O,CI, given to the solid chloride by Skinner and Ruhemann(Trans., 1889, 235) iscontradicted by the authors, who find that thesolid product is not homogeneous, but always contains citric acid andprobably some aconitic acid.Alkyl Substitution Products of Ethyl Dicarboxyglutaconate,and a New Synthesis of aa-Dialkylglutaric Acids. By M,B. B.C. H. B.B. BORGAN10 OHEMISTRY. 1 i'9GVrHZEKT and 0. DRESSEL (Ber., 23, 3179--3186).-The authors havealready described a method by which dialkylglutaric acids containingtwo similar alkyl groups may be prepared (Abstr., 1889, 860). Toprepare disubstituted glutrrric acids containing t w o different alkjlgroups, it is necessary to start with ethyl dicarboxyglutaconate,CH( COOEt),*CH:C(COOEt),.When the sodium compound of thisethereal salt is heated with an excess of ethyl iodide in a sealed tube a t170-180", it yields the ethyl derivative, CEt(COOEt)CH:C(COOEt),,as a colourless oil tioiling without decomposition at 195--202" under11 mm. pressure. I t could not he obtained crystalline, and gives nocoloration with ferric chloride. Alcohol must not be employed in thepreparation of this snbstance, a s i t decomposes the sodium compoundat a high temperature. The fact that the ethyl compound is volatilewithout decomposition, whilst the unalkylated cornpound decomposeson heating with formation of an a-pyrone derivative, is in full accord-ance with the explanation already given by the authors of the latterreaction (Zoc.cit.).On hydrolysis, ethyl ethyldicarboxyglatacon~i te is converted intoeth,ylylutuconic acid, COOH*CHEt*CH:C HCOOH, which is a white,crptalline compound melting at 118-120". Its silver salt is a whiteprecipitate, and fairly stable towards light.Et h y 1 Eenz y ldicarbox yg Zut acoizat e,C(COOEt)2(CHzPh)*CH:C(COOEt)z,is prepared in the manner described by Conrad and Guthzeit (Annulen,222, 258), and is also volatile without decomposition, boiling at 240"(uncorr.) under 11-12 mm. pressure ; i t cr_vstallises from alcohol inglassy, rectangular crystals melting at 78". It is very slcwly reducedby zinc-dust and acetic acid.The ethyl compound, on the other hand, is readily reduced bythese reagents with foim~ation of ethyl eth!/ldicn1.boz?jglzrtnmte,CEt(COOEt),*CH2*CH(COOEt)2, which is also an oil boiling at195-197" (uncorr.) under 10-11 mm.pressure. On treatiticnt withsodium ctboxide and benzyl chloride, it, is converted into ethyl efhyl-beiizyltli~urboxygZufurute, (COO~Et,),CEt-CH2.C(CH2Ph) (COOEt 12,which i s an extremely thick oil boiling at 210-230" under 12 mm.pressure. On hydrolysis, i t yields a syrnpy tetrmarboxylic acidwhich slowly becomes crystalline, and loses carbonic anhydride onheating at 100--810° ; a syrup then remains which on analysis gavennmbers approximately agreeing with those required by ethylbemy2glutul-ic acid, COOH*CHEt*CH,*CH( CH,Ph).COOH. It has not yetbeen obtained pure or crystalline, but the neutral solution of itsammonium salt yields more or less insoluble precipitates with saltsof most of the heavy metals.H. G. C.Thiocarbimidoacetic Acid and Thiohydanto'in. By P.KLASON (Chem. Csntr., 1890, ii, 34; from Ofu. Kongl. Vet. Akad.,1890, 87).-The author considers that Claus and Neuhoffer's reactionof ethyl bromide on thiohydantoin is explained thus :-The ethFlbromide reacts with the alcohol w i t h formation of hydrogen bromide,which then reacts with the tltiohydanto'in with formatiOD of ammoni180 ABSTRACTS OF OHEMIOAL PAPERS.acd thiocrtrbimidoacetic acid, the latter becoming further convertedinbo thioglycollic acid, carbonic anhydride, and ammonia. Ethyl thio-cnrbimidoacetate. CSN*CH2*COOEt, is fortned by the action of cnvbonthiochloride oti ethgl amidoacetate. The carbon thiochlorido isdiluted with ether, and the ethyl amidoacetate added drop by drop,the mixture being kept cool ; ether is then added, filtered from theethgl amidoacetate hydrochloride, the filtrate distilled, the impureethyl thiomrbimidoacetIate distilled with steam, extracted from thewater with ether, and finally distilled in a vacuum.It is thusobtained us a colourless, somewhat thick liquid, having a feebleodour of oil of mustard, boiling at 110" under a pressure of 12 mm.Sy. gr. = 1.1649 at 18"/4".!f'haoh?,~Zar~toih is obtained by heating a mixture of ethyl amiclo-acetate hydrochloride and dry potassium thiocyariate in molecularproportion at, 140-150". The mass is dissolved in water, hydro-chloric acid added, and the solution evaporated.The componndNH*yH2When heated with barium hydroxide, NH-CO 'has the formula. CS<thiohydantoic acid, C3HeN2S02, is formed, which crjstallises in beau-tiful, colourless prisms, very slightlp soluble in cold water. Itercuiicoxide converts i t into hydantoic acid. Ethyl hydsntoate is formedin like mrtnrier to thiohydantoin if potassium cyanate is substitutedfor the thioepmate, and forms botmtitul prisms somewhat readilysoluble in hot water, and tnelting a t 138.3". J. W. L.Hydrolysis of Sulphones. By E. STUFFER (Ber., 23, 3226-324 1 ; corn pa re A bs t r., 1890, 987 i .--Diasopw)) y 1.mlphunediethy Z-methnne, C Et,(SO,Pr@),, is formed i t 1 small quantities, the principalproduct being potassium isopropylsulphonate, when the condensationproduct of diethyl ketone and ihopropyl mercaptan is oxiclised withpotassium per.maiigunat,e and dilute sulphuric acid.It crystallisestrom hot water in small plates, melts a t 97", and is insoluble in coldwater and alcohol, but readily soliible in ether, chloroform, benzene,and hot alcohol. Like diet.hyIsulphonedirnethylmethane (sulphonal),it is not Itydrolysed by boiling 30 per cent. aqueous or alcoholic potash.Pot nssiunz isop ropy lsulp h onat e, C3 H ,S 0, K, cry s tat li ses f rom hotalcohol in plates, and is readily soluble in water.I)iiSobiLfyl.~ulyhov~Ledirn~lh~l~~tharie, (?Me2( SO2-CH2PrS),, preparedby oxidising the condensation product of acetone aad isobutylmercaptan, forms colourless crystals. melts at 64", and is only spa-ringly soluble in hot water, but moderately easily in alcohol, andreadily in chloroform, carbon bisulphide, benzene, and ether ; it, is not,hydrolysed by boiling aqueous or alcoholic potash.The yield of thesnlphoiie is onlg small, as the principal product of the reaction is t!iepotassium salt, of the sulphouic acid.Diisoam y lsulp honed i me t h y kn et l ~ u r ~ e , C Me,( S02.CH2*CH,PrS) ?,obtainedin like manner from isoamyl mercnptan, forms crystalline scales,melts a t 72", and resembles the preceding compound in its behaviourwith solvents nnd alkalis.Diethylsulphonemethane (compare Fromm, Absh,, 1890,55) is noORGANIC 0 HEMISTRY. 181acted on by boiling alcoholic or aqueous potash or by sodinmethQxide i n boiling alcoholic solution, but when heated withsodium ethoxide at a temperature above loo", it is completely decom-posed.Diisobut y lsulp honem et 11 nne, C a,( S 02* C E,PrS) *, prepared by oxid is-ing the condensation product of formrrJdehyde and isobutyl mercaptan,forms colourless crystals, melts at 85": and is soluble in alcohol, ether,chloroform, benzene, and hot water, but insoluble in cold water ; itresembles diethylsulplionemethane i n it3 behaviour with alkali^.Theclibromo-deri d i v e . CBr2(S02*CH,Pi-@),, is a crystalline compoundmelting at 77-78".Propylew dieth yl sulphide is obtained when propylene bromide istreated with ethyl mercaptan and sodium ethoxitie; it, is a mobileoil, cannot be distilled, anti is decomposed by oxidising agents, butwithout yielding propylenediethylsulphone.PTopylens diplrerryl sbilphide can be prepared by boiling phenplmercaptan with propylene bromide and 10 per cent.soda for a fewhours ; it is ~1 heavy nil and cannot be distilled.P1.opyle~ediphe,t!/ls~6lphon., C3HS( S O,Ph),, is formed by oxidiuingthe sulphide with potassium pernianganate ; i t forms colourless,lustrous plates, melts at llS", and is soluble i n hot alcohol, benzene,chloroform, and hot water. but only sparingly soluble or insoluble inether and carbon bisulphide, and insoluble in cold water. Whenboiled witoh dilute potash, it is decomposed into benzenesulphiuio acidtind a colourless oil which is probably phenylsulplionepropyl orphenylsulp honciso propyl alcohol.rCrimethyE~neili~thyl~i~lph~?~e, c,H,(SO,Et),, can be easily preparedby oxidising trimethylene diethyl sulphide, the condensation productof trimethylene bromide and ethyl mercaptan, with potassitim per-manganate and dilute sulphuric acid.I t crystallises in colourlessplates or needles, melts n t 188", and is readily soluble i n hot water.but onlp sparingly i n ethar, chloroform, benzene, cold nlcohol, and(.old water; it is not decomposed by hot soda, in which it is soluble,and it is very stable towwds bromine alid oxidising tigcnts.Trimeth ylenediph en y lsuly hone, C3H6( SO,Ph),, obtained by heatingtrimethylene bromide with sodium benzenesulpbinatc in alcoholicsolution, separates frorn dilute alcohol in crptals, melts at 125-166",rind is almost insoluble in water aud cold alcohol, but moderatelymsilg soluble in hot alcohol.benzene, and ether, and very readily inchloroform. I t is not acted on by boiling soda or by oxidisingagents.A trisidphone of the constitutim SO,Bt*CH,*CMe(SO,Et), is ob-tained whet) chloracctone is heatel with ethyl mercaptan and con-centrated hjdrochloric wid, and the light-yellow oily product oxidisedwith potassiuni pcrmnnganate and sulphuric acid. It crystalligesfrom hot water it1 needles, melts at 137", and is readily solnble in hotalcohol ; it, is completely decomposed by warin soda, yieldirig ethyl-mlphinic Mid. F. S. K.Action of Acid Chlorides on Bases in presence of Alkali.J3y W. MARCKWALD (Urn., 23, 3207-;32 )8).-It has already hee182 ABSTRACT$ OF OHEMIOAL PAPRHS.pointed out by Hinsberg (this vol., p.49) that the reaction employedby Schatten and Bnumsnn for the preparation of benzoyl derivat,ivesis of very general application. The author has found that a benzenesolution of carbonyl chloride also acts in a similar manner onorganic bases i n presence of an excess of alkali, thus forming a readymethod of preparing symmetrically substituted carbamidea ; theurethanes may also be prepared in a similar manner from the dkylchloroformates.In addition to the substituted carbamides which are known, the>C*CH2*NH,, hare been following derivatives of furylamine,prepared.Symmetricit2 D$?urylcarbamide, CO(NH*CH,*C'4Ff,0),.-To obtainthis compound, a mixture of furylamine with aqueous caustic potashis shaken with a slight excess oi R benzene solution of carbonyl chlorideiintil the odour of the latter has disappeared, part of the carhamideseparating out.The bcnzene is evrtporatcbd, the sepai-ated difuryl-cwbamide collected, and recrystallised from benzene. It, formssmall, nacreous plates which are sparingly soluble in all theordinary Rolvants, melts at 128O, and has an intense odour resembl-ing that of the dwarf plume-thistle (Cadma acnulis).Ethyl fiwylc~crbamate, C4H30-C H,*NHCOO Et, is obtained in a cop-responding manner from furylamine and ethyl chloroformate. I t isextinacted from the aqueous solution with ether, and remains, afterdistilling off the latter, as a yellowish oil which has a pleasant odour.On heating, it distils at 240", forming a colourless liquid, which has,however, then an unpleasant d o u r , probably owing to the formationOE traces of furylcarbamine.Rationale of Reactions in the presence of Aluminium Chlorideand Bromide.By G. GUSTAVSON ( J . p. C h m . [el, 42, 51~1-507).--Friedel and Crafts (Abstr., 1889, 241) attributed the act-ion ofaluminium chloride and bromide in facilitating the displacement of thehydrogen in benzene, &c., to the formation OE such compounds asC,H,*Al,CI,, which, however, could only be isolated in the absence ofbydrochloric acid, for this decomposes them. If such be the case,the author Itasertt, that such a componnd as C6H,SO,*A1,C), shouldalso exist, for aluminium chloride brings about a reaction bekweensulphurous anhydride and benzene (Zuc. 4.) ; but there is no evidencethat such a cornpoand is formed when sulphurous anhydride ispassed into a mixture of benzene and aluminium chloride ; indeed,according to Adrianowsky (Abstr., 1879, 915), quite a differentreaction takes place.Friedel and Crafts fail to see how the cornpounds A1cl,(CsH6), &c.,which are formed according to the author's theory (Abstr., 1885,36:3), and are exothermic, can facilitate substitution ; the authorreplies that, i t is equally difficult to explain how hydrogen which hascorn bined with nitrogen in the exothermic compoiind ammonia shouldbe more ready to react with methyl chloride, &c., t h m when i n thefree state.'the author has obtained aud analysed the compoundAlCl,,SC,H,; such compounds as this are deconiposed by heat, andEH-0CH*CHH. G.CORCIANIO OHEWISTRY. 183will not explain those reactions which only take place at high tern-peratures. A. G. B.B.y P. v. D. BECKE(Ber., 23, 3191--3196).-The preparation of these hydrocarhonsi maybe readily carried out by means of Friedel and Crdts' reaction. l thas been shown by Gustsvson (Ber., 11, 1251), Silva (Abstr., 1885,1054), and Kekule and Schrotter, that in the presence of aluminiumchloride tbe prop91 group is converted into isoproppl. and in prepnr-ing the above hydrocarbon it is immaterial whether propyl or iso-props1 bromide is employed. 300 grams of ethylbenzene were there-fore mixed with 50 grams of alQminium chloride, and 450 grams ofpiwpyl bromide gradually added. After remaining for eight days, theproduct is washed, dried, and fractionated ; th3 fractions 189-1 95"and 195-201" contain the meta- and para-ethy iisopropylbenzenerespectively.The fraction 150-155" is isopropylbenzene, the proper-ties ot which agree with the statements of Ciaus and Tonn (Abstr.,1885, 903), except that the author finds the melting point of thesulphonamide to be 93-94O instead of 127". The fraction 179-185"contains dietliylbenzenes, and that boiling at 204-208" consists prob-ably of di-isopropylbenzenes.'l'o obtain the pure hydrocarbons from the fractions boiling at189-195" and at 195-201" respectively, both are sulphonated witha mixture of 1 vol. of concentrated sulphuric acid and 4 vol. offuming acid, the first sulphonic acid being isolated as the barium salt,and the second as the magnesium salt.These are then convertedinto the potassium salts, and the latter hcatcd with hydrochloric acidunder pressure.,~~tethylisoprop?lZbenzene is a colourless, pleasant-smelling liquid,wlrich boils at 190-196", does not solidify at -W", and on oxidationyields isophthalic acid. Barium w~etetl~yEis~rop!~lbenxeiiesul~honatecrystallises in anhydrous, fascicular aggregates of needles, spibrinqlysoluble in water, whilst the coppw salt crydallises with 4 mols. H,Oin blue plates which have a satin-like lustre. The sulplinchkwide audsulphonarrLide are oils.PurethylisqZlrolrylben=ene is 8 liquid which is more strongly refrac-tive than water, boils at 197-198", and does not become solid a t-220".On oxidation, i t is converted into terephthdic acid. Mugne-sium pareChylisn~opy Ebenaenesulpltonate crystallises with 4 mols. H,Oj t i tablets which are sparingly soluble i n water. The copper saltalso crystallises with 4 mols. H20, and forms blue, satiny plates ;whilst the potassium salt could only be obtained as an amorphous,readily soluble mass. The sulphochloride is an oil, and the suiphon-cr?nide only becomes partially solid i n the exsiccator. The s71lphon-anilide, on the other hand, crystallises in nodular aggregates ofprisms melting at 9%-93".Nitl.ol)".rethylisoprop!/lbenzene is obtained by the nitration of thehydrocarbon in acetic acid solution, and forms a yellowish-browu oilwhich boils at 265" with partial decomposition.On treatment withziric and acetic acid, it is slowly reduced to ctmi~oyaret~iyiisoprolryt-benzene, the hydrochloride of which forms fascicular aggregates ofMeta- and Para-ethylisopropylbenzene184 ABSTRAOTS OF OHEMIOAL PAPERS.ireedles, becoming brown in the air. P~reth,/Ziso~l.op?/733henoZ is oh-tained by fnsing the potassium sulphonate with caustic Ptash, and is;I yellow oil boiling at 228--230", almost insoluble in water, butreadily soliible in alcohol and ether.The author has also prepared p~?.ethT/Zprop?IZBPn,zPne wm-n~-ling toSempotowski's method (Abstr., 1890, 54). It boils at 199-200',rind yields, 011 sull-,honation, only one s/rlplronic ((rid, the maqnesiumsalt of which crystallises in smnll prisms containing 4 mols. H,O. andis readily soluble in water.The sdphonamide crptrtllises from diluterllcohol i n small plates which melt n t 84", and the .culphnnaniZide infmciciilar aggregates of slender needles melting at 97-98'.H. G. C.Diisopropylbenzsne. B y E. UHr,HmN (Rw., 23, 3142-3144).-A mixtiire of two hydrocarbons, boilitip at 200-210°, is obtainedi n the preparation of isopropylhenzene (b. p. 153") by Friedel andCraft's method: the two compounds can be separated from oneanother by shakinz the mixtni*e with concentrated sulphuric acid,converting the sulphonic acids thus produced into their copper orbariiim salts, and separating the salts by fractional crystallisation.Bnrium metndiisopropylbenzenesiilphonccte cry s t a l k s in long. needleswith 2 mols. H20, and is only sparingly soluble in water.The copperwit, with 4# rnols. H20, forms long, blnish needles, and is readilyd u b l e . The magnesium salt, witL 4 mols. H20, crystallises in well-defined, prismatic plates, and is rather sparingly soluble in water.The sodium and the calcium salts crystalhe in needles, and are veryrertdily soluble in water.MPtadiisopropiilben,.erLesulp7Lonanzide cryxtallises in colourless plates,and melts at 145".T r L n i t , . c r n e t a d i i s ~ r c ~ ~ l ~ ~ ~ q i ~ c n e forms yellowish needles, and melts at110-111". M e t a d i i s l ~ r ~ y l b e n z e n e , prepared by heating the sulphon-timide with hydrochloric acid at 180", boils at 204", and, on oxidatiouwith dilute nitric acid, is converted into isophthalic acid.Copper nrthcdiiso);rnpylbenzev~~ult~hnnatt! cryhtallises i n plates with64 mols.HzO, and is bpariiiglg soluble in water. The rnagwsium,calcium, and sodium salts are very readily soluble. The suZphonamidemelts at 102", and yields orthodii..o~rc~yZbenzene boiliug at 209", which,on oxidation, is converted into phthalic acid.Nononaphthene and its Derivatives. By I. KONOVALOFF (J.ltuss. Chem. Sor., 22, 4-93 and 118--148).--Seversl years ago, Mar-ktwnikoff and Ogloblin obtained from Caucasian petroleum a seriesof hydrocarbons, " naphllrenes," of the generctl formula CnHZn, havingthe properties of saturated compounds of the aromatic series. Nono-naphthene was obtHined from Balachnna and Bibi-Eibat petroleum bytreating thc fraction boiling between 12.?-140* with fuming sulphuricacid at, 40", washing with aqueous sods and water, di.yinq,and rectifyingover sodium, and, after repeated fractional distillation, ngain purifyingi t in the same manner.The fraction boiling at 135-136" coosistg ofthe hydrocarbon nononaphthene, C9H,, ; its sp. gr., when prepared fromthe first-named source, i s 0.76t1.e (20/23"), from the second 0.7647.As sulphuric acid acts on nononaphthene, it is not without reason thatF. S. KORGANIC CHEMISTRY. 185Mendeleeff recommended that the us3 of this reagent for its purifim-tion should be avoided. With excess of sulphuric acid, nononaphthenegives pseudocumenesulphonic acids. Sulphur or antimony penta-chloride at high temperatures gives indefinite mixtures of thio- orchloro-derivatives. By the action of bromine and aluminium bromide,pa'% of the hydrocarbon is converted into tribromopseudocumene.Nitric acid of sp.gr. 1.4 is without action in the cold, but if thehydrocarbon is hedted at 120-1130", with the same acid diluted withtwo volumes of water, nitro-derivatives are obtained such as CsH15N02 ;this boils at 218-220", and on treatment with hydrochloric acid andtin, an amine, C8Hl5.NH2, isomeric with conijine is obtained. It smellslike that alkaloid, boils between 172" and 177", and gives only in a feebledegree Hofmann's reaction for primary amines. Its sp. gr. is 0.8727at O", and it is a strong baae, combining with acids, and absorbingcarbonic anhydride from the atmosphere.Nononaphthene was heated with hydriodic acid with the object ofhydrogenating it, but nonane was not formed.By the action of chlorine,chlorides were obtained, containing principally C9H&1, boiling at185-187'. The chloride was converted into the iodide C9H,,I byheating it with strong hydriodic acid at 150-160° ; this boils atL08--lllo under a pressure of 200 mm. On heating the chloride or theiodidewith silver acetate and acetic acid, the acetate, CH3*CO0CDHlj, wasobtained ; it boils at 208.5". This, on hydrolysis, yields nonoaaphthybaE~ohoE, C9El7.0H, boiling at 189-192" ; sp. gr. = 0.8972 a t 20"/20° ;and the alcohol, on treatment with phosphorus pentachloride, yields thechloride C9H1,CI, mentioned above and having the same properties.A solution of the iodide in ether, when heated with silver oxide,yields the ether (CDH,,),O, boiling at 300.5"; sp.gr. 0.8662 a t 2Oo/2O0.The elements of hydrogen chloride are easily removed from the chlor-ide, C9H,,C1, with formation of ?iononaphthyEene, C9HI6 ; this boils at135-137", and has sp. gr. 0°8068 a t 0". With bromine, nononaph-thylene yields a dihromide, C9H,,Br2, which is easily split up intohydrogen bromide and the bromo-derivative CSHISBr, but it is im-possible to saturate the compound with bromine up to the limit.Oxidation of nononaphthene and its alcohol with chromic mixturevields a complicated mixture ot acids. Xononaphthene is proved toi,e hexahydropseudocumene [b. p. 135-138" ; sp. gr. 0.7667 (20/0°)].It has hitherto been found to be impossible to convert it by hydro-genation into nonane, the corresponding saturated hydrocarbon ofthe fatky series. B.B.Caucasian Petroleum. By V. MARKOVKIEOFF (J. RUN. Chent. SOC.,22, 23-26).-By fractional distillat ion of the lower boiling portionsof Caucasian petroleum, previously purified by fuming sulphuric acid,the author has obtained a series of fractions boiling between 32" andI 2 , and not further separable by fractional distillation. The relationbetween the boiling points and the densities shows that the higherfractions contain comparably larger proportion of naphtheneshaving a higher density than the corresponding paraffins, whereas thelatter are more abundant in the fractions of lower boiling point. Itis shown that the portion boiling between 57" and 60" contains neithern oVOL.LX. 186 ABSTRACTS OF OHEMICAL PAPERS.hexanaphthene nor benzene, and that it consists principally of di-psendopropyl C,H,,. The fraction 45-48' contains hexane (tri-methylethylmethane) and pentane ; the fraction 52-36" consistschiefly of dimethylethylmethane, whilst the fraction boiling above 60"contains normal hexane. B. B.Action of Thionyl Chloride on the Phenols. By G. TASSINARI(G'azzetta, 20, 362-366).-The action of thionyl chloride on thephenols results in the formation of a mixture of variable quantities ofthree substances, namely (l), a compound of high melting point notexamined further ; (2) a dihydroxythiobenzene identical with thatobtained by the action of sulphur dichloride ou phenol (Abstr., 1889,245) ; (3) chlorinated and snlphuretted resins.Hydrogen chlorideand sulpburous anhydride are also evolved during the reaction.Thionyl chloride has a similar action on ort,hocresol and thymol, theonly difference being that with orthocresol a good deal of the com-pound of high melting point is formed, and but little of the dihydr-oxytbiobenzene, the reverse occurring with thymol ; paracresol isscarcely affected in the cold, only a trifling quantity of liquid chloro-paracresol being formed.The dihydroxythiobenzene previously described (Zoc. cit.) has thefollowing crystallographic characters. The crystals belong to themonoclinic system :--a : b : c = 0*4!1564 : 1 : 0.26415 ; /3 = 86" 48'.The derived hydroxysulphonebenzide crystallises in the rhombic sys-tem :-a : b : c = 0.78133 : 1 : 0.413568 ; /3 = 90".S. B. A. A.Condensation Products of Glyoxal and some Mercaptans.By E. STUFFER (Bey., 23, 3241-3245).-GGyoxal combines withethyl mercaptan in presence of hydrochloric acid, but the productcannot be obtained in a pure condition, nor can it be convertedinto a tetrasulphone by oxidation with potassium permanganate.TetrathiophenyEgZyoxa.2, CE(SPh),*C H (SPh),, is formed whenglyoxal sodium hydrogen sulphite is warmed with phenyl mercaptanin alcoholic hydrochloric acid solution. It separates from alcoholicchloroform as a colourless powder, melts at; 215', and is very readilysoluble in chloroform, but only sparingly in boiling alcohol, andinsoluble in water and alkalis.It dissolves in warm concentratedsulphuric acid with a cherry-red coloration, is readily oxidised anddecomposed by concentrated nitric acid, and combines with bromine,yielding a yellow, oily compound : when treated with potassium per-mangnnrtte under various conditions, i t is either unchanged or com-pletely decomposed, so that the corresponding sulphone cannot beobtained. F. S. K.Nitrometacresols. By W. STAEDEL and A. KOLB (Annuleu, 259,208-227 ; compare Abstr., 1889, 497 j.-The two metanitrocresolswhich are obtained by nitrating pure c~esol, prepared from thymol,can be easily separated by distillation with steam. The non-volatilecompound (m. p. 129') crystallises from water and alcohol in needles,is very readily soluble in benzene, ether, chloroform, alcohol, andhot water, and dissolves in alkaline carbonates with evolution of carbORQANIO CEEMISTRY.187onic anhydride. The ammonium derivative forms long, yellowneedles, and the silver derivative is a yellowish-red compoundalmost insoluble in water. The potassium derivative, C7H,N0,K +2H20, and the sodium derivative, with 2H20, crystallise in yellowplates, and the barium derivative in silky needles. The ethyl de-rivative melts at 53-54', and is identical with the compoundobtained by nitrating metacresol ethyl ether.Orthonitrometatoluidine [Me : NH2 : NO, = 1 : 3 : 61, prepared byheating nitrometacresol ethyl ether with concentrated ammonia a t140-150", cryst.allises from water in slender, yellow needles, melts at134", and is readily soluble in alcohol, ether, and hot water ; whentreated with sulphuric acid and sodium nitrite in alcoholic solution, iti s converted into nitrotoluene (b.p. 220-221").Amidometncresol [Me : OH : NH2 = 1 : 3 : 61, obtained by re-ducing the nitro-compound with tin and hydrochloric acid, is a greypowder melting at 174" with decomposition. The hydrochloride,C,H,ON,HCl, crystallises in colourless plates. The acetyl derivative,C9Hl,N02, crystallises from water, in which it is readily soluble, incolourless plates containing 1 mol. H2O ; these melt at, 80" and losetheir water a t 110-120"; the anhydrous compound melts a t 125",and is sparingly soluble in benzene.Methytquinonec?~lorimide, C,H,NOCl, is precipitated when a con-centrated solution of calcium hypochlorite is added to a diluteaqueous solution of amidometacresol hydrochloride.It cryshllisesfrom alcohol in golden prisms, melts at 75", and explodes at ahigher temperature.Dinitrometacresol ethyl ether [Me : OEt : (N02)z = 1 : 3 : 4 : 61 isformed when the corresponding mononitro-componnd is treated withfuming nitric acid. It crystallises from dilute alcohol in colourlessneedles, and melts at 97".Dinitrometntol~.r6idilze, prepared by heating the preceding compoundwith ammonia at loo", separates from xylene in yellow crystals, melts.at 195", and is only sparingly soluble in alcohol and benzene ; whentreated with nitrous acid under suitable conditions, it is convertedinto a-dinitrotoluene [Me : (NO2)* = 1 : 4 : 61.Trinitrometacresol ethyl ether [Me: (NO*), : OEt = 1 : 2 : 4 : 6 : 31crystallises from alcohol in slender needles or in thick prisms meltingat 75" ; it is probably identical with the compound (m.p. 72") ob-tained by Nolting and von Salis from the silver derivative of trinitro-cresol ; when treated with alcoholic ammonia, it is converted intotrinitrotoluidine (m. p. 136').The volatile nitrometacresol (m. p. 56") crystallises from ether inyellow plates, and is only very sparingly soluble in water, but veryreadily in alcohol, ether, benzene, and chloroform. The potassiumderivative crystallises in red needles, and is very readily soluble inwater. The ethyl derivative, C9HILN03, crystallises from alcohol incolourless needles, melts at 50-51", and is very readily soluble inmost of the ordinary solvents.Nitrometntoluidine [Me : NH2 : NO2 = 1 : 3 : 41, prepared by hest-ing the ethyl derivative with ammonia at 140-150°, crystallisesfrom water in golden plates, melts a t log", and is moderately easily0 188 ABSTRAOTS OF OEEMIOAL PAPERS,soluble in alcohol, ether, benzene, chloroform, and hot water ; ethyInitrite at 100" converts it into pamnitrotoluene.When nitrometacresol ethyl ether (m.p. 50-51O) is treated withnitric acid, it is converted into a, dinitro-compound identical withthat (m. p. 97") obtained from the isomeride described above.F. S. K.Constitution of Thymol and Carvacrol Derivatives. By G.MAZZARA (Gazzetta, 20, 417~27).-Tetracet~ldiamidothy~nol acetate[Me : NAc2 : OAc : Pr : NAc2 = 1 : 2 : 3 : 4 : 6 1, prepared by heatingdiamidothymol hydrochloride with acetic anhydride, crystallisesfrom dilute alcohol in shining, white scales, softens at 179", andmelts at 184-186".It isiasoluhle in alkalis.MeDiacetylamidoethen ylam,idot h!ymol, \CMe, is obtained itsYra bye-product in the preparation of the preceding compound. Itis prepared by heating that compound or its constituents at atemperature of 200" to 260". It crystallises from light petroleum inlarge, colourless, transparent, rhombohedric tables, melts at 92-94',and dissolves in the ordinary solvents. It is decomposed by pro.longed digestion with alkalis yielding products which impart a violetcoloration to the liquid. The action of dilute hydrochloric acidremoves one acetyl group from this compound, leaving monacetyb-amidoethenylamidothy mol, a substance which crystallises from al coho1in yellowish or violet needles melting at 132-139". It dissolvesreadily in alcohol and benzene.It is reconverted into the diacetylderivative by heating with acetic anhydride at 200". It is decom-posed by digestion with alkalis or acids.The action of acetic anhydride on diamidothymol hydrochloride at160" results in the formation of a mixture of di-, tri-, and tetcr-~ c e t y Idialnidothynzol. These compounds are all soluble in potash,forming pink solutions, from which acids precipitate the diacet.ylderivative. They also dissolve in boiling water and in dilute alcohol,crystallising out in white or pale-violet scales.The tetracetyl com-pound melts at 216-222", the triacetyl compound at 238-240", andthe diacetyl derivative at 260-262".MeAcet ylamidoethenylamidocarvaerol, NHdc fl *>,,Me, prepared by\/P'rheating diamidocarvacrol hydrochloride with excess of acetic an-hydride at 210", crystallises from alcohol in yellowish needles andmelts at 190-192". The formation of this ethenyl derivative and oft h e benzenyl derivative previously described (this vol. p. 48) support.the anthor's view, that in dinitrocarvacrol the two nitroxyl groupsare in the meta-position relatively to each other. S. B. A. AORGANIC CHEMISTRY. 189Constitution of Rhodizonic Acid. By R, NIETZKI (Bey., 23,3136-3141).-Tho author agrees with Nef (Abstr., 1890, 1270)that rhodizonic acid has the Constitution C604(OH), [O, : (OH), =1 : 2 : 3 : 4 : 5 : 61, and not the symmetrical constitution [O, : (OH), =1 : 2 : 4 : 5 : 3 : 61.One of the principal facts which points to thisconclusion is that croconic acid hydride, C5H405, a compound whichis formed from rhodizonic acid under the influence of concentratedalkalis, does not combine with ortbodiamines, whereas croconic acid,CbH205, is readily converted into azines. This difference in behaviouris best accounted for by assuming that the hydride has the constitu-COG*OHtion OH*CH<Co.~.oH, and the formation of a coinpound of thisnature from rhodizonic acid can only be explained by assuming thatthe latter has the asymmetrical structure. The existence of dinitroso-resorcinoltetroxime, C6H2(N*OH)4 [(NOH), = 1 : 2 : 3 : 41, seems toshow that the quinone of the constitution CaH20i [04 = 1 : 2 : 3 : 41is also capable of formation, whereas no symmetrical paradiquinonehas yet been obtained; this argument, as well as the behavionr ofrhodizonic acid with orthodiamines, bears out the author's viewsregarding the constitution of rhodizonic acid.F. S . K.Replacement of the Hydrogen Atoms in the MethyleneGroup. By 0. WALLACH (AnnuZen, 259,300-309).-The hydrogenatoms of a methylene group which is in direct combination with basicradicles are readily displaced by negative elements, more especiallyby sulphur ; and in most cases, the reaction proceeds SO well that itcan be conveniently employed for the preparation of various sulphurcompounds.When benzylanilino (1 mol.) is heated with sulphur (2 atoms) at220" until the evolution of hydrogen sulphide ceases, thiobenzanilideis formed ; if, however, the temperature is raised to 250-260", andthe heating is continued, benzenylamidothiophenol (m.p. 115') isobtained. Benzyltoluidine and other benzyl bases behave likebenzy laniline.Tetramet h yldiamidot hiobenzop henone can be easily obtained byheating tetramethgldiamidophenylmethane (50 grams) with sulphur(15 grams) at 230" until the evolution of hydrogen sulphide is at anend ; thiobenzamide can be prepared by heating benzylarnine withsulphur at 180".Tribenzylamine combines with bromine in glacial acetic acid solu-tion, yielding a compound of the composition (C7H7)3NBr2 ; this sub-stance crystallises in golden needles, melts at 157-159", is recon-verted into tribenzylamine by sulphurous acid, and when boiled withwater, is decomposed into benzaldehyde, dibenzylamine, aud tribenzyl-amine.When benzglamine is treated with bromine in glacial acetic acidsolution, it yields a crystalline substance melting at 103O, which seemsto have the composition CH,Ph*NH2Br2 ; this bromo-compound isdecomposed by warm water and alcohol, and also on exposure to theair, into benzonitrile and benzylamine hydrobromide.B, S. K190 ABSTRACTS OF OHEDIICAL PAPERSAction of Paratoluidine and Aniline on Phloroglucinol. ByG. MINUNNJ (Cazzetta, 20, 319- 355).-Phloroglucinol reacts veryenergetically with paratoliiidine or aniline forming compoundsandogous to those obtained by t'he action of the aromatic amines onmonhydric and dihydric phenols.Both symmetrical triparatolyltri-amidobenzene, c&( NH*C7H7),, the product of the action of para-toluidine on phloroglucinol, and triphenyltriamidobenzene, obtainedfrom aniline and phloroglucinol, together with a number of their deriva-tives,have already been described (Abstr., 18€!8,1081). The followingare additional products :-The nitrosyl derivative of triparatolyltri-amidobenzene, C6H3[N(c7EI7)*N0],, crystallises from boiling alcohol inslender, deep-brown needles, melts at 233-234", and dissolves sparinglyin hot benzene and in alcohol after prolonged boiling ; it is readilysoluble in concentrated sulphuric acid forming a dirty-green solution.Diparatoly ldiamidoh y droxy benzene, O H C6&( NH°C7H7) 2, prepafedby heating a mixture of phloroglucinol (1 mol.) and paratoluidme(2 mols.) for six hours at 140-150°, crystallises when pure from a.mixture of ether and light petroleum in colourless needles, meltsat 120-121", and, on exposure to the air, turns grey at first, butbecomes intensely brown after a time.It dissolves readily in coldbenzene, alcohol, and ether, and in hot alkalis, but only very sparinglyin boiling water and in concentrated hjdrochloric acid. It is alsosoluble in concentrated ~ulphuric acid forming a colourless solutionwhich turns brown on heating, aud reddish oc addition of a littlepotassium nitrite. The hydrochzoride may be obtained as a yellow,flocculent, amorphous precipitate which decomposes as soon as it isremoved from the acid solution.The piatinurn saZt,OH°C6H, (NHCTH,) 2,PtCI4,crystallises in brilliant, bronze-coloured scales, insoluble in ether, andonly very sparingly soluble in boiling alcohol ; it is decomposed by hobwater; on heating to 260°, i t is converted into a brown, amorphouspowder.The acetyl derivative, OH*CJ€,(NACC~H~)~, crystallises in colour-less, microscopic prisms, melts at 128-129O, and dissolves in coldalcohol and benzene, and very sparingly in ether. Jt is also spa-ringly soluble in alkalis, and more readily in concentrated acids.Ammonia precipitates i t unchanged from its hydrochloric acid solu-tion.The benzoyl derivative, OBz.C6H3(flBzC7H7), (P), forms a colour-less, crystalline powder consisting of microscopic plates, and meltsat 262-264".It is almost insoluble in ether, and only verysparingly soluble in alcohol and benzene. It is insoluble in alkalis,but dissolves in concentratc d sulphuric acid, and is reprecipitatedunchanged on diluting the solution.The nitrosyl derivative, O~*C6H3(NC7H7*N0)2, crystallises inbrownish-red, microscopic needjes which darken on heating to 230°,but do not fnse even at 260". It is very sparingly soluble in alcoholand benzene, and almost, insoluble in ether.Tbe nitrosy I derivative of triphenyltriamidobenzene, C6E3(NPh*NO)2crystallises from alcohol in brilliant, brown needles, melts at 264-265 ,Its composition is doubtfulORGANIC CHEMISTRY.191and is almost insolublc in alcohol and benzene. It dissolves in coldconcentrated sulphuric acid forming a solution which appears dark-green by reflected light, and copper-coloured in the magnesium light.Dipheny ldiamidoh?ydroxy benzene, OH-C6H3( NHPh),, is prepared byheating phloroglucinol with anil ioe in the theoretical proportionsfor six hours a t 140-150". It crystallises from a mixture of etherand petroleum in slender, white ueedles which acquire a grey tingeafter some time, melts at 96-95', and dissolves readily in cold alco-hol, benzene, and ether, but only sparingly in water, alkalis, andhydrochloric acid. On cooling its solution in potash, a substanceseparates out, readily soluble in water. It dissolves in cold concen-trated sulphuric acid, and the solution turns blue on the addition ofa little sodium nitrite, and brownish-red when a larger quantity isadded.The hydrochloyide, OH*CsH3( NHPh),,BHCl, is an amorphous,brownish-yellow powder which is decomposed by hot water; itmelts at S5-90°, and is soluble in alcohol, but not in ether. Theplatl:num salt, OH*C6H3(NHPh),,PtCl,, crystdlises in large,. yellow-ish-brown plates which darken at 230"; it dissolves readily inboiling alcohol, but is insoluble in ether. It is decvmposed by boilingwater.The acetyZ derivative, OH°C6H3(NPhAc)2, forms a white, crystal-line powder which melts at 149-150", and dissolvea readily in boilingalcohol and benzene. It is moderately soluble in hot alkalis and incold concentrated acids. Ammonia precipitates from its hydrochloricsolution a white powder soluble in excess.The benzoyl derivative,OH*C6H3( NPhBz),, is obtained by treating the base with benzoicanhydride. It crystallises from alcohol in large, bright-yellowneedles, melts at 184-185", and dissolves readily in the ordinarysolvents, and also in boiling alkaline solutions and in cold concen-trated sulphnric acid. The nitrosyl derivative, OH*C6H3(NPh*N0)2,crystallises from boiling glacial acetic acid in bright-red needles, andblackens without melting at 250" ; it is almost insoluble in the ordi-nary solverlts, but dissolves in cold concentrated sulphuric acid.Attempts were made to prepare a dihydroxy-derivative,by moderating the reaction between phloroglucinol and pamtoluidine,but without success, the inonhydroxy-derivative being formed inevery instance; a similar failure atteaden an attempt to preparemixed derivatives of the type C6H3(NH*C7H7),*NHPh. From theforegoing results, it appears that phloroglucinol, a trihydric phenol,reacts more energetically with aromatic amines than the dihydricphenols, which in turn are more active than the monhydric com-pounds.The energy of reaction must, therefore, depend directly onthe number of OH-groups present. Moreover, in view of the completeanalogy between the action of ammonia and that of the substitutedamines. it seems mobable that mhloramine. the moduct of the actionC6H3( OH),*NH0C7H7,of amionia on phoroglucinol, & also a derivati;e of trihydroxybenz-as indi- enc, and not of the secondary phloroglucinol, Q H2*C0 *$l H,CO*CH2*C0 'cated by Baeyer (Abstr., 1886, 350).S. B. A. A192 ABSTRACTS OF OEEMICAL PAPERS.Consecutive Tetramidotoluene. By R. NIETZKI and R. ROSEL(Ber., 23, 3216-3219).-A mixture of the mono- and di-nitro-derivatives of diacetylmetatoluylenediamine is obtained when di-acetyl metatol us1 enediamine is mixed with carbamide nitrate, qndthen gradually introduced into nitric acid (6 parts), which has beenpreviously distilled with sulphuric acid, the temperature being kepta t from 5 to 10". The two compounds are precipitated with ice andhydrolysed with dilute sulphuric acid or dilute alkalis ; the mono-and di-nitrometat,oluylenediamine obtained in this way can be easilyseparated from one another, as the latter aloae is soluble in alkalis,being reprecipitated on the Itddition of an acid.Dinitrometatoluylenediamine, C6HMe (NO,) 2( NH,),, forms slender,golden needles and melts above 300".Tetramidotoluene suZphate, C6HMe( NH2)d,H2SO4, is obtained whenthe dini tro-compound just described, or tetrisoni trosoresorcinol[Me : (NOH)o = 1 : 3 : 4 : 5 : 61, is reduced with stannous chloiidearid hydrochloric acid ; the filtered solution is treated with sulphuricacid, then mixed with a considerable quantity of alcohol, the precipi:tated sulpbate dissolved in moderately dilute hydrochloric acid andreprecipitated with alcohol ; i t cry stallises in small, almost colourlessplates.When excess of sulphuric acid is added t o a hydrocldoricacid solution of this salt, a compound of the compositionCsHMe(NH, ),,2H2S04is precipitated in Emall plates.Tetramidotoluene cannot be obtained by decomposing one of itssalts, as it rapidly oxidises on exposure to the a i r ; solutions of itssalts are colonred brown by ferric chloride and other oxidising agents,but a definite oxidation product could not bc obtained.A qzcinoxaline of the composition C35H2iN4 is gradually depositedin yellowish-red needles when tetramidotoluene snlphate is heatedwith b e n d arid sodium acetake in alcoholic solution; it melts at222-225", and dissolves in concentrated sulphuric acid yielding ared solution, the colour of which changes to yellow on the addition ofwater.Croconic acid also combines with tetramidotoluene, yielding adark-brown azine, which crjstallises in needles, but is so insoluble inall ordinary solvents that it cannot be purified by recrystallisation.When tetramidotoluene sulphate is heated with sodium acetate andacetic anhydride, a compound of the composition C15H20N404 isobtained ; this subst,ance crystallises in colourless needles, melts at305", is moderately easily soluble in hot water, and is probably atriacetylethcnyltpetramidotoluene of the constitutionCs'IIMe( N HAc),<T->CMe.It dissolves in diluie hydrochloric acid, and ou adding ammonia tothe solution, a colourless, very readily soluble base melting a t 282" isprecipitated ; judging from the analysis of the picrate, this base isprobably diacetylethenyltetramidotoluene. F.S. KORGANIC CHEMISTRY. 193Diazo-compounds. By H. GOLDSCHMIDT (Bw., 23, 3220-3222).-The author has determined the molecular weight of meta- andpara-nitrodiazobenzene nitrate aud of diazobenzene chloride, inaqueous solution by Raoult's method ; the experiments have shownthat in very dilute aqueous solutions these salts are completely dis-sociated, but that in more concentrated solutions the observedmolecular weight increases rather rapidly, more quickly, in fact, thanis the case with most metallic salts; the electrical conductivity ofsolutions of diazo-salts is also being investigated.Aldoximes. By E. BECKMANN (Ber., 23, 3:319-3331, and 3331-3341).-Salicylaldoxime (m. p. 57") may be converted into an isomericmodification by the action of hydrochloric acid, either at the ordinarytemperature or on heaking.The a-benzyl ether of this compound isprepared by the action of sodium ethoxide and benzyl chloride, andcrystallises from warm alcohol in slender, colourless, interlacedneedles which melt at 62-63".The same compound is also obtained by heating an alcoholic solu-tion of salicylaldsh-j-de with a-benzylhydroxylamine hydrochlorideand hydrogen sodium carbonate, The corresponding P-bewyl ether isformed in a similar manner from p-henzylhydroxylamine, and crystal-lises from dilute alcohol in pale-yellow, lustrous, rectangular plateswhich melt at 99-100".-4CTION OF PHENYLCARBIMIDE ON THE BENZALDOXIl/I Es.-T he phenylisocyanate employed in the following experiments boiled a t 161-162",and was absolutely free from hydrogen chloride.P-Benzaldoxime isdissolved in 12-14 parts of absolute ether, and treated at 5" withrather less than the calculated quantity of phenylcarbimide ; a copiouswhite precipitate is immediately formed, consisting of mici*oscopic,quadratic plates which melt at 74-75' with evolution of gas; onboiling with dilute potash, carbonic anhydride, aniline, and diphenyl-carbamide are formed. On warming equivalent quantities of 6-benz-a1 doxime and phenylcarbimide dissolved in benzene, and evaporatingthe solution, crystals are deposited which melt at 94" with evolutionof gas; the substance is isomeric with the previous compound, andhas already been prepared by Goldschmidt (Absfr., 1890, 251).Carbonic anhydride and a trace of diphenylcarbamide are formedby the action of dilute potash. The first of these isomerides is verysparingly soluble, and is converted into the higher melting derivativeon warming with benzene, but hhis latter cannot be transformed intothe lower melting compound.Neither of the substances reacts withphenylcarbimide ; with hydrogen chloride, both yield the compound(m. p. 134") described by Goldschmidt (Zoc. cit.). By the action ofdilute soda in the cold, the lower melting compound yields chieflyP-benzaldoxime, whilst benzonitrile is the principal product from thehigber melting modification.By the action of phenylcarbimide on a-benzaldoxime in etherealsolution, a compound separates which melts at 73" and is identicalwith the above derivative from 8-benzaldoxime ; if this substance isremoved and the solution allowed fo remain for a short time, a secondcompound crgstallises out in needles which melt at 135"; this hasF.S. K194 ABSTRACTS OF CHEMICAL PAPERS.previously been described by Goldschmidt. a-Benzaldoxime is, there-fore, less stable than has hitherto been supposed ; it is also found thatby warming, or by keeping the 8-aldoxime for some time, the yield ofthe P-derivative is increased. The author suggests that the twocompounds obtained from p-benzaldoxime and phenylcarbimide arerepresented by the following formula :-AH PhAH Ph(M. p. 7 4 O . ) (M. p. 94O.)Benzalbenznmide, NHBz*C7H7, is obtained by the action of benzoicchloride on p-benzaldoxime benzyl ether, and crystallises from benz-ene in colourless plates which melt at 105".Acetic chloride andphosphorus oxychloride act in a similar manner, but hydrogen chloridein benzene solution causes no change. The compound may be pre-pared synthetically from benzylamine and benzoic chloride. Onbeating the amide with hydriodic acid, benzyl iodide, benzoic acid,and ammonia are formed, whilst in similar circumstances p- benzald-oxime benzyl ether yields a small quantity of benzoic acid and benzyl-amine. Goldschmidt prepared a compound (m. p. 121") by the actionof phenylcarbimide on B-benzaldoxime benzyl ether ; this result isconfirmed. On heating with concentrated 11 ydriodic acid, benzyliodide is formed ; boiling hydrochloric acid is without action, but onheating at 140", complete decomposition takes place ; the compound isunchanged by snlphuric acid at ordinary temperatures.By the action of sodium ethoxide on the carbanilido-product dis-solved in alcohol, carbonic snhjdride is eliminated, and a basic com-pound of the formula C,H,,JV, is obtained, which crystallises fromdilute alcohol in large, flat, rectangular plates melting at 99-100".The hydrochloride crystallises with difficulty.The same compoundis formed by tke action of benzanilidiimido-chloride on benzyl-amine, and it must therefore be regarded either as symmetricalbenzylphenylbenzenylrtmidine, or as a quiiiazoline derivative (seebelow). The compound is not acted on by hydrochloric acid andalcoholic ammonia ; on heating with hydriodic acid, i t yields benzoicacid, ammonia, and aniline.On heating the carbanilido-derivative with alcoholic ammonia at100" for an hour, benzylideneaniline is formed, together with a viscid,oily liquid which yields benzylidenephecylhydrazoxe on treatmentwith phenylhydrazine ; its niolecular weight is 111, as determined byRaoult's method ; the compound contains two CHPh groups, togetherwith the complex NPh, but its exact constitution is not yet deter-mined.Of the three formula for /3-benzaldoxime, namely, PhC:N(OH)CiH7,OH*CPh:N*CJ37, and PhC€€*N*C,H,, the author has previously ad-vanced the first two ; the above results point, however, to the absence'ORQANIO OHEMISTRY.195of a hydroxyl group, and consequently the third one would appear tobe the most probable. The compound formed by the action of phenyl-NH- CHPhcarbimide would be represented by the formula 1 >NPh, CHPh.0420which would account for its great stability; by the eliniination ofcarbonic anhydride, an amidine or quinazoline derivative would beformed, with the formula C6H5*CH2*NH*CPh:NPh orrespectively. J.B. T.Dyes of the Primuline Group. By E. TRAUTMANN (Chem. Centr.,1890, ii, 440-441 ; from Mon. Sci. [4], 4, Sll--S20).-1f clehydro-thiotoluidine, prepared by heating paratoluidine with sulphur (Green,Trans., 1889, 227 ; Gattermann and Pfitzinger, Abstr., 1889, 867), beheated with methyl alcohol and hydrogen chloride or iodide at150-200", the salts of the ammonium baseCsH3Me <:>CGH,.NMtl,*OHare formed ; the chloride has been introduced into the market underthe name thio$avin, and is a similar dye to anramine. The primulinebase is prepared by heating thiotoluidine or dehydrothiotoluidine, oreven paratoluidine, with sulphur; its constitution has not yet beenestablished.Treatment wit.h fuming sulphuric acid converts it intothe sulphonic acid, the sodium salt of which is primuline. (For thesimilar dyes obtained from metaxylidine and pseudocumidine, seeAbstr., 1889, 602.) Dehydrothioxylidine unites with a-naphthol-a-sulphonic acid, forming the dye named " Erika." Thiazole- yellow issodium amidoazodehydrothiotoluidinesulphonate ; i t dyes unbleachedfibre greenish-yellow and cannot be deazotised on the fibre.Parachloracetotoluidide and Metaparanitrochloracetotolu-ide.By H. ECKENROTH and A. DONNER (Ber., 23, 3287-32$9).-Parachloracetotoluidide has previously been obtained by the action ofchloracetic chloride on pamtoluidine, and may be prepared by heatingparatoluidine (1 mol.) with chloracetic acid (2 mols.) at 80-90" fortwo hours ; the product is treated with water and recrystallised fromalcohol. If the temperature is allowed to rise somewhat, a secondcompound is formed, which is being further investigated; it issparingly soluble in water, but dissolves in dilute potash, and is pre-cipitated by hydrochloric acid ; from alcohol, it crystallises in whiteneedles melting above 230" with decomposition.J. W. L.Nitrochloroucetofoliiidide, N02.C6H,Me*NH*CO*CH~Cl[Me : NO2 : NH = 1 : 3 : 41,is prepared by the action of nitric acid at ordinary temperatures onthe chloracetic derivative, and cry stallises from alcohol in yellowneedles which melt at 122" and yield metaparanitrotolnidine on treat-ment with potash.J. B. T196 ABSTRAOTS OF OHEMIOAL PAPERS.Action of Potassium Hypobromite on Phenylsuccinamide. ByS. HOOGEWERFF and W. A. VAN DORP (Rec. Trav. Chim., 9,33-68).-1na previous communication (Abstr., 1889, SSl), the authors have shownthat chlorine, bromine, hydroxyl, and nitrosyl are extremely mobilewhen combined with nitrogen, compounds containing such a combina-tion readily undergoing an intramolecular change, in which thenegative element or group is displaced by a more positive radicle. Incontinuation of these researches, they have investigated the action ofpotassium hypobromite on phenylsuccinamide, and the properties ofthe bromamido-compound thus obtained.The phenylsuccinamide required for these experiments was pre-pared by the method given by Menschutkin (this Journal, 1872,497).15 grams of this substance is dissolved in a solution of 18 grams ofpotash and 12 grams of bromine in 300 C.C.of water, then dilutedwith 600 C.C. of water, acidified with acetic acid, and the precipitatethus obtained washed with water. The product could not be obtainedpure, but was found to contain bromine, and from its reactions is un-doubtedly a bromamidop~enyZszicciiux;nzide, NHBr*C4H402*NHPh. Onwarming its solution in alcohol or acetone, an intramolecular changetakes place, parubromopheiLyZsuccinamid~, NH2*C4H4O2*NH*C6H43r,being formed.The latter is sparingly soluble i n cold water and ether,more readily in hot water, and very easily in boiling alcohol andacetone. It crystallises i n needles or plates which melt at 213-215"with decomposition. On boiling with aqueous potash, it yields firstgarabroniophenylsuccinamic acid and ammonia, the former decom-posing on further heating with potash into pnrabromaniline andsuccinic acid. Parabrornoplien?lLsuccinamic acid crystallises in needles,melts at 186-187", and is readily soluble i n alcohol and acetone,Rparingly in ether and water. It may also lie prepared by the actionof alkaline potassium hypobromite on phenylsuccinamic acid. Itsbarium salt forms needles or plates, and its copper salt is a pale-blueprecipitate.By the action of warm dilute potash on brornamidophenylsuccin-amide, the bromine is displaced by hydroxyl, and an intramolecularchange takes place at the same time.To carry out the reaction,10 grams of phenylsuccinamide are converted into the bromamide, andthe latter is dissolved in a solution of 6 grams of potash in 34 C.C. ofwater, 50 C.C. of concentrated potash solution is then added, and thewhole warmed for 2+ hours at 55-60". On the addition of hydrochloricacid, a precipitate is obtained, which is purified by dissolving it inpotash, reprecipitating with hydrochloric acid, reducing its alkalinesolution with sodium amalgam, and recrystallising from hot water.Its composition was found on analysis to be C10H12NBOB.On passinghydrogen chloride into its alcoholic solution and adding sulphuricacid, it very readily yields an ethyl salt, and therefore contains acarboxyl group. It loses the elements of water on boiling with aceticchloride, forming a substance which is reconverted by alkalis into theoriginal compound, and on fusion with potash decomposes intocarbonic anhydride, aniline, and P-amidopropionic acid. From thesefacts, it follows that the acid has the constitutionNH Ph* C 0 *NH * C H2* C H,* C 0 OHORGANIC CHEMISTRY. 197and it may be termed 23hrnyl-~-urei'~~prop~onic acid or phsnyl-P-lactur-amic acid. It crystallises in needles or plates melting when quite pure at171-172", and is readily soluble in alcohol, acetone, warm water, andwarm acetic acid, sparingly in ether, and almost insoluble in benzeneand light petroleum.The calcium salt, (C1UHllN203)2Ca, forms ccn-centrically grouped needles, and the silver salt, Cl,HIJV"OsAg, anamorphous, white precipitate, which is fairly stable towards light.The ethyl salt, C1J3,,N203Et, crystallises from water containing a littlesodium carbonate, in needles, melts at 84-85', and is readily solublein alcobol, ether, and benzene, sparingly in light petroleum.As already stated, the acid is split u p on fusion with potasb intocarbonic anhydride, aniline, and P-amidopropionic acid. The latteris best isolated as the platinochloride of its ethyl salt, which is ob-tained by passing hydrogen chloride into the alcoholic solution of theacid, evaporating, and treating the alcoholic solution of t8he residuew i t h platinic chloride solution.It separates in yellow needles, con-taining water OC crystallisation which is given off a t 90-loo", the saltthen having the composition ( CaHl~N02)2,H2PtC16. It is readily solublein water, melts at 193' with evolution of gas,and is identical with thecompound prepared synthetically from P-iodopropionic acid. Thehydrochloride, C5HllN02,HC1, forms bygroscopic crystals.The compound obtained by the action of acetic chloride onphenylureldopropionic acid has the composition CloH1,-,N2O2, andcrystallises in needles which melt at 231-234O, and do notvolatilise without decomposition. It stands in the same relation tophenylureidopropionic acid as hydantoi'n to hydantoic acid, and has,therefore, the const'itution CO< NH.cH2>CHz, and may be termedphenyIhydrouruci1.By the further action of acetic chlcride a t 10Go,or by acting with an excess of the latter 011 the acid, phenyZacetyE-hydrouracil, Cl2HI2N2O3, i s obtained, and crystallises i n needles meltinga t 135-138".That phenylureiidopropionic acid has really the constitution aboveassigned to it has been further shown by its synthetical formationfrom phenylcsrbamide and p-amidopropionic acid. On heatingthese two compounds together at 135", the following reaction takesplace :-NPh-CONHPh*CO*NH, + NH,*CH,*CH2*COOH =NHPh*C O*NH*CH2* CHz.COOH + NE3.The compound thus obtained is identical in all respects with theacid above described, but the yield is not good.The formation of phenyl-/3-urefdopropionic acid from phenyl-succinamide is very difficult, and perhaps impossible, to explain, if tholatter has the svmmetrical constitution usually assigned to it, namely,NH,*CO*CH,*CH,.CO.N~Ph.It has, however, been shown by Auger(Abstr., 1888, 952) that tbyrnmetrical succinamide can exist', and t h eauthors believe that phenylsuccinttmide has also the asymmetrical con-, the bromamido-compound then be- stitution CO--0>C<NH2 IC H2*CH NHP198 ABSTRACTS OF CHENIOAL PAPERS.coming CH2'CH2 I NHPh. The potassium salt of the latterCO --O>'<NHBrundergoes an intramolecular change, forming the compoundwhich by the further action of potash yields QH2*CH2*rKCOOK*CH,-CH,*NH*C(OH) (OK)*NHPh ; this then loses the ele-ments of KOH, forming phenyl-P-ureidopropionic acid,CO - 0- CBrNHPh'COOK*CH2*CH2*NH*CO*NHPh.Wben parabromophenylsuccinan~ide is treated with potassiumhypobromite, it yields an unstable brornamide, which is readily con-verted into the corresponding bromophenyZurei;doprop~onic acid,CIOHL1BrN203, by the action of potash.This acid is readily solublein warm alcohol, sparingly in ether, benzene, and hot water, andcrystallises in flat needles which decompose at 229". On fusionwith potash, i t yields parabromaniline, and its alkaline solutionis reduced by sodium amalgam to pknylure'idopropionic acid. Itscalcizm salt is a very voluminous precipitate, and its silver salt formswhite flocks.By the action of potassium hypobromite (1 mol.) on phenylnreido-propionic acid, no monobromo-componnd could be obtained, but with2 mols.of hypobromi te, a small quantity of dibromopheny Zureidopropionic:acid, CI,,H,,Br2N2Os, was formed, crystallising in needles which melt at201-202" and yielding dibromaniline (m. p. 78-81') on fusion withpotash. If 3 mols. of hypobromite are employed, tribrowwphenyl-zcrezdopropionic acid, CloH,Br3N203, is obtained, and is also formed insmaller quantity with the dibromo-compound when only 2 mols. ofhypobromite are used. It separates from acetic acid in crystals whichmelt, a.t 219-220" with decomposition, and yields symmetrical tri-bromaniline on fusion with potash.Carbamide Derivatives of Amidocinnamic Acid.By F. W.ROTHSCHILD (Ber., 23, 3341-3346) .-Orthouramidocinnamic acid,NH2*C0.NH*CsH4*CH:CH*COOH, is prepared by the action ofpotassium cyanate on orthamidocinnamic acid hydrochloride, and crys-tsllises from water in small, pale-yellow needles which dissolve inammonia and also in hydrochloric acid ; the aqueous solution has anacid reaction.H. G. C.Orthamidocinna WI ic acid thiocgalanate,CNSH,NH,*C,H,*CH:CH*COOH,is obtained in a similar manner to the previous compound, and i Fdeposited from water in tufts of prismatic crystals which melt at152" with evolution of gas. On heating the compound at 110-120"€or 18 hours, ortltothioItl.amidociiLnamic acid,NH2*CS*NH*CsH,.CH:CH*CO OH,is formed, which melts at tL36--239", and is insoluble i n alcohol, butdissolves in hot glacial acetic acid or ammonia.0rthoaZlylth.iouramidociniiumic acid,C3Hs*NH*C S.NH*CsH4*CH:CH*COOEORQANIO OHEMISTRY.199crystallises from a smali quantity of acetic acid on the addition ofwater in white needles which melt at 204-208" with decomposition.NHPh*CS*NH*C6H,*CH:CH*COOH,Ort hop hen$! t hiouramidocinnamic acid,crystallises from glacial acetic acid, and melts at 235-237".By the action of carbon bisulphide on orthamidocinnamic acid at loo",a compound is obtained which is probably cirthocnrbocinnamyldithio-carbamio acid, CSSH*NH*CsH4*CH:CH*COOH ; it cvystallises fromwater in white, microscopic prisms, melts at 185--187*, and is solublein ammonia but insoluble in hydrochloric acid.Metatliiocyunamidocinnamic acid is prepared by the action of thio-cyanic acid on metamidocinnamic acid ; it crystallises from alcohol,melts at 148-149", and is very readily soluble in water and alcoholi n the cold.The corresponding para-derivative crystallises from waterin pale, yellowish-brown needles, which remain unmelted at 272",but decompose on suddenly heating. It yields a white silver salt.On evaporating an aqueous solution, and heating the residue for sometime at loo", parathiouranzidociicnainic acid is obtained as a yellowsubstance insoluble in alcohol ; it remains solid at 273", but melts withgas evolution when heated OIL platinum foil.Aromatic Alkyl Ketones ; their Oxidation by PotassiumPermanganate. By A. CLAUS (J. pr. Chem.c%J, 42, 508-516 ; com-pare Abstr., 1890, 769, 979).-Paracymyl methyl ketone [Me : Ac : Pr= 1 : 2 : 41 is a nearly colourless oil which boils at 249-250" (un-cow.), and does not solidify at -10". The oxime was obtained. Thephenylh ydraxide forms lustrous, colourless needles which melt at 134"(uncorr.), By reduction with zinc-dust in alcoholic potash, the ketoEeyieldsparac~naylmethyEcarBinol [Me : Pr : CHMeaOH = 1 : $ : 21, anuncrystallisable Dil which boils above 300". The constitution of thisketone is sethled by the fact that it yields methylisophthalic acid[Me : (COOH), = 1 : 2 : 41 (m. p. 332"), identical with Jacobaen'sp-xylidenic acid (Abstr., 1882,188) ; thepotassium (with 2 mols. H20),barium (with 2 mols. H20), and silver (with 1 mol.H,O) salts of thisacid, and the chloride, and the amide are described ; further oxidationconverts this acid into trimellitic acid [l : 2 : 43 (m. p. 210°, nncorr.).Pa~-acymylgE?/oxylic acid [Me : COCOOH : Pr = 1 : 2 : 41, obtainedby oxidising the ketone in the cold with potassium permanganate, isa thick, yellow oil ; it decomposes at 220", and dissolves in the usualsolvents except water; the calcium (with 2 mols. H20), barium (with1 mol. H20), and silver salts Were obtained. When reduced withsodium amalgam, this acid yields paracywtylglycollic acid[Me : CH(OH)*COOH : Pr = 1 : 2 : 41,which forms crystals melting at 124" (iincorr.), and soluble in theusual solvents, except cold water ; the sodium, potassium, calcium.(with 24 mols. H,O), barium (with 3 mols. HJO), silver, copper (with8 mols.H20), and lead salts are described.By heating paracjmyl methyl ketone with ammonium sulphide in asealed tnbeparacymylacetaiitide [Me : Pr : CH2CONHz = 1 : 2 : 41 isJ. B. T200 ABSTRAOTS OF CHEMIOAL PAPERS.obtained; this crystailises in thin, lustrous scales, melts at 123" (un-corr.), sublimes, and dissolves in the usual solvents, exceptl cold water.ParacymyZacstic acid is obtained by saponifying the amide ; i t crystal-lises in flat, lustrous, colourless needles which melt at 70" (uncorr.),and dissolve in the usual solvents, except cold water; the sodirmt (wit112 mols. H20), potassium. (with 1?j mols. H20), calcium (with 4 11101s.H20), barium (with 6 mols. H20), and silver salts are described.By E.GUENEZ (Cowpt. rend., 111, 681-682).-This compound can be prepared by Moissan's reaction. Silverfluoride atid benzoic chloride in equivalent proportions are heated ina sealed tube a t 190" for tive to six hours. The product is distilledfrom the silver chloride, and even if excess of silver fluoride has beenused, the liquid must be heated again in a sealed tube with moresilver fluoride, in order to ensure the complete decomposition of thebenzoic chloride.Benzoic fluoride is a colourless liquid with an odour resembling thatof benzoic chloride, but much more irritating. It boils at 145", burnswith a smoky flame with a blue edge, is heavier than water, by whichi t is decomposed into benzoic and hydrofluoric acids, and is rapidlydecomposed by solutions of alkalis, especially on heating.Benzoicfluoride attacks glass with great rapidity, with formation of siliconfluoride, an alkaline fluoride, and benzoic anhydride.Conversion of Cinnamic into Isocinnamic Acid. By E.ERLENMEYER (Ber., 23, 3130--3131).-Since both a- and P-bromo-cinuamic acid yield benzaldehyde on oxidation, the bromine atom mustbe in the a-position in both compounds ; it is probable, therefore, thatthe so-called 8-bromocinnamic acid corresponds with isocinnamic acidand the a-bromo-acid with cianamic acid. This view is rendered veryprobable by the fact that when the @-acid is treated with hydrogenunder certain conditions, it yields isocinnamic acid and variable quan-tities of cinnamic acid ; the iso-acid obtained in this way exhibits allthe properties of the natural isocinnamic acid discovered by Lieber-mann.F. S. K.A. G. B.Benzoic Fluoride.C. H. B.Metaxylalphthalide. By E. HEILMANH (Ber., 23, 3157-3168).-Ne tatol u y lace t ic acid is prepared bay heating metat olu ylacetoni trilew i t h three parts of concentrated hydrochloric acid a t 100" for 4-5hours. O n fusing metatoluylacetic acid with an equal weight ofphthalic anhydride, together with a small quantity of anhydroussodium acetate, water and carbonic anhydride are eliminated, and asubstance with the formula Co<O ->C:CH*C6H4Me is formed ; ifthe group CH.C6H4Me is termed xyEaZ, then this compound would becalled metaxy ZaZphthaZide. It crystallises from alcohol in pale-yellowneedles melting at 152-153", and is very sparingly soluble in theordinary media; the yield is 64 per cent.of the theory. On treat-ment with potash, xylalphtltalide is hydrolysed, and the unsaturatedacid which is first formed changes spontaneously into the com-pound C6H~Mc.CH~'C0.C~H~*cooH ; this is deposited from alcoholC6HORGANIC GflE,WSTRY. 201on the addition of water, in long, lustrous crystals which melt at11 1-1 12". The corresponding oximidoluctone,is prepared by the action of hydroxylamine on the acid, and crystal-lises from dilute tllcohol in white, lustrous needles which melt at133-134", and are insoluble in alkalis.By the action of alcoholic ammonia on xylalphthalide, methylde-oGC!/benzozncurboxyla?nide is formed; i t is difficult to isolate and readilyloses the elements of water, naetaxylalphthulimiLEine,CO < zg4> C:CH*C6HIMe,being obtained ; this crystallises from alcohol in needles which meltat 165".Nit~o-xyla~hthalimidine, CO< GH4> C:C (NO2)*C6H4Me, isprepared by the action of nitrous acid on xylalph thalimidine ; it crys-tallises from alcohol in yellow, lustrous needles, and melts at157-159". The reaction is explained by assuming that au unstabledinitro.derivat,ive is first formed, from which the mononitro-compoundis produced by the elimination of nitrous acid. Dinitro-xylalphthalie,CO<~6~>C(N02)*CH(N02)*C6H4Me, is prepared by the action ofnitrous acid on xylalphthalide, and crystnllisss from acetic acid inwhite, lustrous, rhombohedra1 plates, which soften a t 125" and meltat 133" with evolution of gas.C HNitro-xylalphthalide,is prepared by heiting the previous compound with dilute alcohol ;it crystallises in yellow, lizstrous needles, and melts at 144" withdecomposition.Nitro-xylalphthalide is dissolved in potash, and the solution acidiiiedwith hydrochloric acid ; the product consists of a mixture of phthalicanhydride and metatoluylnitromethurte, C6H4Me*C:H,*N0, ; this corn-pound is separated by distillation in a current of steam, and is &yellow, viscid liquid which decomposes on distillation, has a peculiar,offensive smell, and yields metaxylylamine on reduction.Nitro-xylalphthalide is decomposed on heating a t 190°, phthalicanhydride and rnetatoluyl isocyawate being formed; the latter is acolourless, oily liquid, which boiis at 190-200°, and yields metatoluyl-carbarnid0 on treatment with ammonia ; the vapour rapidly attacksthe eyes.By the action of phosphorus and hydriodic acid on nitro-xylalphthalide, a compound is obtained which is isomeric with xyld-phthalide, and is therefore termed iso-xylalyhthalide; it is slowlydeposited from alcohol in long, slender, white crystals, which melt a t92-93O. The constitution of the compound is probably representedby the formula I >C*CTH,. C6H4* CHco-0 - -YO-NH>C.C,H;, is prepared by heating C6H4* CH I ~ ~ - ~ y Z a ~ h ; t h a l i m i d i n e ,VOL. LX. 1202 ABSTRAUTS OF UHEXICAL PAPERS.the previous compound with alcoholic ammonia at 100" ; crystallisesin small, lustrous needles, meltR at 196", and is very sparingly solublein the ordinary media.Meta~oluyEchloroisop.llinoline,is obtained by the action of phosphorus oxychloride on the previous com-pound ; it crystallises in white, Iustrous needles, and melts a t 43-44".On heating with hgdriodic acid at 170°, and treating the productis formed as a with potash, metatoly lisoquinoline, C6H4<colourless, viscid liquid, whicb crystallises after some time, and meltsat 51-52; i t is deposited from methyl alcohol in long, lustrousneedles. The picrate, hydrochloride, sulphate, and ylutii~ochloride areall crystalline. J. B. T.CH:TCH:C*C7H,'Ssogallic Acid Phenylhydrazide. By C. BOTTINGER (Aimaten,259, 873--377).-The phenylhydrazine derivatives of tannin andgallic acid (Abstr., 1890, 163) are very similar in properties, and havethe same reducing power as regards alkaline copper solutions ; whenthe tannin derivative is heated with hydrochloric acid at 120", it isdecomposed into gallic acid, phenylhydrazine, and a very small quantityof a reddish-yellow, crystalline, neutral substance ; the author namesit, tl~erefore, isogallic acid phenylhydrazide.Isogallic acid phenylhydrazide is converted into an unstable acetylderivative on boiling with acetic anhydride ; i t is completely decom-posed by boiling alkalis, a property which it has in common withgallic acid phonylhydrazide.F. S. K.Condensation Products of Amido-acids with Benzene-sulphonic Chloride. By s. G. HEDIN (Ber., 23, 3196-3199 ; seealso Hinsberg, this vol., p.&).-For the preparation of the abovecondensation products, the amido-acid is dissolved in aqueous potash,and an equivalent quantity of benzenesulphonic chloride added insmall portions alternately with caustic potash, warming and shakingwell during the process. After filtering, if necessary, the liquid isacidified, and the product, being, as a rule, sparingly soluble i n coldwater, may then be readily purified.Alanine yields the compound SO2Ph-NH-C2H4*COOH, crystallisingfrom hot water in slender needles ; this melts at 126", but forms an oilunder water at lOO", and is readily soluble in hot water, alcohol,ether, and ethyl acetate.The 1eucin.e compound, S0,Ph.N H*CsHlo*COOH, crystallises inbeautiful, long needles which melt at 86", and are less soluble in waterthan the foregoing compound, but readily soluble in alcohol, ether,acetic acid, and chloroform.The uspartic acid derivative, SOzPh*NH-C2H3( COOH), crystallisesin splendid, rhombojidal crystals melting at 170".The nlutamine compound, S02Ph*NH*C3H,(COOH),, does noORGANTO OHEMISTRY.203separate on the addition of an acid, but must be extracted withether, and on the evaporation of this it remains as a syrup whichgradually solidifies over sulphuric acid, but is not thus obtained quitepure. It is distinguishcd from the other condensation products byits ready solubility in water.Tyrosine yields two compounds, one of which is sparingly, andthe other readily, soluble in water.The former has t.he compositionS02Ph*NH*C2H3(C,H4*OH)*COOH, but the latter has not been ob-tained pure.Tolueneparasul phonic chloride also readily forms condensation pro-ducts with amido-acids. Moreover, fibrin, after treatment withpancreatic juice, combines with benzenesulphonic chloride, forming anoil, but it is uncertain whether this is a mixture or not.An attempt was made to prepare benzenesulphoneg lycocine,S02Ph*NH*CH2*COOH, by feeding dogs with sodium benzcnesulphon-ate, a process coi-respondiDg to the preparation of hippuric acid fromsodium benzoate. The results obtained, however, were negative, aswere similar experiments in the human organism.Benzenesulphinic Acid and Ethylsulphinic Acid. By W.AUTENRIETH (Annalen, 259, 362-364) .-Pure, dry benzenesulphinicacid does not readily undergo oxidation on exposure to the air; itssodium salt is very stable, and is not decomposed to any appreciableextent when its aqueous solution is heated a t 180" for 12 hours.Ethylsulphinic acid is best prepared by oxidising ethyl mercaphnwith potassium permangnnate, converting the sulphonic acid thusproduced into the chloride, and reducing the latter with zinc-dust inalcoholic solution.The pure acid is unstable, but the dry sodiumsalt is only slowly oxidised on exposure to the air. F. S. K.Sulphone Derivatives of the Crotonic Acids. By W. AUTEX-EL. G. C.R I E T E - ( A ~ ~ & ~ , 259, 332-3357).-~-Pi~~~ylsul~honeisocrotonic acid,can be prepared by heating a moderately concentrated .CH,*g*SO,PhH*C*C 00 R 'aqueous solution of sodium P-chlorisocrotonate with sodium benzene-sulphinate at 140--150" for six to eight hours, precipitating the acidwith sulphnric acid, and then extracting with ether.It can alsobe obtained by treating ethyl p-diphenylsulphonebutyrate withcold, concentl-ated potash (compare next abstract) ; the yield isalmost quantitative in both cases. It crystallises from water inneedles, melts at 126-127", and decomposes at a higher tempera-ture ; it is moderately easily soluble (1 in 20) in boiling, but onlysparingly (1 in 390 at, 15') in cold, water. It is decomposed by tinand warm concentrated hydrochloric acid with liberation of mer-captan, and boiling alkalis decompose it completely with eliminationof benzenesulphinic acid, but it is not acted on by bromine in boilingchloroform solution.The potassium salt, CloHgS04K + 3H20, crya-tallises from water in lai*ge, transparent, efflorescent plates, and isreadily soluble in water and alcohol. The barium salt, (C10H9S04)2Ba + 2*H20, magnesium salt (with 6 mols. H,O), and zinc salt (with6 mols. H,O) crystallise well, and are moderately easily soluble in water.P 204 ARSTRAOTS OF OHEMICAL PAPERS.The silver salt, CloH,S04Ag, crystallises from water in well-definedplates, and decomposes suddenly at 240-245". The ethgl salt,Cl,H,S04Et, is a colourless oil.So2Ph*!?*Me is prepared by p- P ~ e n y lsullphonecro tonic acid,heating an aqueous solution of the sodium salt of (3-chlorocrotonicacid with sodium benzenesulphinate at 160-180° for eight hours ;the yield is quantitative.It crystalliseij from water in lust~ousplates, melts at 158" with previous softening, and is moderately easilysoluble in ether, alcohol, arid benzene, but only very sparingly in lightpetroleum; it is soluble in 262 parts of water at 15" and i n 3.~8 to4 parts of boiling water. When heated at 200-210" €or 20 hours, itis completely converted into the isomeride (m. p. 127") describedabove, but attempts to bring about t h i s intramolecular change bymeans of sulphnric acid, iodine, alcohol, and water were unsuccessful.The potassium salt, CIUHgS04K + 1$H20, is deliquescent, and doesnot crystallise well. The barium salt, (CloH,S04),Ra + H20, is veryreadily soluble in water.The magnesium salt (with 7 mols. H20)and the zinc salt (with 6 mols. H,O) separate from water in large,transparent crystals. The copper salt forms small crystals containing1 mol. 8,O. The silver salt, C1UH9S04Ag, crystallises from water inverv small needles, and decomposes suddenlv a t 198-200".H~CCOOH'/3-Et~~lsul~honeisocrotonic acid, CH3*g*S0'Et can be prepared by H.C .COO H'treating ethyl P-diethylsulphonebutyrate (compare Baumnnn, Abstr.,1887, 123) with potash in the cold, or by heating sodium p-chloriso-crotonate at 140-150" with sodium ethylsulphinate in aqueous solu-tion. It separates from cold water in well-defined crystals, melts a t98", and is readily soluble in alcohol, ether, chloroform, and water.,but only moderately easily in benzene.It is slowly decomposed byalkalis into tetrolic acid and ethylsulphinic acid, and when treatedwith tin and hydrochloric acid it yields mercaptan, but it is not actedon by bromine in boiling chloroform solution. The silver salt,CsHgS04Ag, forms large, well-defined crystals, and decomposes onexposure to light ; the other metallic salts do not crystallis:, well,The ethyl salt, CsH14S04, is a colourless oil which cannot be distilled.The stereochemical isomeride of /%ethylsulphoneisocrotonic acidcould not be obtained. 3'. S. IC.Sulphur Derivatives of Ethyl Acetoacetate, Ethyl Methyl-acetoacetate, and Ethyl Ethylacetoacetate. By W. AUTENRIETH(Annulem, 259, 365--373).--Ethyl p-diphanTlIsulphonebutyrate,CMe( SO2Ph),*CH2*C0OEt, can be obtained by adding sulphuric acidand potassium permanganate to a benzene solution of ethyl a-dithio-phenylbutyrate (compare Beumann and Escales, Abstr., 1886, 878)until a permanent coloration is produced.It separates from alcoholin well-defined, lustrous crystals, melts a t 97", and is readily solublein hot alcohol, ether, and benzene, but only sparingly in cold alcohol,and insoluble in water; when treated with potash, i t is convertedinto ~-phenylsulphoneisocr.otonic acid (compare preceding abstract)ORQANIC CHEMISTRY. 205Eth,yl a-ethyl-P-diethylsulphonebutyrate, CMe( S02Et),*CHEt.COOEt,is formed when ethyl a- ethyl-/3-di thioet hyl butyrate, the condensationproduct of ethyl mercaptan and ethyl ethylacetoacetate, is oxidisedin a similar manner.It crystallises from boiling water in lustrousplates, melts at 87-88'. and is readily soluble in ether, benzene, andalcohol ; it is not acted on by concentrated potash or ammonia in thecold, but on boiling with potash, it is gradually decomposed, yieldingsmall quantities of an acid melting at 102-103', the nature of whichcould not be determined.Ethyl a-methyl-p-diethylsulphonsbutyrate, prepared in like manner,crystallises from water in plates, melts a t 79", and is only sparinglysoluble in cold, but readily in hot, water ; it is not acted on by coldalkalis, but when boiled therewith, it is completely decomposed.Ethyl a-ethyl-Pdithiopheny Ebutyrate, CMe( SPh),.C.HEt.COOEt, isobtained when hydrogen chloride is passed into a mixture of ethylethylacetoacetate and phenyl mercaptan.I t separates from akoholin large, transparent crystals, melts a t 70-71", and is readily solublein benzene, alcohol, and ether, but insoluble in water.E t h y l a-ethyl-&diphenyIsulphonebutyrate, C20H24S206, prepared byoxidising the preceding compound in the manner described above,separates from alcohol in crystals, melts a t 111", and is insoluble inwater, but readily soluble in alcohol, benzene, and ether ; when boiledwith potash, it yields only a trace of an acid. F. S. K.Indene and Cinnamene in Coal-tar. By G. KRAEMER andA. SPLLKER (Ber., 23,3276-3283 ; compare Abstr., 1890,496).-TheIiigher fractions of the light oils obtained from coal-tar contain ahydrocarbon of the composition CgH,, to which tho authors give theN --name indene, as it has the constitution C6HHd<gz2>CH.This compound is isolated in the following manner from the frac-tione boiling a t 176-182", the yield of the pure substance beingabout 20 per cent. of the crude oil employed :-A quantity of picricacid, sufficient to combine with the unsaturated compounds (deter-mined by titrating it portion of the oil with bromine), is dissolved inthe hot liqnid, the crystalline precipitate, which contains as impuri-ties all the naphthalene and a little cumarone, is treated with steam,and the indene in the distillate purified by precipitation with picricacid in toluene solution.The picrate is obtained in this way ingolden needles melting at 98" ; it decomposes slowly on exposure tothe ai:, but quickly when heated with water, and it explodes whenheated in the dry state.Indene is a oolourless oil of sp.gr. 1.04 at 15', which turns yellow-ish on keeping, the colour disappearing again on exposure to light ; itboils at 179*3-180*5" (cow.), is converted into a resinous compouni!(p-arindene) by concentrated sulphuric acid in benzene or etherealsolution, and into a very insoluble, infusible substance, which con-tains it large quantity of sulphur, by energetic treatment with concen-trated sulphuric acid. On oxidation with boiling 30 per cent. nitricacid, it yiclds phthalic acid. The dibromide, CgH8Br2, prepared bytreating the hydrocarbon with the theoretical quantity of bromine i206 ABSTRACTS OF CHEMICAL PAPERS.ethereal solution, forms transparent, prismatic crystals, melts a t43-45", and is readily soluble in all ordinary solvents except water andlight petroleum ; it readily undergoes spontaneous decomposition withevolution of hydrogen bromide and formation of a resinous substame.Indene hydroxybromide, C9H9Br0, is formed when the dibromide iswarmed with water or boiled with 10 per cent.alcohol ; it crystallisesin colourless needles, melts at 130-131", and is soluble in water andalcohol.Hydrindene, C9H,o, is obtained when indene is reduced with sodiumand alcohol ; i t is a colourless oil of sp. gr. 0.957 at 15", and boils at176-176-5" (COIY.). It forms a sulphonic acid, the salts and amide ofwhich are very like the corresponding derivatives of benzenesulphonicacid.Cinnamene can be isolated from coal-tar in the form of the crystd-line dibromide, C8H8Br2, by treating well-cooled, crude xylene withbromine and evaporating the solution.The red cdoration which is produced on dissolving impurenaphthalene in sulphuric acid is due to the presence of indene, andthe red coloration observed in the case of phenol is probably due toa similar cause.F. S. K.Synthesis of Indigo with Phenylglycocine. By K. HEUMANN(J. p r . Chem., [S], 42, 520).-The author claims priority as to themethod for the synthesis of indigo published by Lederer (this vol.,p. 75), he having already patented the method. Lederer is mistakenin supposing that indigo is left when the melt is dissolved in water ordilute sulphuric acid ; any that may be formed is only produced byoxidation by the a i r ; some substance like indigo-white is the actualproduct of the fusion, and oxidation is necessary to convert this intoindigo.A.G. B.Synthesis of Indigo from Anilidoacetic Acid. By A. BIEDER-MAEN and R. LEPETIT (Ber., 23, 3289-3291).-Aniline and chlor-acetic acid are mixed together in molecular proportions and fusedwith 3-4 parts of soda, together with sufficient water to form a,paste; as soon as the mass becomes orange-coloured, it is quicklycooled, dissolved in water, and the solution oxidised by means of acurrent of air ; indigo is at once deposited, the yield being 9.5 percent. It is probable that in the first instance anilidoacetic acid isformed ; two molecules then combine together with elimination ofwater and hydrogen.Indigo may also be obtained by the fusion ofanilidoacetic acid and sodium, the product being then oxidised withair as before. Indigo is directly prepared by the fusion of a mixtureof oxanilic acid and anilidoacetic acid in molecular proportion withexcess of soda ; the yield is a little less than with anilidoacetic acidalone. J. B. T.The author is further investigating the subject.Condensation of Cinnamene with Methylbenzene Deriva-tives. By G. KRAEMER and A. SPILKER (Bey., 23, 3169-3174).-Crude xylene containing cinnamene is treated with concentrated sulph-uric acid, when two layers of liquid are formed, the heavier of whicORQAMCI OHEMISTRY. 207contains sulphonic acids.The lighter oily portion is separated, washedwith soda, and distilled in a current of steam; the residue after fraction-ation in a vacuum, yields phenyZtolzLylperLtalze, CH2Ph*CH2*CH2*C6H4Me ;this is a colourless, viscid liquid which boils at 293-294", and has asp. gr. of 0.987 at 13". It is probable that in the first instancecinnamene and sulphuric acid combine to form an additive com-pound, which then condenses with xylene according to the equa-tion CH2Ph*CH2.SO4H + 2C6H*Me2 = CH2Ph*CH2*CH2*C6H4Me +~6~3Me2*S03H + H20. It is found that other methylbenzene deri-vatives condense with cinnamene in a similar manner, but benzeneitself does not react in this way. On passing the vaporised substancethrough heated tubes, hydrogen and methane are eliminated, andmethylanthracene (m.p. (LOO3) is formed ; the yield is 62.5 per cent.of the substance employed.Corresponding anthracene derivatives are obtained from the con-densation products of cinnamene and toluene, metaxylene, andpseudocumene respectively.The authors point out the bearing of their work on the theoriesregarding the formation of the higher boiling constituents of coal tar,and concinde with some polemical remarks on the Duismore processfor the manufacture of coal gas.Cinnamene Derivatives of Aromatic Hydrocarbons andtheir Conversion into Anthracene and Methylanthracenes.By G. KRAEMER, A. SPILKER, and P. EBERHARDT (Ber., 23, 3269-3276 ; compare preceding abstract) .-The compounds formed bythe condensation of cinnnamene with xylene are most probably ap-,and not ay-derivatires of propane as was previously supposed ; thisview would explain their ready transformation into anthracenederivatives.J.B. T.Hetctxylenecinnamene (al-l-phenylmetatol~~~ro~an~),CHMePh.CH2*C6H4Me,prepared by gradually adding concentrated sulphuric acid to amixture of metaxglene and cinnamene, is a colourless, feeblyfluorescent oil of sp. gr. 0.987 at 13" ; it boils a t 240" under a pressureof 110 mm., and at 311-312" (corr.), and is miscible with alcohol,ether, benzene, and light petroleum, but insoluble in water. Whenpassed through n red-hot tube, it is almost completely converted intomethylanthracene (m. p. 207").Parccxylenecinnamne (up-phenylmetatoluy $propane), C16H18, obtainedfrom paraxylene in like manner, boils at 302-303" (corr.), andresembles the preceding compound very closely.Ortho-xylenecinnnamene (up-phenylortho toluylpropane), C16H18, boilsat 316--317" (corr).Pseudocumenecinnamene (ap-pFuenyExylzJ~ro~a?~e),CBMePh*CH2*C6H3Me2,is obtained by the condensation of cinnamene with trimethylbenzene ;it boils a t 324" (corr.) and is readily converted into dimethyl-anthracene (m.p. 235").Toluenecinnamene (@-diphenylpropane), CHMePh*CH2Ph, pre208 ABSTRACTS OF CHEMIOAL PAPERS.pared from toluene in like manner, is a colourless liquid boiling at291-293" (corr.) ; when heated strongly, it yields only small quanti-ties of anthracene.Condensatioii products of benzene with cinnamene could not beobtained. I?. s.K.Condensation Products of Paranitrobenzyl Cyanide. By. P.REMSE (Rer., 23, 31334136) .-A compound of the constitutionCHPh:C(CN)*CsH4*N0, is formed when sodium ethoxide is graduallyadded to a mixture of paranitrobenzyl cyanide (1 mol.) and benzal-dehyde (1 mol.) until a blue coloration is produced. It crystallisesfrom alcohol in yellow needles, melts at 175-176", and is soluble inglacial acetic acid, benzene, and chloroform, but only sparingly inalcohol and ether, and insoluble in water.The condensation product obtained in like manner from orthonitro-benzaldehyde and parani trobcnzyl cyanide has the compositionCIsHgN3O4 ; it crystallises from glacial acetic acid in large, yellowishneedles, melts at 184-185", and is soluble in chloroform, benzene,alcohol, and ether, but insoluble in water.Metanitrobenzaldchgde and .paranitrobemy1 cyanide also condenseto form a compound of the composition Cl5H9N3OP, which crystallisesfrom alcohol in yellow needles, melts at 195", atid is soluble in mostordinary solvents except water.A compound of the constitution OMe*C6H4*CH:C ( CN)*C&T4*NO2can be obtained by treating anisaldehyde with paranitrobenzylcyanide as described above; it crystallises from alcohol in yellowneedles, melts at 165-166", and is soluble in ether, benzene, aridglacial acetic acid.The condensation product of cinnamaldehyde and paranitrobenzylcyanide has the constitution CHPh:CH*CH:C;( CN).C6H4*N02 ; i t crys-tallises from glacial acetic acid in yellow needles, melts a t 205-'206",and is soluble in benzene and chloroform, but more sparingly inalcohol and ether, and insoluble in water.F. S. K.Condensation of Unsaturated Hydrocarbons with Phenols.By W. KOENIGS (Bey., 23, 3144--3146).-When a mixturo of iso-amylene and phenol is treated with a mixture of concentrated sulph-uric acid (1 vol.) and glacial acetic acid (9 vols.) at the ordinarytemperature for 1 to 2 days, a considerable quantity of parisoamyl-phenol is formed,Hydrox.ydiphenyZethme, CHMePh*CsH4*OH, is obtained whencinnamene is treated with phenol under the same conditions as thosedescribed above ; the yield is about, 40 per cent. The reaction productis submitted to distillation with steam and, as soon as the whole ofthe phenol has passed over, the receiver is changed, the residueheated to 16G--170", and the hydroxydiphenylmethane distilled withsuperheated steam; the oily product is then converted into thebenzoj-1 derivative (m.p. 83") by Baumann's method, and the latter,after recrystallisation from alcohol, hydrolysed with alcoholic potash.The phenol obtained in this way solidifies on cooling, and forms asodium derivative which crptallises in colourless needlesORQANIC CHEMISTRY. 209Resorcinol seems to yield condensation products with amylene andwith cinnamene just as readily as phenol.Diphenyl Derivatives from Alkylquinola. By E. NOELTING andP. WERNER (Ber., 23,3246-3252) .-Diethyltolupuinol, C6H3Me( OEt),,can be obtained, together with the monethyl derivative, by heatingtoluquinol with ethyl bromide and sodium ethoxide in alcoholicsolution €or 5 to 6 hours a t 130-140"; the two compounds areseparated by treating the product with soda, in which the diethylderivative is insoluble.I t is a colourless liquid of sp. gr. 1.0134a t 15", boils at 247-249" (con.), and solidifies a t a low temperature,melting again at, 8-9" ; it is insoluble in water, but miscible withalcohol, ether, benzene, and chloroform in all proportions.Ethyltolupuinol, C,H,Me(OH)*OEt, is obtained when the alkalinefiltrate from the preceding compound is acidified and then extractedwith cold benzene; it crystallises from dilute alcohol in plates,me1 t,s at 116-1 17", and boils at 253-287".QcH2Me(OEt)*?c6H2Me( 0Et)eC.l'is formed when the diethyl derivative described above is dissolved intt mixture of dilute acetic acid and sulphuric acid and a concentratedsolution of sodium dichromate is g~adually added.It crystallises fromalcohol in greenish-black needles which melt at 139", and, whencrushed, give a reddish-brown powder; it, is precipitated from itssolution in boiling glacial acetic acid on the addition of water inreddish- brown flocks. It resembles very closely the cedriret-likeoxidation product of the dimethyltoluquinol (compare Nietzki,Abstr., 1883, 465), than which it is, however, much more readilysoluble in alcohol and glacial acetic acid.Dieth y ltetrhydroxyditolyl, OH.C6H2~Ie(OEt)*C6H2Me( OEt)*OH,prepared by reducing the preceding compoand with sulphurousanhydride in boiling alcoholic solution, crystallises from dilute alcoholin colourless needles, melts at 132-133", sublimes with partial de-composition, and readily oxidises on exposure to the air; it is onlysparingly soluble in water, but moderately easily in the ordinaryorganic solvents.Dimethoxyditolylquinone (compare Nietzki, loc.cit.) and diethoxy-ditolylquinone are reconverted into the corresponding qiiinols byphenylh ydrazine, phenylhydrazinesulphonic acid, and sodium hydro-gen sulphite; attempts to convert the quinols into derivatives ofdiphenylene oxide were unsuccessful.F. S. K.Diethoxydimethyldiphenylquinone (diethoxyditolylquinonej,Diacetyldimet hoxydiiol,ylquinol,OAc*C6H2Me ( Olfe)*C6H23/Ie( OMe)*OAc,is formed when dimethoxyditolylquinol is boiled with acetic an-hydride and sodium acetate ; it crystallises in colourless needles,melts a t 123", and is readily soluble in glacial acetic acid, boilingalcohol, and benzene, but insoluble in water and alkalis.Bromodimethylquinol, CaH3Br(ODle)2, can be obtained, togethe210 ABSTRACTS OF CHEMICAL PAF'ERS.with the dibromo-derivative and a liquid boiling at 246-260", whichis probably bromomethylquinol, by treating dimethylquinol withbromine (1 mol.) in cold glacial acetic acid solntion ; it is acolourless oil of sp.gr. 1.445 a t 15", boils at 262-265" (corr.),and is insoluble in water, but readily soluble in the ordinary organicsolvents. When treated with potassium dichromate and sulph-uric acid under suitable conditions, it yields a very small quan-tity of a cedriret-like compound, which, on reduction, is convertedi n to a colourless, crystalline leuco-compound. The nitro-compoundN0,*C6H2Br(OMe),, prepared by nitrating with acid of sp. gr.1.4in well-cooled acetic acid solution, cry stallises from glacial acetic acidin orange-yellow needles, and melts at 152-153". Warm nitricacid converts dibromodimethylquinol (Hahermann, Ber., 11, 1137)into FL nitro-compound, which crystallises in orange prisms and meltsa t 188".Dibromodimethylqninol, nitrobromodimethylquinol, nitrodibromo-dimethylquinol, and nitrodimethylquinol cannot be converted intocedriret-like compounds.Dimethyl23a9.axyZopuinoZ, C6H2Me,(OMe), [Me, : (OMe), = 1 : 4 : 2 : 51,prepared by heating paraxyloquinol with sodium methoxide andmethyl iodide in methyl alcoholic solution for 8-10 hours, crystal-lises from dilute alcohol in colourless plates, melts at 108", and issoluble in ether, but insoluble in water.Tbe correspondingdiethyl derivative melts a t 111-112", and not at 105-106", as statedby Stadel and Holz.Diethylmetaxy ZoquinoZ is a colourless oil boiling at 240-249".The corresponding ortho-compound, C6H2Me2(0Et), [ Me2 : (OEt), *=1 : 2 : 3 : 41, forms colourless plates, melts at 68-69', and is rea.dilysoluble in alcohol, benzene, ether, &c., but insoluble in water.Cedriret-like oxidation products cannot be obtained from the xylo-quinol derivatives described above.Orthomethylbenzidine. By R. HIRSCH (Ber., 23, 3222-3226).-0rthomethylbenzidine can be prepared in the following manner(compare D.R.-P. 34112) :-A solution of nitrobenzene (1 pazt) andorthonitrotoluene (4 parts) in alcohol (5 parts) is boiled with sodiumhydroxide (about 0.5 part) and zinc-dust added until the solutionbecomes grey or bright yellow ; the alcohol is then evaporated, theresidue carefully treated with a quantity of hydrochloric acid justsuflicient to dissolve the zinc hydroxide, but nob the organic bases,and the solution filtered. The residue, which consists principally ofhydrazobenzene and its homologues, is then dissolved in warmdilute hydrochloric acid to convert these compounds into the cor-responding benzidines, the excess of acid expelled from the filteredsolution, the bases precipitated with sodium sulphate, and the sulph-ates decomposed with sodium carbonate.The mixture of the threebases (benzi dine, ortho toluidine, and orthome th ylben zidine) obtainedin this way is repeatedly extracted with boiling water, and the com-bined extracts carefully treated with dilute sulphuric acid to precipi-tate the sulphates of benzidine and orthomethylbenzidine ; these saltsare decomposed, and the mixture of bases again extracted (5 times)F. S. KORQANIO CHEMISTRY. 211with boiling water (20 parts), when pure orthomethylbenzidine isdeposited from the first two extracts, on cooling, in lustrous platesmelting a t 115". I t melts a t about 90" under water, forms a diacetylderivative melting a t 310°, and a benzylidene derivative, whichcrystallises from alcohol in yellow plates, and melts at 217".F.S. E.Diphenyl Bases. By E. NOELTING and P. WERNER (Ber., 23,3252-3266) .--DitoZyline 11 ydrochloride, CI~H16N2,2HCl, is obtained,together with tolidine hydrochloride and other compounds, whenorthohydrazotoluene is treated with warm concentrated hydrochloricacid (4 parts). The solution is heated to boiling, then allowed tocool, the tolidine hydrochloride and a'zotoluene separated by filtra-fion, and the filtrate concentrated by evaporation ; after filteringagain, the solation is rendered alkaline, extracted with ether, theether evaporated, and the residue heated at 250" until free fromorthotoluidine; it is then dissolved in hydrochloric acid, the di-tolyline reprecipitated from the filtered solution, extracted with ether,and converted into the hydrochloride by passing hydrogen chlorideinto the dried ethereal solution.This salt crystallises in colourlessneedles, and is very readily soluble in water, but only sparingly inhydrochloric acid ; in its aqueous solutions, bromine-water produces aslight, dirty-green coloration which changes to violet. Tbe free baseis a colourless, flocculent compound which rapidly oxidises on expo-sure to the air. The sulphate is very readily soluble. The colouringmatters obtained from ditolyline do not dye cotton fibre.Parabromazobenzene (m. p. 82O), identical with the compoundobtained by Janovsky and Erb (Abst'r., 1887, 478) by bromincltingazobenzene, can be prepared from amidoazobenzene by Sandmeyer'smethod ; when treated with st,annons chloride in alcoholic solution, itis converted into bromodiphenyline (bromobenzidine) .Pariodarobenzene, C12HBN21, prepared in like manner, crystallisesfrom alcohol in yellowish-brown needles, melts a t lOY, and is solublein ether and benzene, but insoluble in water.The correspondinghydrazo-compound crystallises in colourless needles melting atIododiphenyline hydrochloride, prepared by treating the azo-com-pound with stannous chloride in alcoholic solution, crystallises incolourless needles, and is readily soluble in water, but o d y sparinglyin concenti-ted hydrochloric acid. Bromo- and iodo-diphenylineyield coloured azo-compounds which impart to nnmordanted cottononly a very slight coloration.When metadiiodazobenzene is treated with hot concentrated hydro-chloric acid, it yields iodazobenzene and large quantities of benzidine.Azobenzencparasulphonic acid is converted into hydrazobenzene-parasulphonic acid by hydrogen sulphide in ammoniacal solution, andnot into benzidinesulphonic acid as stated by Griess (AnnaEen, 154,213) ; on treating the ammoniacal solution with hydrochloric acid,benzidine sulphate is precipitated.Ethoxpazobenzene, N P h 3 *C6H4*OEt, is converted into a base ofthe constitution NH,*C,H,*C,H,( OEt)*NH,, when it is treated with105-106*212 ABSTRACTS OF OHEMICAL PAPERS.the theoretical quan tit7 of staxtnous chloride and hFdrochloric acid inalcobolic solution ; the colouring matters obtained from this base donot dye nnmordanted cotton.Orthotozyzazophenol, C6H4Me*N:N*C6H4*OH, prepared by treatingdiaaorthotolyl chloride (1 mol.) with an alkaline solution of phenol(1 mol.) and precipitating the product with an acid, crystallises fromft mixture of benzene and light petroleum in dark-red or orange-yellowplates, melts at 102-103", and is very readily solizble in alcohol,ether, benzene, and alcohol, but only sparingly in water and lightpetroleum.Orthotolyldisuxophenol, ( C6H4Me*N,),c6H3*OH, is obtained when alarger quantity (2 mols.) of the diazochloride is employed in the abovereaction ; it crystallises from alcoholic chloroform in slender, brownneedles, melts at 146", and is readily soluble in chloroform, butinsoluble in water.OrthotoZyZazophenetoZ, C6H4Me*N,*C6H4*OEt, prepared by treatingthe phenol with sodium ethoxide and ethyl bromide, crystallises fromalcohol in orange plates, melts at 53", and is only sparingly solublein water, but readily in alcohol, ether, benzene, and chloroform;stannous chloride, in alcoholic solution, converts it into a diphenylbase from which fast dyes cannot be obtained.Paratolyluzophenetoil, C16H16N20, crystalliseR from alcohol in large,golden plates, melts at 121-12Z0, and is insoluble in water andalcohol, but moderately easily soluble in cold alcohol, and readily inboiling alcohol, chloroform, &c.Purafoly Zhydrazophenetoil, CIJHleN20, prepared by reducing thepreceding compound with hydrogen sulphide in ammoniacal alcoholicsolution, crystallises in colourless needles, and readily oxidises onexposure to the air; it is insoluble in water, but readily soluble inboiling alcohol.Acids do not convert it into a diphenyl base, butdecompose it into toluidine and amidophenetoil.Ph en yluzort hocresetoi'E, NPh: N- C6H3Me.0E t, prepared from phenyl-azorthocresol, crystallises from alcohol in slender, orange needles orprisms, melts at 59", and is soluble in benzene and ether, but in-soluble in water. The corresponding hydrazo-compound, C1,HI6N2O,crystallises in colourless plntes, melts at 76", and is readily soluble inhot alcohol, but insoluble in water; it readily oxidises on exposureto the air, and it is decomposed by hydrochloric acid yielding adiphenyl base from which fast azo-dyes cannot be obtained.2 1 1 42 1 1 3 4O?.thotoZyZazo?.thocre~oZ, C6H4Me*N:N*C6H3Me.0H, crystallises fromalcohol in red prisms, melts a t 132", and is soluble in benzene andether, but insoluble in water.The hydraso-compound, C16H20N20, isa colourless, crystalline substance which melts at 7d0, and readilyoxidises on exposure to the air; the diphenyl base, produced fromthe hydrazo-compound by intramolecular change under the influenceof hydrochloric acid, does not yield any colouriiig matters which dyeunmordanted cotton fibre.OrthotoZy Zdisazorthocresol, ( C6H,MeDN,)",6H2Me.0H, crystallises inslender, brown needles, melts at 148.5", and is insoluble in waterORGANIC CEEMISTRT. 213but soluble in alcohol, benzene, chloroform, and alcoholic soda. Theethyl derivative, .CySH?4N20?, prepared by treating the phenol withsodium ethoxide and ethyl bromide, crystallises in golden needles,melts at 102', and is soluble in cbloroforrn, benzene, and ether, butinsoluble in water and alkalis.4 1 1 3 4Paratoly lazo r t?wcresol, C6H4M e*N:NC6H3Me*0 H, forms orangecrystals, melts at 163", nndis insoluble in water, but readily soluble inalcohol, ether, chloroform, and alkalis. The ethyl derivative,Cl6HI8N2O, crystallises iu orange needles, melts at 73-74", and i sreadily soluble in alcohol, ether, and benzene, but insoluble in water.The h y drazo-compound, C16H2,JV20, prepared by reducing thc ethylderivative, crystallises in colourless needles, melts at 87", and i.ireadily soluble in alcohol, but insoluble in water ; it readily oxidiseson exposure to the air, and when treated with hydrochloric acid itdoes not yield a diphenyl base, but is decomposed into an azo-com-pound and an amido-compound.Pnratol~ldisazorthocresok; C21HwN40, forms small, prismatic crystals,melts at 164*5", and is insoluble in water, and only sparingly 8olublein alcohol.The ethyl derivative, C,H2,N40, crystallises i n yellow,microscopic needles, melts at 107-108", and is soluble in hat ether,benzene, and chloroform, but insoluble in water and alkalis.PherLylazoparaci-esetoi'l, NPh:N*C6H3Me*OE t, prepared by heatingthe corresponding phenol with ethyl iodide and sodium ethoxide iiJalcoholic solution, crystallises from alcohol iu red plates, melts a t48", aud is soluble in ether and benzene, but insoluble in water andalkalis.The hydruzo-compound, Cl,Hl8N2O, crystallises in colourlessneedles, melts at 105", and is soluble in alcohol, benzene, &c., butlinsoluble in water.Metl~ylethozy benzidiite, NH2*C6H4*C6H2Me( OEt)*NH,, is formedwhen phenylhydrazoparacresetojil is treated with moderately con-centrated hydrochloric acid, and the hydrochloride produced decom-posed with ammonia. I t crystallises from light petroleum in slender,colourless needles, melts at 107", and is very sparingly soluble inwater, but readily in ether and alcohol ; its azo-derivatives dye un-mordanted cotton, but not so readily as the corresponding benzidinederivatives.Orthototylazo27aracresol, C14HllN20, forms red needles witb a bluereflex, melts at 98", and is soluble in alcohol and chloroform, butinsoluble in water and dilute alkalis.The ethyl derivative, C16H18N20,crystallises in red prisms with a blue reflex, melts at 82-83", andresembles the preceding compound in its behaviour with solvents.The hydrazo-compound, C16HPON20, prepared by reducing the ethylderivative with hydrogen sulp hide in ammoniacal alcoholic solution,crystallises in colourless plates, melts at 138", and is insoluble inwater, but soluble in alcohol.DimethZ!lethoxybeizzidi.ne, NH2*CI,H3Me*C6H3Me(OEt).NH2, is formed,together with a small quantity of the azo-compound, when thehydrazo-compound just described is treated with hot dilute sulph-uric acid; it crystallises from dilute alcohol in colourless needles,melts at 75", and is readily goluble in alcohol, ether, and chloroform214 ABSTRAOTS OF OHEMIUAL PAPERS.but only sparingly in water; it yields coloured azo-compounds whichdye unmordanted cotton fibre.Paratolylazoparacresetoil, C lBH18N20, crystallises from alcohol in redneedles, melts a t 171", and is readily soluble in ether and benzene.The corresponding hydq*azo-compound, Cl,&N20, forms colourlessneedles, melts at 153O, and is insoluble in water, but soluble in alcohol,benzene, &c.; when treated with hydrochloric acid, it yields a basewhich is analogous to diphenyline, and from which azo-compounds,having only a very feeble colouring power, are obtained.Orthonitrophenylcinnamic Acid and Phenylhydrocarbo-stpil. By A.OGLIALORO and E. ROSINI (Gaxsetta, 20, 396-402).-0rthonitrophenylcilznainic acid, CI5HllNO4, is prepared by heating amixture of dry sodium phenylacetate (1 mol.), orthonitrobenzaldehyde(1 mol.), and acetic anhydride (4 mols.) for six hours at 160". Theimpure acid obtained is partially purified and then converted intothe barium salt, ( C15HlIN04)2Ba,5H20, which crystallises i n tufts ofpale-yellow needles, The pure acid crystallises in small, pale-yellowprisms, begins to soften at 292", and melts a t 195-196". It issparingly soluble in water, but freely in hot alcohol ; it also dissolvesi n ether and in benzene. From some of the alcoholic solutionsobtained iu the preparation of this acid, another barium salt may beobtained containing 8 mols.H20.On reducing a diluted alcoholic solution of the acid with sodiumamalgam, the product consists of a mixture of several substanceswhich may be separated by fractional solution in water, dilute andabsolute alcohol. The portion extracted by dilute alcohol crystallisesin yellowish needles, melts at 173-174", and has the composition ofpl~enylhydrocarbostyril, C15H,,N0. It is very soluble in hot alcohol,moderately in chloroform and benzene, but only sparingly i n etherand light petroleum. Attempts made to prepare hydrophenylindolefrom thi5 compound by fusing it with potash were unsuccessful.Naphthyl Methyl Ketones. By A. CLAUS and H. TERSTEEGEN( J . pr. Chem. [23, 42, 517--519).-Thc crystals obtained by pro-longed cooling of a-naphthyl methyl ketone below 0" (Abstr., 1887,272) are /3-naphthyl methyl ketone.P-Naphthy 1 methyl ketone is best obtained by acetylising naphthalenein the cold and with exclusion of direct sunlight ; the process is slowand the yield poor ; it is freed from the a-ketone by crystallisationand pressure ; it sublimes with steam in small, transparent leaflets,melts at 51-5-32" (uncorr.), boils undecomposed at 301-303"(uncorr.), and dissolves freely in alcohol, ether, and chloroform.The oxirne forms colourless crystals which melt at 145" (uncorr.), andthe acetyl compound of this melts a t 134".The phenylhydraside meltsat 171 " (uncorr.).a-Naphthyl methyl acetoxime melts at 114O, and a-napbthyl methylketone hydrazide at 146" (uncorr. ; compare Absitr., 1887, 271)./3-NupIhth ylglyox~~lic (P-naphthoy Zformic) a d , obtained by oxidisingthe ketone with potassium permanganate, is a greenish-yellow oilwhich slowly crystallises and melts a t 75' (?); it is pretty freelyF.S. K.S. B. A. AORGANIC CHEMISTRY. 215soluble in water; the barium salt is anhydrous; the potassium andcai'cium salts crystallise with 1 mol. H20. By reduction, it yieldsp+mphthylgZycolZic acid, which crystallises in small needles, snblimes inlong needles, and melts at 176" (uncorr.) : it is little soluble in water;its barium, salt is auhydrous. a-Naphthylglycollic acid melts at163" (uncorr.).p-NaphthyEacetic acid is obtained by reducing the glycollic acid withhydriodic acid ; it crystallises in lustrous, silvery leaflets which meltat 142" (uncorr.) ; its nmide melts at 200" (uncorr.).Naphthasultonsulphonic Acids and a-Naphtholsulphon-amidosulphonic Acids.Rg A. BERNTHSEN (Ber., 23, 3085-3096).-When naphthasultone, the " naphtholsulphonic acid-S." of theSchollkopf Aniline and Chemical Co.'s Germ. Pat. 40571, is sulphon-ated with concentrated sulphuric acid, and the melt poured intowater, a-naphthol-b-disulphonic acid (" S. acid " [OH : SO,H : S03H= 1 : 4 : 1'1) is obtained (Schiillkopf Go., Zoc. cit.). The author findsthat this acid is not the immediate productl of sulphonation, butresults from hydration of the initially-formed naphthasultonsulphonicacid-8.Naphthasultomulplphonic acid 6 is obtained as sodium salt when1 part of naphthasiiltone is gradually stirred into 8 parts of cooled5 per cent, anhydrosulphuric acid, left for about an hour until aportion is found to be completely soluble in water, and then stirredinto an externally-cooled mixture of 12 parts of ice and 16 parts ofsaturated brine.The sodium salt, I >CloH,*S03Na + 3H20, whichseparates aftler some time, crystallises in thin scales or tables, ismuch more soluble in water than the sodium salt of nnphtha-snltonsnlphonic acid E (Abstr., 1890, 387), and in aqueous solutiongives no colour reaction with ferric chloride. On treatment withalkalis or alkaline carbonates, or by boiling with dilute ( 5 per cent.)snlphuric acid, or prolonged boiling with water, it is converted intosodium 1 : 4 : 1'-a-naphtholdisulphonate, whilst the latter, on treat-ment with suitable dehydrating agents, such as concentrated sulph-uric acid at 1 OO", yields the naphthssultonsulphonate. The solutionin concentrated ammonia, on addition of hydrochloric acidr gives aprecipitate of the sodium salt of naphtholsulphonafmidosulphomc acid 6,OH.CloH5(S02*NH2)*S03Na + 2H20, which crystallises in rhomb-likescales or plates, resembles the c-compound (Zoc.cit.) in properties,and forms similar azo-dyes.The azo-dyes obtained from the salts of naphtholsnlphonamido-sulphonic acid E give much bluer or redder shades, are less solublein water, and crys tallise better than those from a-naph tholdisulphonicacid E . The dyes formed by the action of diazotised xylidine,snaphthylamine, and benzidine give respectively very blue-claret,wine-red, and bluish-violet shades, are scarcely affected by acids, and,on reduction with stannous chloride and hydrochloric acid, yield thesodium hydrogen salt of an amidonaphthoZdisulphonic acid (probablyThe azo-dyes obtained with diazotised xylidine dissolve in concen-A. G.B.0-so,OH :NHz: S03H: S03H = 1 : 2 : 3: 1')216 ABSTRACTS OF OAEMICAL PAPERS,trated aulphuric acid with a magenta colour, wbich, after a shorttime, changes to yellow ; a corresponding colour-change occurs alsowith the other dyes named, and is due to hydrolysis of the SO,.NH,radicle with the production of ammonia and the correspondingazo-colouring matters derived from a-naphtholdisulphonic acid C.A more remarkable change is that brought about by alkalis.The bluish-red azo-dye obtained with diazotised xylidine, whenwarmed for a short time with alkalis or alkaline carbonates, changescolour to a bright reddish-yellow, and a corresponding change toyellow or red shades ensues under like conditions with the other dyestufls named.The azo-dyes formed can be salted out from solution,and, unlike the parent colours, are very sensitive towards acids,changing coloor to blue or violet, and thus resemble many of theamidoazo-dyes. Moreover, they crystallise well, are resy soluble i nwater containing some alkali, and i n an acid bath produce shades onwoolwhich are distinctly bluer than those from the parent dyes. Onreduction with stamous chloride and hydrochloric acid, the " altered "xylidine dye, which gives a cochineal shade on wool in an acid bath,yields a sparingly soluble compound, C,oH8N2S205 + 2 H20, crystallis-ing in long, flat needles. This compound dissolves readily in alkalis,is precipitated from the alkaline solutions by acids, and by prolongedboiling with phenanthrayuinol in acetic acid solution, forms anazine.I t is a derivative of, but not identical with, 1 : 2 : 3 : 1 ' -orthonaphthylenediaminedisulphonic acid, and is regarded by theauthor as the anhydride, r" >CloliL(NH,)*S03H, of this componnd,the action of alkalis on the azo-dyes obtained from naphtholsulphon-atnidosulphonic acid 6 being represented thus :-i s 0 2NH2*S02~C,nH4(OH)(S03H)*N2.R = yH >CloH,( SO,H)*N,-R + H20.. SO2Sodium hydrogen 1 : 2 : 3 : l'-orthona~hth~lene:diaminedisulphon~te,S0,H.CI,,H,(NH,),*S03Na + 3H20, crystallises in small needles, ismuch more soluble than tlie salt of the anhydride, and forms anDinaphthyl Picrates.By R. WEGSCHEIDER (Ber., 23, 3199-3201).-Of the dinaphthy 1 picrates, only the aa-compound has pre-viously been prepared. aS-Dinaphthyl picrate, CmH,, + C6H3N3O7,may be readily obtained by mixing boiling alcoholic solutions of thehydrocarbon and picric acid, and crystallises in golden-yellow needlesmelting a t 155 -156". For the preparation of PP-dinaphthyl picraie,the constituents must be dissolved in boiling benzene; the saltseparates out on cooling in microscopic, orange prisms, which havethe composition CmH11,2C6H3N307. The author. regards the hydro-carbon obtained by Bischoff, by the action of methyl chloride onnaphthalene in presence of aluminium chloride (Abstr., 1890, 1145),as probably identical with /3p-dinaphthyl.By A.PIcmT and S. ERL~CH (Chsm. Centr., 1890,ii, 350-351 ; from Arch. sci. plzys. ntct., GenBze [ 3 ] , 23, 552).-Thenziue on treatment with phenanthraquinone. w. P. w.H. G. C.ChrysidinesORQANIC CHEMISTRY. 217authors have pursued the investigations already commenced byPictet (Abutr., 1890, 390), and have studied the action of heat onthe two benzylidenenaphthylamines, which are obtained by heatingbenxaldehyde with the two naphthylamines. By passing the vapour9f these compounds through a red-hot tube, two new bases, of theformula CnHIIN, are obtained, the constitutional forinula being,probably, v6 These bases, which correspond with the phen-anthridines, and are sirni1a.r to them in their properties, are, there-fore, a- and ,9-chrysidine. Their alkaline solutions have a bluefluorescence, they form yellow salts with acids, and the solutions ofthe latter have a green fluorescence.Reduction with tin and hydro-chloric acid converts them into secondary bases. a-Chrysidine meltsat 108", P-chrysidine at 126".CloH6.N *J. W. L.Turpentine. By R. G. DUNWODY (Chern. Ceutr., 1890, ii, 241-242 ;from Amer. J. Pharm., June, l890).--The author finds ver.y consider-able variations in the specific rotatory power and the specific gravityof oil of turpentine. I n 1'2 samples, the former varied from 2.60" to36.64" in a 200 mm.tube, before rectification, and from 3.90" to33-62" after rectificatioii. The specific gr;trit.y at 15" varied fromWe56 to 0.676 before, and from 0.851 to 0.873 after rectification. Theoils commenced to boil at 155-159", and the last portions distilledbetween 165" and 170" ; the principal part distilled at 160-162". Theauthor has not found Allen's test with caitor-oil, for the detection ofpetroleum in turpentine, of much value, since an admixture of65 per cent. OE the former escaped detection by means of this test.I n pure glacial acetic acid both petroleum and turpentine are perfectlymiscible, but of acetic acid containing 1 per cent. of water, more andmore is required for complete solution, the greater the proportion ofpetroleum which is present, as is shown in the following table :-Petrcleum ...........1 2 3 4 5 7 8 C.C.Oil of turpentiue.. .... 9 8 7 6 5 3 2 ,,Acetic acid + 1 percentR,O .......... 40 GO 80 110 150 230 270 ,@From the pitch remaining in the retort, after tbe distillation of theturpentine, the author has separated, with light petroleum, two wellciytsllised substances, the one being abietic acid, melting at 131",:tnd the other, II new substance, having the compositiori 72-72-8 percent. carbon, 9-7.5-9.50 per cent. hydrogen, 18*25-17.70 per cent.oxygen ; arid melting at 1'25-1'26". J. W. L.Terpenes and Ethereal Oils. B y 0. WALLACH (AnnuZen, 259,309--324).--Phole glycol dincetate, CloH160( OAc)*, is formed, togetherwith pinole and pinole glycol, when pinole dibromide is warmed withsodium or silver acetate i n glacial acetic acid solution ; the productis Furified by fractional distillation under a pressure of 13 mm.Itcryst,allises well from wa-ter, and melts at 97-98".Pinoh ylycol, C1&60(OH)2, can be prepared by boiling thsVOL. LX. 218 ABSTRAOTS OF OHEMIOAL PAPERS.diacetate with very dilute sulphnrio acid, or by treating the bromidewith freshly precipit-ated silver oxide; i t cryRtttllises from light petro-leum in needles, melts at 125", is very readily soluble in chloroform,and is converted into the diacetate by boiling acetic anhydride.Piitole hydrate, CIOHL8O2, is obtained, together with cymene, whena well-cooled glacial acetic acid solution of crude pinole is saturatedwith hydrogen bromide, and then shaken with verp dilute soda in t h ecold, in ordcr to decompose the additive product ; after separatingthe cymene bp distilling with steam, the hydrate is extracted fronithe alkaline solution by shaking with ether.Pinole hydrate crystnl-lises in needles or plates, melts at 13l0, and is moderately easilySohbk! (1 in 30 at 1.5") i n water, but more readily in alcohol ; i tcrystallises unchanged from boiling glscivl acetic acid, but whenwarmed with dilute sulphuric acid, it is converted into pure pinole.It is identical with the crystalline substance which was formed, aswas first observed by Sobrero (Annulerr, 80, 106), when oil of tur-pentine is exposed to direct sunlight in presence of oxygen (compareArmstrong, Proc., 1!390, 99).Piriole, on oxidation with potassiunipernisnpanate, yields terebic acid and considerable quantities OFoxnlic acid and carbonic acid ; pinole hydrate, under the same condi-tions, gives terpetiylic acid, carbonic acid, and oxalic acid ; pinoleglycol seems to give the same oxidation products as the hydrate.Pure pinole is easily prepared by boiling a benzene solution ofpinole dibromide with the theoretical quantity of sodium, i n the formbf fine wire, until decomposition is complete ; the filtered solution isevaporated, and the residual pinole puritied by fractional distillatioil.PinoZe tribromide, Cl,,H150Br3, is obtaiiied in small quantities inthe preparation of the dibromide from crude piiiole ; i t crystallisesfroni ethyl acetate in needles, and melts at 160" with decomposition.Fenchole, an Isomcride of Camphor.By 0. WALLACH and F.HARTMANN (AnnuZen, 2 5 9, 384-m) .-A liquid of tjp. gr. 0.934,possessing a strong odour of camplior, and boiling at 190-1%", cmbe isolated from oil of fennel ; it has the compositiori CI,,H160, and isnamed by the authors fenchobe. The whole chemical behaviour OFfenahole is that of a position-isorueride of camphor, as will be 8eenfroni the experiments described below ; it combines with bromine illwell-cooled light petroleum solution, yielding a bright-red, crystalline,unstable additive product, which is reconverted into fencliole ontreat,ment with soda ; it also yields with sodium, a solid cornpuulld,which seems to be convertdd into an acid by carbonic anhydride.Fenchole oxime, CIOHIR:N*OH, crystallises from nlcobol in slenderneedles, and from ethyl acetate in well-detined crystals, a : b : c =1.3047 : 1 : 0.55259, fl = 76" 'LO', which melt at 148-149", and arevery like those of camphor oxime in appenrana The hyclrochtoridc,Cl0H,,NO,HC1, melfs at 118--119O, and is decomposed by alcohol.The anhydride, CIOHILLN, prepared by dissolving the oxime in dilutesulyhuric acid, is a colourless liquid, boiling at 217-219" ; it call bedisnnguished from tbe anhydride of camphor oxime by the fact thatj t yields tt crystalline hydrobromide, CloH,,N,HBr, which is, however,very unstable.I?.S. ElORGAX'IC CHEJIISTRY. 219Isqfenohle oxime, CioH17N0, is formed when fennhole oximeanbydride is boiled with alcoholic potash for five to six hours; itcrystallises from alcohol in plates, melts at 113-114', and is readilysoluble in alcohol, ether, and acids, and moderately soluble in water.Fencholenic acid, C,H,,O,, iR obtained when isofenchole oxime isboiled with alcoholic potash for four days, but some of the oximeremains unchanged.It is an almost colout'lt~ss liquid, boils a t257--ft6Oo, and forms a sparingly soluble silver salt and a deliquescentammonium salt. El. S. K.Rose-oil. By V. MARKOVNIEOFF (Bey., 23, 3191) .-Rose-oil con-sists, as is well known, of liquid constituents and stearoptene. Thelatter melts a t .36.5O, and has all the properties OE a paraffin; itis perfectly inodorous, and k, thsrefore, of no value with regard tothe quality of the oil.The liquid Fortion or eleoptene boils withinnarrow limits, and appears to be a mixture of two substances, CloH,oOand CloH,,O, one of which is an alcohol, and forms the chief con-st ituent of rose-oil. H. G. C.9-Methylpyridine. By C. SroEHR (Rer., 23, 3151--3157).-l'heproduct obtained by the distillation of strychnine or of brucine is uothomogeneous. Alter purification, however, it yields p-methyl-pyridine, which boils at 142-143", and is identical with the synthe-tical product from glycerol, acekamide, and phosphoric anhydride.The mercurochloride melts a t 145---146", the platitiosochloride a t257-257*5", and the platinochloride at 201-202". Ladenburg(Abstr., 1890, 1432) gives three melting points for this last compound(from syuthetical /3-methylpyriditie), which range between 191" itlid198' and it is suggested that he had to deal with varying mixtures ofthe two platinum compounds.Ladenburg's theory of the constitutionof pyridine, so far as it is based on the existence of two p-methylderivatives, is thus proved to be erroneous. J. B. T.A New Class of Acridines: Phenylcarbazacridine. By D.B~ZZA I ~ R I (Gazzettcz, 20, 407-41 7).--Yhenylcarbazacridine, CuH,,N,is formed when a mixture of pure carbazole (20 grams) with benzoicacid (15 grams) and fused zinc chloride (45 grams) is heated forfive hours at 120-130", a:id the alcoholic solution of the productprecipitated with strong aqueous ammonia. The product when purecrystallises fyom alcohol in minute, white scales, turna green onheating to 150", and melts at 186.5".It dissolves in most of theordinary solvents, hut oiily sparitiglg in absolute alcohol, and not a t ;dli n water. J t crystallises frotn benzene in groups of rectangular laminae,and from xylene in peculiar, spherical tufts. With acetic acid, itforms an intense green solution, which is dichroic when conceatrated(0.25 per cent.), appearing emerald-green by reflected, and garnet-red by transmitted light. It is not affected by boiling with alkalis,and only partially decomposed by heating with soda-lime. I t is dis-solved by benzoic: chloride. but not further affected.The methigdide, CI9HIlN,MeI, prepared by heating the base withrnetbyl iodide at 140", crystallises in brownish-yellow plates.soluble i nn 9 220 ABSTRACTS OF CEHMIOAL PAPERS.alcohol and acetic acid. From these solutionn, the base is reprecipitrttedon the addition oE water. Boiling alcoholic potash decomposes itinto the free base, methyl alcohol, arid potassium iodide. On gentlyheating, i t is similarly split up into the base and methyl iodide.The hydrochloride forms e merald-green scdes, soluble in acetic acidand in alcohol, bnt not i n water. It dissociates even in alcoholicsolution, and is only stable in presence of an exccss of free hydro-chloric acid. It is completely decomposed by boiling water. Thesrclphate forms n green, shining mass, soluble in acetic acid and inalcohol, but not in water. I t is gradually decomposed by boilingwater, and the alcoholic solution is unshble in the absence of freefiulph-uric acid.The picrate and hydriodide crgstrtllise in greenplates decomposed by water, atid forming unstable alcoholic solu-tions. Thc chromute crystallises in scales decomposed by water andalcohol.Benzoylcarbazole, C,9H13N0, is obtained by heating carbazole withbenzoic anhydride at 240'. It cqstalliseu from alcohol in white,acicular prisms, melts at 95.5", dissolves in benzene, ether, &c., butonly sparingly in alcohol. It i s decomposed by alcoholic potash intoc+rbazole and beiizoic acid. Its formation and decompositioii, togetlerwith the analogy to ncetylcarbazole, estitblish for this corn pound theconstitution C,,H,NBz. On heating it with ziiic chloride at 130-150",7, he nv 1 carbazacr id in e is formed.prepared by reducing phenylcarbazacridine with zinc-dust, crystallisesi n yellowish 1e:tves which turn brown and melt at 172", and dissolvesin acetic acid, alcohol, and ether, but not in water.It reduces silvernitrate in alcoholic solution, and picric acid i.mparts to it an orangecoloration. It has no basic properties, but acids and potassiiiru per-inanganate convert it into phenylcarbazacridirre.When carbazole is heated with benzoic acid and zinc chloride at1 50-160°, there is formed, besides the acridine described and resinousproducts, a compound of unknown constitution, which crystalliseafrom boiling alcohol in tables which melt at 210". and are stainedFellow by picric acid. At 200-21 O", no phenylcarbazacridine isformed, the products consisting mainly of resins.At 280", the massis gradually carbonised. S. B. A. A.Thiazoles. By K. HUBACHER (Annulen, 259, 2.18-253 ; compareHnntzsch, Abstr., 1889,413, 723, and 1890,1238) .-ThThiopropionamide,C3H:NS, can be prepared by treating propiooamide with phosphoruspentasulphide, as described by Hantzsch (loc. cit.) in the case ofthiacetamide; the yield is, at the most, 10 per cent. of the amideemployed. It crystallises in yellowish plates, melts at 42-43', andis very readily soluble in benzene, but only spaiingly in et.hei*, aloo-hol. and water. Ix- Met18 y 1- p e t h y lthiazole, RHAS>CEt, is obtained when thiopropi-CMe-Nonamide is treated with chlora-etone in alcoholic solution, and thORQANIC UHIEIUISTRY.221product decomposed with soda. I t is a colourless liquid, boils a t1.59*5-160" (i28.5 mm.), has a n odour of pjridine, an6 is misciblewith alcohol and ether. but is only sparingly soluhle in cold water.The plntinochloride, ( CeHgNS)?, H ,PtCl,, forms small, y ellowish-redcrystals, and melts a t 177" with decompositioii.a- t'heny 2-pet11 y l f himole, CllH ,,NS, is f orni ed when thiopropion-amide is treated i t h bromncetophenone in like manner ; the productis dissolved in dilute hydrobromic acid, and the crystalliiie hydro-bromide, which is deposited from the filtered solution, decomposedwith soda. The base is a colonrless oil, of agreeable odour, boils at295" (729 mm.), and is insoluble in water, but miscible with alcoholand ether.The platinochloride, (C,,H,,NS),,HzPtC16, fcrms light-yellow, microscopic crystals, and melts a t 128-129" with decomposi-ti o n . The h ydrohromide, C I ,H rlNS, HB r, c r p tal lises in col our1 essneedles, melts at 68-70", and is decomposed by cold water or whenkept over sclphuric acid.p- PheiyltiriazoZe, C9H,NS, is formed when thiobenxamide is heatedat 100" lor several hours with dichlorether and sodium metate i nalcoholic solution ; the dark, resirroue product is extracted withdilute hydrochIoric acid, the base liberated with soda, and distilled.I t is a colourless oil boiling at 266-268" (73'2 mm.). The hydro-ch loridp, C9H,NS,HC1 + '2H20, crystallises from dilute hydrochloricacid i n plates, melts at 61-62', loses its water over sulphuric acid,and is immediately decomposed by water.The plafinochhride,(C9HiNS),.H2PtCI, + 'LH20, is a yellow, crystalline compound melt-i n g a t 173-17.5" with decomposition; it loses its water at, 110".The picrate crystallises in yellow needles, melts at 124-125", and isonly very sparingly soluble in water, but readily in hot alcohol.a-MethyZ-ppheny lthiuzole, CloH9N8, prepared by treating thiobenz-amide with chloracetone i n alcoholic soluiion, is an oil boiling at277-5-278' (724 mm.).ap- Diphenylthiuzole, CI5HlINS, obtained from thiobenzamide andbromacetophenone in like manner, crystallises from alcohol in colour-less plates, melts st 92-93', boils above 360" without decomposition,and is readily soluble in alcohol and ether ; i t is a very feeble base,but its salts are unstable and cannot be obtained in a pure con-dition.Ethyl a-methyl-p-phenyltF,iaroEecarboxylate, 8 P~'S>C*COOEt, isN*CMeobtained when t.hiobenzamide is warmed with ethyl chloracetoacetate,and t,he salt thus produced docomposed with soda; it crystallisesfrom ebher in yellow needles, and melts at 43".The correspondingacid, CllH9NS, prepared by hydrolysing the ethereal salt with alco-holic potash, crystallises in colourless needles, niclts at 202--204*5",and, when heated more strongly, sublimes in long needles, being atthe same time partially decomposed into carbonic anhydride andmethylphenylthhzole. It is readily F;oluhle in alcohol, but onlysparingly in ether, and almost insoluble in water; in its neutralsolutions many metallic salts produce a precipitation.A mixture of nu*ious compounds, which contains a-chloropropalde222 ABSTRACTS OF OHEMICAL PAPERS.hyde, can be obtained by gradually adding sulpharyl chloride to anethereal solution of propaldehyde in which ba.rium carbonate issuspended ; the etbercal solution is washed with water and sodiumcarbonate consecutively, dried, and then submitted to fractionaldistillatiori; the portion passing over between 60" and 15U" wasemdoved in some of the exDerirnents described below.L . , CMebCHONp~-D.'meEhyZthiazole, I I >CMe, is formed in small quantitieswhen crude a-chloropropaldehyde is warmed wi t8h thiacetamide, theproduct boiled with hydrochloric acid, aud then treated with soda ;it is purified by distilling with steam, and then submitted to frsc-tional distillation. It is a colourless liqnid, boils a t 148-150"(734 mm.), and is sparingly solublein water, but readily i n ether andalcohol.The ylatitr ochhride, (c?,H,NS) 2, H2P tCl,, crystalhes illprisms and melts at 202' ; the picrate crystallises in sniall, yellowneedles, melts at 166-167", and is sparingly soluble in water.~-,~ethy1-~-arnidotl~iuzole7 caH6N2S, is obtained by heating crudea-chloropropaldehyde with thiocnrbamide ; it crystallises from waterin yellowish plates, melts at 94-95", and is rendily soluble in alco-1101, but less ieadily iu ether, and only sparingly in cold water. Theplatinochlo~ide forms nodular, crystalline aggregates, and melts a t18 1-182" with decomposition.ap-uil3henyl-~-arnidobhiaeole7 C,,H,zN,S, can be prepared by warm-ing bromod eoxy benzoin with thiocarbamide and decomposing theprodnct with dilute sodium carbonate.It crjstallises from alcoholin yellowish needles, melts a t 185-186", and is readily soluble inalcohol, but only sparingly i n ether, and ins3lnble in water. The hydro-broinide, C,,H2,N2S,HBr, crystalliaes in needles, melts a t 215- 217"withpartial decomposition, and is only sparingly soluble in dilute hydro-brornic acid.a~-DiyhenyZ-p-methyZtl/iazoZe, C16HlJNS, can be obtained by treatingan alcoholic solution of thiacetamide with bromodeoxybrnzoln ; it. i:,purified by means of the hydrochloride, a crystalline compound melt-ing at 96-97'. The baqe crysfallises in colourless needles, melts at51-53', and is insoluble in water, but readily soluble in alcohol andether.Tripheny?thiuzoZe, C,, H,,NS , prepared from th iobenza mide andbromodeoxy benzoin, crystallises in colourless, well-defined prisms,melts at 86-87", and is readily soluble in other, but more sparingly inalcohol, and insoluble in water.It, crystallises unchanged from hot con-centrated hydrochloric acid, in which i t is only very ~paringly soluble.Pheriylhpdroxythiazole (m. p. 204') is formed when bromaceto-phenone is treated with xanthogennmide under various conditions.The ethyl derivative of phenyloxypseudotbiazole is obtnined whenphenylhydroxythiazole is treated with sodium ethoxide and ethyliodide a t 140-150". It crystallises from ether in colourless plates,melts at 71", and is decomposed by concentrated hydrochloric acid at220" yielding ethglamine ; it has, therefore, the coiistitution expressedby the formula 1 1 E'.S. K. CH*S*COC Ph*N E t >ORGANIC CHEMISTRY. 223Trimethylthiazole, Methylethylichiazole, and Thiazolecarb-oxylic Acids. By T. ROUBLEFF (Annulem, 259, 253 -276).-&th!/lcc-chlorometh ylacetoacetate, COMe*CMeC I-COOEt, is obtained whensulphuryl chloride is gradually added to well-cooled ethyl methyl-acet>oacetate. It is a colourless liqnid of sp. gr. 1.0592 a t lti.5", witha pleasant, rather pungent odour, and boils at 192-194' (corr.), Itdoes not yield a salt with c3pper acetate under any conditions ; thecorresponding bromo-compound, obtained by brominating ethylmethylacctoacetate, gives a copper salt, and can be readily convertedinto thiazole derivatives.I t is evident, therelore, that chlorine andbromine, at the ordinnry temperature, displace different hydrogenstonis in ethyl methylacetoacetate (compare Hantzscb, Abstr., 1890,1238; it has, however, been stated by Genvresse (Corryt. rend., 107,18T) that both a- and ychloro-derivatives are formed when ethylacetoacetate is treated with chlorine a t 170".Tr&meth y 1 thiazole, GMeoS>CMe, is formedCMe*Nwhen crude methylchlorethyl ketone, prepared by hydrolysinq ctliyl a-chlormethylsceto-acetate with 40 per cent. hydrocbloric acid, or by chlorinating methylethyl ketone with snlphuryl chloride, is warmed with thiacetamide ;the product is boiled with dilute hydrochloric acid, the filtered ~olu-tion mixed with soda, and the precipitated oil extracted with ether.TrimethTlthiazole can also be obtained by brominating methyl ethylkctone in ethereal solution, and treating the methyl bromethylketone produced with thiacetamide.It is tt colourless liquid ofsp. gr. 1.0130 at l G o , boils at 366*5-167*5" (corr.), and is moderatelyeasily soluble in cold water. The platinochloride, (C,H,NS),,H,PtCl,,c~ystallises in orange prisms, and melts at 232-233" with decomposi-tion. The hydrochloride is a crjstalline, deliquescent compoundmelting st lf%-174°. The aurochloride is sparingly soluble in boil-ing water, frorn which it cryst;lllise.s i n gellow needles melting atlS5-I 56".The picrate crystallises from hot water in yellow prismsmelting at 133", and the mercurochloride crystallises iu small platesmelting at 118-119".E t h y l bromo.methy Zacetru cefat e, C H2Br C 0-C HMe*C OOE t, preparedby brominating ethyl methylacetoacetate, is an oil of sp. gr. 1.1'381at 16.5', with a disagreeable, pungent odour ; its alcoholic solutiongives a reddish-violet coloration with terric chloride, and a green,crystalline precipitate with copper acetate.>C*CHMe*COOEt, is formedwhen thiacetamide is treated with ethyl bromomethylacetoacetate ;i t is a thick, dark-brown oil, and on hydrolysis with alcoholic soda, ityields ail oily acid fihicb, when distilled with lime, is converted into14 - methy l-a-et h yl thiazole.p- Methy Z-a-eth y ZthaazoZe, CsH9NS, purified by fraction a1 distillation,is an oil boiling at 169-171" (corr.).7Me:NEthyl methylthiazolepropionate, 8-CHThe platinochloride,forms reddish-jellow prisms, and melts at 182 -183" with decom224 ABSTRACT3 OF CHENLCAL PAPERS.position. The picrute crystallises from water in well-defined, lemon-yellow prisms, melt.ing at 114-115c, and the mercurochloriclt? crystal-lises i n prisms melting at 138-139'.NGMeC Me* S a~-Dimethylthinzole-~-ca?.bozy7ic.acid, I I >C*COOH, i s obhinetlwhen the ethyl salt (compare Hantzsch, Abstr., 1869, 724) ishydrolysed with alcoholic potash. It crystallise~ frcm hot waterin long, colourless needles or small prisms, melts at 22T withovolution of gas, sublimes without decomposition, and is onlymoderately easily soluble in hot water, hut, more readily in alcoholand ether.The salts of the alkaline earths are readily soluble inwater, but in neutral solutions of the ammonium srtltp, nbany mctallicsdts prodnce a precipitation. The silver salt, C,HsNS*COO Ag, crys-tallises from boiling water in colourless needles, and qnicklg darkenson exposure t.0 light. The hydrochlode, C6H702NS,HCI, crystallisesfrom cold dilute hydrochloric acid in transparent plates, and isdecomposed by wattJr, or when heated at 70". The acid is COIN-pletely destroyed by potassium permanganate, but it is not acted OILbv boiling concentrated nitric acid. Y s*!?CooH Can be 01)-N*C *CO OH' p- M et h y It li iazo 1 edicar boxy tic acid, C Me<tairred by warming ethyl chloroxdacetate, prepared by txeating ethyloxalacetate with snlphuryl chloride, with thiacetamide, and hydro-lysing the product with alcoholic soda.It crysttillises from warmwater in loug, colourless needles with 1 mol. HsO, mblimes below100". melts at 169" with evolution o€ carbonic anhydride, aud i sreadily solnble in cold water and alcohol, but very sparingly i n ether,carbon bisulplide, benzene, &c. The barium salt, CsH3NS0,Ba + 2H20,cqstallises in colourless needles, and loses the whole of its water at130". The mercury salt, C,H,NSO,Bg + 3+H,O, is colourless andcrystalline, and loses its water at 113". Most of the other salts, exceptthose of calcium, magnesium, and the alkalis, are sparingly soluble inwater.~-J1Zethljlthiazole-P-carbo.ry7ic &iJ, C,H,O,NS, is formed with evolii-tion of carbonic anhydride, when 1 he dicai*b~xylic acid just describedis heated for some time at 170-li2".It crystallises from water insmall, colourless needles or prisms containing 1 mol. H20, loces itswater a t 70-go', aud melts at 144-145"; it is readiiy soluble incold water, but more sparingly in alcohol, ether, and chloyoform, andalmost insoluble in carbon bisulphide and benzene. The salts are allreadily soluble, except those of silver, copper, and mercury.Eth yc, ~-amidcltkiazoleL3icnrbox~late, CsHI2OIN2S, is obtained in thcform of the hydrochloride when ethyl chloroxalacetn1,e is mixed witlitbiocarbamide ; when the crystalline salt, which is only very spar-ing1.Y soluble in water, is treated with potassium carbonate, the baseis liherated, and can be purified by crjstallisation from ether-alcohol.It forms well-defined prisms which contain 8 mol.C2H60, and melt!at go", the alcohol-free compound melting at 11 2".~-AmidothiuzoZedic/irbox~l~c acid, C5H4N2S04, prepared by hydro-lysing the ethyl salt with alcobolic soda, cq-stttllises from hot wateiORQANJC OBEMISTRT. 223in yellowish needles with 1 mol. HzO, loses its water at lSO", melts rtt229-230" with complete decomposition, and is only sparingly holnblein most ordinary neutral solvents. Attempts to corivert this acidand its ethyl salt into ap-thiazoledicarboxylic acid by means of nitrousacid were unsuccessful. F. 8. I(.Diazo-compounds of the Thiazole Series.By M. WOHMANYfrlnnalen, 259, 277-300).-A compound of the compositionC1H9N3O3S, which seems from its behaviour to be the diazo-hydrate, Isformed when ethyl meth~l~midothiazolecarboxylaie (10 grams), prc-pared as described by Zurcher (Abstr., 1889, 7 d 5 ) , is dissolyed in aniixtme of 33 per cent. hydrochloric acid (30 c.c.) and water (200 c.c.),and sodium nitrite (25 grams), dissolved in water (100 c.c.), graduallyadded to the cooled soltitioil ; after expelling the nitrous acid witoh a,stream of air, the precipitate is quickly separated by filtration, wasliedwith very dilute nitric mid, alcohol, and etfber consecutively, and then~*ecrystaIlised from cold ether, from which i t separates in small,yellowish plates.It melts and explodes at 99-1@0", is rather un-stable, gives Liebermann's reaction, and is moderately easily solubloiu glacial acetic acid, alcohol, benzene, and light petroleum, but moresparingly in ether. In some respects, it bebares like an aromaticdiazo-compound, being soluble i n alkalis aiid cold concentrated acids,and giving dyes witli pbenols ; in otherg, it behaves like a nitroso-derivative, and, when treated with most ordinary reducing ageuts, i sreconverked into the amido-compound.Ethyl hydrazomethjlthiaaolecnrboxylate is obtained in an impurecondition 1,s carefully reducing the diazo-compound described abovewith zinc-dust and dilute ammonia. I t is a crystalline, verg unstablocompound, which reduces Fehling's solution in the cold, and combinesreadily with aldehydes and ketones in acetic: acid solution, yieldingcrystalline compounds ; the condensation product obtained withacetone forms brigh t-yellow needlee arid is unstable.E t h y l met h y E c h l o ~ o t l ~ i c i z o l e c ~ ~ b ~ ~ l u t e , C,HeO,N SCJ , can be pre-pared by.gradually adding the diazo.compound to warm 15 to 18per cent.hydrochliwic acid, and heating the mixture until the evolu-tion of nitrogen ceases; the solution is then diluted with water,the product distilled with steam in order to separate it from theazimido-compound described below, and then treated with dilutehydrochloric acid to free it from ethyl met113 lamidothiazolecarb-oxylate. It crystallises from alcotlol in transparent prisms, melt8 at30-51", has a sweet, sharp taste, and a fruity odour ; it i8 soluble inconcentrated hjdrochloric acid and dissolves freely in most ordinaryorganic solvents, but is insoluble in water.Ethyl m e t h y 1 bromothiuzolecarboxylate, C,H,O,NSRr, prepared bytreating the diazo-compound with bydrobromic acid in a similarmanner, crystallises from alcohol in large, colourlcss plates, melts a t70-71", and resembles the chloro-derivative i n chemical and physicalproperties.The corresponding iodo-compound, C1H,02NSI, is formedS - C*N:N*OH .of ethyl metbylthiazolecarboxylate, COOEtC<CMe.226 ABSTRACTS OF CHEMICAL PAPERS.in small quantity wben the diazo-compound i R tteated wikh 2 to 3per cent. hydriodic acid, the principal product, however, being regene-rated amido-compound ; it separates from alcohol and glacial aceticticid in crystals melting at 86-87", and resembles the chlorinatedderivative very closely.The yield of the iodo-compound i p only5 to 10 per cent., whereas in the case of the chlorinated and bromin-ated derivatives the yield is €0-70 per cent. of the ethyl methyl-amidothiazolecrtrboxylate employed.Ethyl inethyEazintidothiazoleca~~J~x~jlate, ClbHli04NJ32, is graduallydeposited in orange-red needles when the diazo-compound is boiledwith alcohol or heated for a long time with almost any neutral sol-vent. It separates from alcohol and glacial acetic acid in crystals,melts at 22&225", and is moderately easily soluble in benzene andlight petroleum, but more sparingly in ether ; i t dissolves freely inmineral ncids, but it is oiily very sparingly soluble in, and is decom-posed by, alkalis. On reduction with zinc-dust and hydrochloric acid,i t is converted into ethyl methplamidothiazolecarboxylate, and 011hydrolysis with alcoholic potash it is converted into the correspond-itig acid, CI,,H9O4N5S2, which crystallises in slender, yellowish-rediicedles, melts at 214" with decomposition, arid is almost insoluble inall ordinary neutral solvents.Met hy lchlorothiazolecarboiy Z~~ a c i d , C5H40,NSCl, is ob hained whenthe ethyl salt described Rbove is hjdrolysed with cold alcoholicpotash, biit the product is always mixed with some methylhydroxy-tlhiazolecarboxylic acid, from which i t can only be imperfectlyseparated by fractional crystallisation.It seems to melt at about144-145", and is very readily soluble in all organic solvents, but onlymoderately easily in hot water. The s i l v e r salt, C5H3O2NSC1Ag,crystallises in colourless needles.The bromo-acid, C,H402NS Br, and the iodo-acid, C5H4O2NS1, werealso obtained in an impiire condition ; the former seems to melt atnb jut 16'2--164", tbe htter at about 179-176", with decomposition.Methylhydroxythiazoleca~7~o~~:ybic acid, CsH5O,NS, is formed whenmethylchlorothiazolecarboxylic acid is heated at 170*, but it is bestprepared by fusiiig the ethyl salt of the chlorinated aaid with concen-trated potash. I t crystallises frow alcohol in small needles, melts atC 6 C O 2.22and hot water, but only sparingly in ether, and almost insoluble inbenzene and light petroleum.The um?noniu,m salt, CSHRO9N2S,crystallises from water in large prisms with 3 mols. H20, and meltsat 138" with liberation of carbonic anhydride, bt.ing transformed intomethg lhydroxpt,hiazole (m. p. 102") ; t h i s hydroxy-compound is alsoobtained when the acid is carefully heated.Ethyl metltylthiaiolecnrboxylate, C,H,O?NS, can be easily preparedby treatinp the chlorinated derivative with zinc-dust and acetic acid a t:c temperature below 50". It crystallises in transparent prisms, meltsat 27-28', boils a t '292-233" (726 mm., thermometer entirely invapour), is volatile with stcam, and is very readily soluble in dlordinary solrsnts except water. The corresponding a c i d , CbH502NS,prepared by hydrolpsing the ethyl salt with alcoholic potash, crys-tallises from hot water iu nacreous plates, and from alcohol in smallwith decomposition, and is moderately easily soluble in alcohoORQANlC CHCMISTRT.227needles, melts at 257" with decomposition, and is almost insoluble inbenzene and light petroleum ; most of the Ealts of the heavy metalsare insolnbie. F. S. I(.Synthesis of a Diamidocarbazole from Benzidine. ByE. TAUBER ( Uer., 23, 3.L66-33"69).--l)iamidocarbazole sulphate,CL2HIIN3,H2SO4, can be obtained by heating metadiamidobenzidinehydrochloride (compare Abatr., 1890, 783) with 18 per cent,. hydro-chloric acid (6 parts) for 10 bours at 180-190", and treating tbefiltered solution of the product with excess of hot dilute sulphuricacid ; it crystallises in colourless needles and is almost insoluble inboiling water.The base, CI2Hl1N3, crystallises from hot alcohol i nflat, lustrous needles, and turns black at 200°, but without melting ;it is not identicad with the diamidocarbnzole obtained by nitratingcarbazole and reducing the product (compare D. R.-P., No. 46438).The hydrochloride is moderately easily soluble in water but is pre-cipitated from the solution in crystals on the addition of hydrochloricacid. The tetrazo-derivatives of the base dye unmordanted cotdonvery readily, the ~liarles being the same as those obtained with thecorresponding benzicline dyes. F. S. K.Tritspine and other Rare Opium Bases. By E. KAUDER(Arch. Yhnrm., 228, 419--431).-Tlie rarer alkaloids were sought forin large quantities of the mother liquor, obtained in the preparation afmorphine, &c., on a manufacturing scale. The results largely conttrniand extend those previously obtained by Hease.After removing therelatively large quantities of morphine, codeine, narceine, thebaine,papaverine, and narcotine still present in tbe mother liquor, a coti-siderable amount, of cryptopine was the first product. The motherliquor, diluted with water, warmed t o 60", and poured into water cowtaiuing excess of sodium hydroxide, gave a dark, resiiious precipitate.'l'he filtrate, further treated with hydrochloric acid, ammonia, $c.,gave only narcotine and laudanine. Lanthopine and coclmiine we7 enot detected. Laudanine, whilst soluble in sodium hydroxide, canalso be methylated.so t h a t it ranges with morphine. The mcthyl etherof laudanine, melting at 213", is iiot identical with laudanosine. Thedark, resinous precipitate above desc~ibed was dissolved in a littlenlcohol. treahed with ether until precipitation ceased, the ether filteredoff, and treated with acetic acid water. Excess of potassium iodideadded to this solution precipitates almost, the whole of the alkaloids,with much resin. After 24 hours, the mother liquor was poured ofl,the residue mixed with a little alcohol and set aside for several days.JAlnrge quantities of iodides thus crystallised out, which were pressedand washed with a little alcohol. No more crystals could be ob-tained from the tenacious mother liquor containing mcst of the resin.The iodides were convert,ed into tbe free bases, and hhese dissolved iuhydrochloric acid and concentrated.After the addition o€ an equalvolume of alcohol and then alcoholic ammonia, crystals of protopin t',and a new base, tritopine, separabed. The filtrate from these wantreated with much ether, the ether agitated with oxalic acid water,the aqueous solution concentratud and treated with more oxalic acid228 ABYTHACITS OF CEEMICAL PAPERS.After 24 hourp, a few hard crystals of protopine and cryptopincbinoxalste hrtd formed. Yurther treatment of the mother liquor witlipotassium iodide, &c., separated small quantities of cryptopine, prot-opine, and tritopine, whilst still further concentration yieldedlaudanosine, easily purified by crystallising from light petroleuni.Tritopine, C12HMN201, melts at 182".I t is easily soluble in chloro-form, slightly in ether ; 1 part dissolves in 40 parts of boiling alcohol,from which it crystallism in transparent prisms. Several salts oEthis base are described. The relative amounts of the bases found WCI'C'npproximately, Inndanosine, 1 ; tritopine, 2 : protopine, 3.5 ; laudanine,29; cryptopine, 70. J. T.Atropamine. By 0. HESSE (Chew. Celih., 1890, ii, 446-447 ; fromPharm. Zeit., 35, 471).---l'be author hag separated an alkaloi'd fromthe roots of dtropa belladonna, wbich he has named atropamine. i l tordinary temperatures, it is solid, but is quite liquid at 60". It isprecipitated from solutions of its salts by potash or soda as an oil ; itis readily soluble ill alcohol, ether, and chloroform.It has theformula C,,H2,N02; i t contains 1 mol. H& less than atropine,hyoscyamine, and hyoscine, and is isomeric with belladonnine. Itforms haloid S R ~ I S , wbich crystallise very beautifully ; this distill-guisbes it from belladonnine and other atropa alkaloids.A 2 per cent. solution of the hydrochloridshas, according to Berlin, no mydriatic action. Protracted boilingw i h alcoholic solution of barium hydroxide causeh a decampositionwith formation oE tropine and an acid which is neither tropic, atropic,nor isatropic acid. By the act.ion of hydrochloric acid, atropamineig converted into belladonnine, and is then furt.her transformed as byheating with alcoholic barium hydroxide. Atropamine is very readilydecomposed by acids, and hence it has been overlooked in the past.The acid above referred to, the nature of which has not been deter-mined, sometimes causes a smell of bitter almond oil if mixed withpotassium permanganate, a reaction which is not produced witha t ropamine. J.W. L.It is opt'ically inactive.Root Constituents of Sccrpolia atropo'ides. By E. SCHMICT(Arvh. Yhwrm., 228, 435-441). A new investigation, in whichthe bases were precipitated as auroohlorides, yielded hyoscyamine.but only a very small aiiiount of atropine, and a minute quar1tit.yof aurochloride, which agreed as to its melting point, 198-199",and analysis with the hyoscine ccmpound. Scopoletin has beenproved to be identical with methylsesculetin by Takshashi (Abstr.,J889, 255).I?. Schmidt IIHS found by the application of Zeisel'smethod (heating with hydriodic acid, Ssc.) that scopoletin containsonly one methosyl group. The asculetin produced by this re-action was isolated and analysed. The methylaesculetin of Tie-niann and Will melts a t 184", whilst scopoletin melts at 199--200",FO that one is probably the a- and the other the P-methylmculetin ;but which is which has not been determined. J. TORGANIC OKEMISTKY. 229Alkaloid8 of Chelidonium majus. By F. SELCE (AT&.Pharm., 228, 441--462).-Besides the two alkaloids chelidonineand chelerythrine, I!!. Schmidt found strong evidence of thepresence of a-ho?ttochelidotiilze, p-homochelidonine, arid ft third baseseemingly idelrtical with protopine, an alkaloid obtained by Besse fromopium.The author has separated and investigated these tbree newbases. The following qenei-al method is used to extract the bases fromthe root of the plant. The dried and palverised material is repeatedlyextracted with alcohol containing acetic acid ; after filtration anddilution with water, the alcohol is distilled off and tbe resin separatedis removed by another filtration. The filtrate is treated withammonia and shaken up with chloroform ; the chloroform solution onevaporation leaves a residue which is dissolved iu the least possibleamount of alcohol containing hydrochloric acid. After cooling, the:~lcoholic solution is separated by 61t.ratlion from the undissolved andcrystalline portion, consisting of chelitlonine and protopine hydro-chlorides.The alcokolic solution is diluted with water, freed fromtilcobol, strongly diluted with hydrochloric acid water, filtered, andtreated with ammonia in excess. The fi1trat.e contains P-homo-clielidonine, which may he extracted by shaking up with alcohol.'l'he precipitate contains a-homochelidonine and chelerythriue ; thelattcr can be obtained by long digestion with et'her./3-Homochelidonine, CleHIJ(OMe)2N03, appears as well formed,colourless, seemingly monoclinic crystals, whiceh melt at 1.59". Asolution (1 : 100) gjves a white precipitate with mercury cllloride,phovphotungstic acid, and potassium cadmium iodide ; jellowish-white with potassiaru mercury iodide and phosphoruolybdic acid ;yellow with bromine-water ; reddish-yellow with potassium bismutho-iodide.Concentrated sulphuric acid gives a beautiful violet coloration.Froehde's reagent yields a transien t ycllow, violet, and green coloration.which becomes a beautiful blue, and finally an intense moss-green.Erclman's reageut gives a yellow, passing quickly to a beautifulviolet, which gradually become3 dirty-violet. Concentrated nitricacid produces a yellow coloor. Vanadium sulphuric acid gives yellow,violet, and intense blue ; after a time this become green. The alkalo'idis easily soluble in hydrochloric, sulphuric, nitric, and acetic acids.The hydrochloride, platinochloride, crnd anrcichloride are described.a-Homocl~elicZori,ine, C,,H,,(OM *)dN03, forms large, rhombic crystals,when recrystallised from it.s solution in ethyl acetate, which melt a t182".Its solution (1 : 100) yields precipitates similar to those givenby the &base, with the addition that tannin gives tt white pre-cipitate, soluble in excess. concentrated ~ u l p hiiric acid dissolves thebiise, with the gradual formation of pale-yellow streaks. Concentratediiitric acid gives a yellow coloration. Wroehde's reagent prodncey adirty brownish-green and then bro wnish-yellow tint,. Erdniann'aTeagent and vanadium sulphuric acid yield a reddish-yellow colora-t ion. The hydrochloride, pla.tiuochloride, and aurochloride aredescribed and analysed.Protopine ( Y ) wa3 finally obtained in colourless crystals from i t ssolution in a mixture of much chloroform with little ethyl acetate ;its melting point is 20'7''.The amount obtained was insufficient t230 ABSSTHAOTS OF OHENICAL YAPEHS,admit of a determination of its formula, but C,Hl,NO, is indicated,and Zeisel's method does not indicate the presence of methoxylgroups. Its reactions with precipitants me the same as those givenfor a- homochelidonine. J. T.Alkaloids of the Rhizome of Veratrum album. By G.SALZDERGER (Arch. Pharm., 228, 462--483).-Besides the threecry stallisable bases, jervine, rubi jervine, and pseudojervine alreadyknown, the author has isolated two new ones, protouerutriizs, anextremely powerful poison, and protnveratridine. Two methods ofextraction were followed : one, the baryta method, is relatively rapid,and gives jervine, ruhi jervine, and protoveratridine, but no proto-veratrine ; the other, the metaphosphoric acid method, yields proto-veratrine and pseudojervine, with small amounts of jervine and mbi-jervine.The yield varies considerably, and the method of dryingthe rhizome is not without influence on the result. The moderatelypnlverised rhizome was mixed with barium hydroxide and water, andextracted with ether. The extract was freed from ether at the lowestpossible temperature in a gentle current of hydrogen. The dark-green syrup thus obtained gave a crop of crystals mainly consistingof jervine. Recry stallisation f rorn alcohol separated a little proto-vemtridine, and furhher treatment by Wright and Luffs process withdilute sulphuric acid yielded a small amount of rubijerrine.Tliemother liquor from the crude jervine by further treatment yieldeda lit>tle more protoveratridine and rubijervine, and other uncrystal-lisable and decomposition products. Protoverrttrine can be easilyextracted from t>he drug by cold water, but cannot be obtained in acryhtalline form by this means. To obtain the crystalline base, therhizome is freed from fatty and resinous compounds by treatment,with ether, and an alcoholic extract of the residue is prepared. Thisextract is freed from alcohol in tl vacuum, mixed with much acetic.acid water, quickly filtelud from the insoluble residue, and treatedwith solid met'aphosphoric acid, until no further precipitate appears.The voluminous precipitate contains much amorphous matter,besides insoluble compuunds of jervine and rubijervine.The filtrateis treated with excess of ammonia, filtered, and shaken up with ether,and from the ether extract the protoveratrine crystallises out whet1the ether is distilled off. By rec:*gstallisation from strong alcohol,the base is purified and separated from some IittJe remaining rubi-jervine and jervine. Theauimotiiacal solution, aftper reinoval of ether, was further treated withchloroform, when pseudojervine was obt-iined. Protoveratridine isnot obtained by this metaphosphoric acid process, which would indi-cate this base to be a decomposition product of protoverstrine.Protoreratl-ine, CaH51NOII, crystallises from dilute Polutions inmicroscopic four-sided plates, which melt with charring ah 245--250°.'l'lie base is insoluble i n water, benzene, and light petroleum ; chloro-form and boiling 96 per cent.alcohol dissolve it somewhat ; cold etherscarcely touches it, boiling ether takesup a little more. Dilute acids,with the exception of acetic acid, dissolve it. The base is exceetl-ingly poisonous; a minute amount applied to the nose causes violentThe yield was about 0.3 gram per kiloORGANIC CEEXISTRT. 231sneezing. Concentrated sulphuric acid dissolves the rrlkalo'id slowlywith the production of a greenish colour, which passes to cornflowerbloe, and after some hours becomes violet. With the same acid audsugar, the first formed greenish colour becomes olive-green, thendirty green and finally dark brown ; this is very different from thecolours yielded by veratrine. When warmed with the strong acid, thesolution is first light, then dark cherry-red, and exhales the odour ofisobutyric acid. Concentrated hydrochloric and phosphoric acids givethe same reaction. Dilute solutions of 6 d t S of this base are quanti-tatively precipitated by ammonia ; precipitates are also produced byNessler's test, gold chloride, potassium mercury iodide, potassiumcadmium iodide, pbosphotungstic acid, and picric acid, whilst noprecipitate is produced by tannin, platinic chloride, or mercuric chlor-ide. The aurochioride, a golden -yellow, amorphous compound, w%.obtaiued and analysed.Protoverutridiua, C,,H,,N,O,, occurs as colourless, fonr-sided plates,which melt at 265". It is almost insoluble in alcohol, chloroform,methyl alcohol, and acetone, and insoluble in benzene, light petroleum,aud ether. I t is not poisonous, and does not cause sneezing, bnt itnsolutioii in dilute acids has a very bitter taste. Concentrated sulphuricacid gives first a violet, then a cherry-red colour. Its solution it1concentrated hydrochloric acid becomes light-red on warming, as isthe case with veratrine, but wit11 a decided odour of isobutyric acid.Dilute acids readily dissolve the base, and the solutions give cry6tal-line precipitsks with ammonia. The sulphuric acid solution givescopious precipitates with phosphor nngstic, picric, and tannic acids,aud with potassium mercury iodide, but gives no precipitate withplatinum chloride, potassium cadmium iodide, or with Millon'sreagent. Yrotoveratridrne platinochloride, (C,,H,,NO,),,H,PtCl, +6Hz0, was precipitated as large, six-sided plates on adding alcohol toa mixed solution oE platinum chloride and a salt of the base. Pseudo-jervine has been already described by Wright and Luff ; they foulld itsmelting point to be 299," ; the antlior makes it 300" to 307". Jervine,C36H37N03, melts a t '158" to 242", Wright and Luff iound 237". Theli y droc Iiloride, nitrate, pltltiiioc hlor i d e, and auroc hloride are described.Wright and LuE's formula is confimed, and not the one given byTobien. Rubijervine, C,RH4,N0, + H20, melts at 240" to 246" ;Wriglit and Luff found 236'. Five bcasic compounds have t h u s beendetermined with certaiutly in white liellebore root.By A. PARTHEIL ( 1 3 P r . 23, 320l-3d03) .-The alkaloiclprepared by Husemaun and .Marin& from the seeds of the laburnumand other kinds of Cytisus, to which they gave the name of cytisine,may be readily obtained in the following manner. The coarsely-powdered seeds are extracted with alcohol containing hydrochloric?acid, the ftlcoliol distilled OH, the residue treated with water, andfiltered through a wet filter to remove any fatty oil, the filtratetreated with lead acetate, and after separating the precipitaled colour-ing matter, made alkaliile with caustic potash, and shaken with amyIalcohol. 'the latter solution is then extracted with dilute hydro-chloric acid, thu solution evaporated, the ciudt: cytisirie hydrochlorideJ. T.Cytisine232 ABSTRAOl'S OF OHEMICAL PAPERS.thus obtained treated with dilute alcohol to remove colouring matters,and recrystallised several times from water. The salt then formswell-dev eloped, colourless, trans parent prisms. Its PZatitLochZoridecrystallises in golden-yellow needles, which have the compositionCllH,,N,O,H,PtC1, + 2bH20, are tolerably soluble in water, anddecompose on heating without melting. The aurochEom'de,C1,H14N20,HAuC14, crystdises in short, reddish-brown, hook-shapedneedles, which melt at. 21'2-213" (uncorr.) with evolution of gas.From the analyses of these double salts, it follows that cytisine hasthe composition CIlH,,N20, and not C2,H2,N30 as given by HiisemannRnd MarmB. The same formula has already been given by Gerrardto ulexine, obtained from the seeds of Ules europceus (Abstr., 1886,1048), which, as Koberth as already suggested, on physiological grounds(Deutsch. Med. Wochenechr., 1890,406) msv be identical with cvtisine.Both compounds are being a t present'f urther investigated."H. G. C.Products of the Artificial Digestion of Glue. By F. KLUG(Chent. Centr., 1890, ii: 328-319 ; from Centr. PhysioZ., 4, 189-191).-Glue, obtained from the refining of fine French gelatin, is pre-cipitated from its solution by. picric acid, chromic acid, tannin,ylatinic chloride, mercuric chloride and iodide, potassium iodide, andhydrochloric acid. These precipitates dissolve in hot water, arid arereprecipitated on cooling. Alcohol, phosphotungstic acid, Hiid hydro.chloric acid, basic lend acetate, arid ammonium sulphate also precipi-tate it, the precipitates being, however, insoluble in hot water. Withaodium hydroxide and copper sulphat.e, its solution is coloured violet-Idue. Acetic acid and potassium ferrocganide cause no precipitatiort.nllillon's reagent causes a Aocculeut precipitate, soluble in the hotliquid ; if the solution be boiled, i t is coloured red. Nitric acid andsodium hydroxide colour hot glue solutions slightly yellow ; copprrsalphate causes a blue coloration. Glue, therefore, may be distin-guished from egg albumin by the precipitate obtained with picric aciddissolving on heating and by the biuret reaction, whereas with nitricticid neither precipitixtion nor yellow coloration ensues. It is to henoted, however, t h a t concentrated solulions of sodium chloride, ammo-nium sulphate, and gallic acid form precipitates with picric acid whichdissolve in warm liquids. By artificial digestion, glue becomes COU-verted into three mbstances, glutose and glutznopeptone, whichdissolve, and upoglutin, which remains in the liquid as a tlocculentr e k h e , to the amount of 5.69 per cent.Apoglulin dissolves completely in sulphuric acid, but only imper-fectly in the other mineral acids and in acetic acid. Wheu boiledwith nitric acid, it becomes coloured yellow ; sodiuru hydroxide andcopper sulphate colour i t violet; boiled with Millon's reagent, i t iscoloured red ; i t is not digested by pancreatic juice.Glutose is precipitated from the solution of digested glue by the ad&-tiou of ammonium sulphate or alcohol, and it may be precipitated, afterre-solution in water, by addition of sodium chloride, and then acelicacid and concentrated solution of sodium chloride. That, part whichis precipitited by salt bas been named by the author protoglutose; theremaining portion, which is separated on the addition of acetic aciPHYSIOLOGICAL CHEMISTRY 233and sodium chloride, he names deuteroghtose. Glutose, precipitated by9S per cent. alcohol, separates as a sticky, white mass. It is alsoprecipitated by picric and chromic acids, phosphotungstic acid andhydrochloric acid, mercuric iodide, potassium iodide and hydrochloricacid, platinic chloride, and mercuric chloride ; all these precipi-tates, that by phosphotungstic acid excepted, are dissolved on warm-ing the solutions, and are again precipitated on cooling. When boiledwith nitric acid, it is neither precipitated nor coloured yellow ; butif sodium hydroxide is added, the solution becomes yellow. Sodiumhydroxide and dilute copper sulphate colour the solution violet-red ;copper aulpbate alone colours it blue.Glutinqeptoite is also obtained by the digestion of glutose, and maybe precipitated by means of a mixture of alcohol and ether. When driedon the water-bath and in the desiccator, it appears as a yellow, brittlemass, very readily soluble in water, wbicb distinguishes i t readily fromglutose. Picric acid causes a precipitate only with concentratedsolutions, which redissolves in an excess of the reagent, and also byheating ; chromic acid and platinic chloride cause no precipitation ;sodium hydroxide and highly dilute copper sulphate solution cause arose-red coloration ; copper sulphate alone, a green coloration ;Millon’s reagent causes a milkiness, which redissolves on boiling. Itbecomes precipitated by saturating the solution with either sodiumchloride or ammonium sulphste. The following are the elementaryanalyses of glue, apoglutin, and glntose.C. H. N. 0 and 5. Ash.Glue.. . . . 42.75 7-00 15-61 36-64 0.88Apoglutin . . . 48.39 7.50 14.02 30.09 5.22Glutose . . , . . 40.06 7.02 15.86 37.06 2-14J. W. L

ISSN:0368-1769    

DOI:10.1039/CA8916000159

出版商:RSC    

年代:1891

数据来源: RSC

摘要:

PHYSIOLOGICAL CHEMISTRY. P h y s i o l o g i c a l Chemistry. 233 Roteid Absorption. By R. NEUMEISTER (Zeit. Bid., 27, 309--373).-Many observers have found that a proteid may be absorbed without previous conversion into peptone ; for instance, in the case of nutrient enemata. It also appears that a first stage in the action of the digestive juices is simply to dissolre the proteid ; changes of the natnre of hydration then follow. Hasebroek (Abstr., 1887, 609) showed that this was the case with fibrin. It is equally true for coagulated white of egg, although whether the dissolved albumin is the same as the original albumin is uncertain ; i t is certainly not a globulin ; serum albumin, vitellin, and other proteids are also similarly simply dissolved, in the first instance, by the gastric and pancreatic secretions.Casein and haemoglobin are exceptions to t,his rule. Casein is first converted into an insoluble curd by the rennin of the stomach, and hemoglobin is decomposed into hsematin and a, proteid residue. When various prote'ids are introduced directly into the blood stream, there are differences again noticeable. Casein and hemo- VOL. LX, r234 ABSTRACTS OF CHEMICAL PAPERS, globin solutions act like foreign substances, and are excreted by the kidneys, Egg albumin is similarly got rid of; b u t in case of blood transfusion, thero is no albuminuria ; the same is truc for the injection of serum, or of solutions of pure serum albumin, of sgntonin (pre- pared either from white of egg or myosin), and of crystalline phyto- vitellin. These proteids, among which are to be noted several which are not normal constituents of the blood, are thus directly assimil- able, without, having undergone peptonisation.In fact, it is well known that albumoses and peptones introduced into the circulation are not assimilable, but, like other foreign sub- stances, are excreted by the kidneys (compare Abstr., 1888, 516). Dextrose is similarly got rid of, if its percentage in the blood is higher than normal; the question thus arises, whether peptone shoald be considered as on all fours with dextrose in this respect. That it cannot be, but that it is an absolutely foreign substance is shown by the fact that practically it all appears in the urine, and that i n normal blood no peptone or peptone-like substance is present. The word peptone may here be conveniently employed to include the albumoses, for all these products of proteolysis are in this respect the same (including hetero-albumose and atmidalbumin, concerning which experiments are now, for the first time, given).Peptone thus disappears rapidly from the blood after injection ; this occurs also when none can escape from the kidneys, either by ligaturing the ureters, or by injecting such a large amount that the lowering of blood pressure so produced stops urinary secretion. Under these circumstances, it is discharged into the intestinal canal. Peptone is therefore a form of proteid not assimilable by living cells. Previous experimenters have attemptod to answer the ques- tion where the peptone formed in the alimentary canal is reconverted into normal prote'ids.Salvioli could find none in the blood circulat- ing in the stomach walls, although the stomach was full of peptone. Hofmeister corroborated this ; and in the present research a number of observations, in which an artificial circulation was kept up, led to the same conclusion that some element, either in the interior of the alimentary canal or in the wall of the same, effects the disappearance of peptone; no other tissue produces this change. The general outcome of these experiments is as follows ; without doubting the existence of micro-organisms which cause the disappearance of peptone ( M . restitueny of J. Brinck, Abstr., 1889, 632 ; compare also N. Popoff, Abstr., 1889, 632), it is probable that the regeneration of albumin from peptone occurs not before, but concomitantly with, absorption.The methods of Brinck and Popoff were not carefully conducted from a chemical standpoint ; no doubt their peptone was mixed with albumin ; they put t5is mixture into the stomach, and withdrew i t after half-an-hour ; by that time the paptone had been absorbed, and the fluid, minus its peptone, was now able to keep the frog's heart beating; whereas, their conclusion was that the peptone had been converted into serum albumin. The question then arises, do the ljmphojid cells or the epithelium cells of the stomach and intes- tinal walls produce this effect? The fact that the white blood corpuscles are not able t o effect the change when peptone is injectedPHY SIOLOGICATA CHEXISTRY.235 into the blood stream is considered sufficient to refute the conclusion arrived at by others that the lymph cells are the active aKents ; in fact, most physiologists are now pretty well agreed that it is the epithelial elements with which, in this connection, we have to reckon, and their dehydrating action on the peptones is comparable to that of the liver cells in converting sugar into glycogen. The question whether the liver cells have any action on peptone is an interesting one. In most animals, artificial circulation of fluid containing peptone through the recently-removed and still-living organ led to a negative result; but in the case of the rabbit, the livqr cells were found to possess the power seemingly limited in other animals to the columnar cells of the wall of the alimentary canal. It cannot be, however, supposed that weighty conclusions can be drawn from an exceptional case; and even in the rabbit, the liver cells cannot normally fulfil this function, since the portal vein is always free from peptone, as in other animals.Such observations are also of importance in view of Seegen’s remarkable conclusion that the forma.tion of sugar in the liver occurs, not a t the expense of the hepatic glycogen, but of the peptone brought to the liver by the portal vein (Abstr., 1888, 172). Much of the present paper is devoted t o an examination of Seegen’s work, and the general nature of the criticisms, and of the experiments performed to negative his assertions, will be gathered from what has preceded this. Throughout this paper, great care is taken to point out the methods to be adopted in the separation of peptones and albumoses from one another, and from other proteids, and the fallacious results obtained before the time of the introduction of ammonium sulphate as a reagent for this purpose.Among the points taken up, it is shown that a so-called peptone described as existing in eggs (W. Fischel, Abstr., 2886, 166) is not a true peptone. The namepseudopeptone is suggested for it. Cystin in Pancreatic Digestion. By E. KULZ (Zeit. Biol., 27, 415417).-The question, as to what becomes of the sulphur of proteids during digestion has never been completely answered. In the present examination of the products of an artificial pancreatic diges- tion, no hydrogen sulphide was evolved.The insoluble products were removed by filtration, and the filtrate concentrated ; during this process, a precipitate formed, but after removal this was not found to contain cystin. The final filtrate, after o, time, deposited 8 white precipitate insoluble in water, but soluble in ammonia. The ammo- niacal solution was diluted with large quantities of water, and six- sided crystals separated, which, after purification by recrystallisation, gave all the reactions of cystin. Whether this is always the case, or if bacteria are concerned in the process, are questions that have still to be settled. W. D. H. W. D. H. The so-called Liver of Helix pomatia. By M. LEVY (Zkit. BioE., 27, 398414).-The chief intestinal gland of the snail Eelix yomatia is a digestive gland, but is not analogous to any of the abdominal glands of the higher animals.The weight of its organic r 2236 ABSTRACTS OF CHEDfICAL PAPERS. constituents is very constant, being the same in summer and winter, and in great measure they are the same in kind in all periods of the year. The alcoholic extract of the gland shows the chlorophyll spectrum (MacMunn’s enterochlorophyll). The digestive ferments present are a diastatic, n peptic, but not a tryptic one. The peptic ferment appears to be idantical with Krukenberg’s helicopepsin. The diastatic ferment disappears during the winter sleep ; it is capable of digesting raw starch, but has no effect on cellulose. A fat emulsifying action is shown by the secretion in the summer time, but this also disappears during hibernation.The ferment by means of which this action is brought about is not identical with the one described by Schmiedeberg (Arch. exper. Path. Pharm., 14) as histozyme. Histozyme, which was separated from pigs’ kidneys, is concerned in the splitting up of hippuric acid. The snail’s ferment has no such action. Glycogen with sinistrin was generally present in the organ, but all tests for bile gave a negative result. A list of the substances separable from the organ is as follows :- (1.) In the alcoholic extract : Chloropliyll, lecithin, oleic acid, fatty (2.) In the ethereal extract : A trace of fat. (3.) In the aqueous extract : Sugar, globulin (coagulating at 66”), glycogen, sinistrin, hypoxanthine, and other bases precipitable by phosphotungstic acid ; in the ash, potassium, sodium, calcium, magne- sium, iron (traces), manganese, chlorine, and phosphoric and sulphuric acids.Jecorin was also absent. acids, ash, chlorine, and phosphoric and sulphuric acids. In winter animals, silica was found in addition. W. D. H. Organic Basis of Various Shells. By W. ENGEL ( Z e d . Biol., 27, 374--385).-Numerons previous researches liave been directed t o the determination of the inorganic constituents of egg shells, b u t those relating to their organic constituents are scanty. The shells of a number of snakes, which were preserved for micro- scopic purposcs in Kleinenberg’s solution, were freed from picric acid by prolonged washing with water, alcohol, and ammonia. Elementary analysis of their organic substratiim gave the following percentage results :-C, 54.68 ; N, 16.37 ; H, 7-24 ; 0, 21.1.These coincide very well with the percentage composition of elastin, as worked out by previons investigators. The reactions of this sub- stance are, moreover, identical with those of elastin; Rome slight differences in solubility, especially in alkalis, are not considered suffi- cient to negative the general conclusion tbat the material in question is elastin, since elastin prepared from various sources itself exhibits similar differences in solubility. The cover of the incubating cells of wasps was next investigated ; and although the quantity of material available was not sufficient for elementary analysis, the colonr tests and solubilities of the substance are so like those of fibroin, with which it was carefully compared, that the conclusion is drawn that the material in question is fibro‘in.Lastly tbe egg shells of the Aplysia were examined; their organic constituent ap2eared to be allied to keratin by its reactions, and inVEQETABLE PHYSIOLOGY AND AGRICULTURE. 237 elementary analysis i t was found to be intermediate between conchiolin and elastin. The general conclusion drawn is that the substance in question is one of the keratins. Action of Yeast on the Animal and Human Organism. By J. NEUMAYER (Clrem. Centr., 1890, ii, 247-248; from Inaug. Diss. Miinchen. Hygien. Inst.) .-The author finds that the various yeasts pass through the alimentary canal without suffering any change, and are not acted 09 by the gastric juice, and that they may be eaten without any harm to the aiiima.1, provided that all fermentable sub- stances aro absent, otherwise inflammation of the stomach ensues.This injurious action is not due to the yeasts, or the principal pro- ducts of their fermentive action, but to abnormal fermentation pro- ducts formed at the high temperature of the body; if the fermenta- tion proceeds at law temperatures, these injurious products are not formed a t all, or only in illsignificant amount. Subcutaneous injection of the yeasts causes their destruction, without, however, producing any ill effects on the animal. W. D. H. J. W. L.PHYSIOLOGICAL CHEMISTRY.P h y s i o l o g i c a l Chemistry.233Roteid Absorption. By R. NEUMEISTER (Zeit. Bid., 27,309--373).-Many observers have found that a proteid may beabsorbed without previous conversion into peptone ; for instance, inthe case of nutrient enemata.It also appears that a first stage in theaction of the digestive juices is simply to dissolre the proteid ; changesof the natnre of hydration then follow. Hasebroek (Abstr., 1887,609) showed that this was the case with fibrin. It is equally true forcoagulated white of egg, although whether the dissolved albumin isthe same as the original albumin is uncertain ; i t is certainly not aglobulin ; serum albumin, vitellin, and other proteids are also similarlysimply dissolved, in the first instance, by the gastric and pancreaticsecretions. Casein and haemoglobin are exceptions to t,his rule. Caseinis first converted into an insoluble curd by the rennin of the stomach,and hemoglobin is decomposed into hsematin and a, proteid residue.When various prote'ids are introduced directly into the bloodstream, there are differences again noticeable.Casein and hemo-VOL. LX, 234 ABSTRACTS OF CHEMICAL PAPERS,globin solutions act like foreign substances, and are excreted by thekidneys, Egg albumin is similarly got rid of; b u t in case of bloodtransfusion, thero is no albuminuria ; the same is truc for the injectionof serum, or of solutions of pure serum albumin, of sgntonin (pre-pared either from white of egg or myosin), and of crystalline phyto-vitellin. These proteids, among which are to be noted several whichare not normal constituents of the blood, are thus directly assimil-able, without, having undergone peptonisation.In fact, it is well known that albumoses and peptones introducedinto the circulation are not assimilable, but, like other foreign sub-stances, are excreted by the kidneys (compare Abstr., 1888, 516).Dextrose is similarly got rid of, if its percentage in the blood ishigher than normal; the question thus arises, whether peptoneshoald be considered as on all fours with dextrose in this respect.That it cannot be, but that it is an absolutely foreign substance isshown by the fact that practically it all appears in the urine, and thati n normal blood no peptone or peptone-like substance is present.The word peptone may here be conveniently employed to include thealbumoses, for all these products of proteolysis are in this respect thesame (including hetero-albumose and atmidalbumin, concerning whichexperiments are now, for the first time, given).Peptone thus disappears rapidly from the blood after injection ;this occurs also when none can escape from the kidneys, either byligaturing the ureters, or by injecting such a large amount that thelowering of blood pressure so produced stops urinary secretion.Underthese circumstances, it is discharged into the intestinal canal.Peptone is therefore a form of proteid not assimilable by livingcells. Previous experimenters have attemptod to answer the ques-tion where the peptone formed in the alimentary canal is reconvertedinto normal prote'ids. Salvioli could find none in the blood circulat-ing in the stomach walls, although the stomach was full of peptone.Hofmeister corroborated this ; and in the present research a numberof observations, in which an artificial circulation was kept up, led tothe same conclusion that some element, either in the interior of thealimentary canal or in the wall of the same, effects the disappearanceof peptone; no other tissue produces this change.The generaloutcome of these experiments is as follows ; without doubting theexistence of micro-organisms which cause the disappearance ofpeptone ( M . restitueny of J. Brinck, Abstr., 1889, 632 ; compare alsoN. Popoff, Abstr., 1889, 632), it is probable that the regeneration ofalbumin from peptone occurs not before, but concomitantly with,absorption. The methods of Brinck and Popoff were not carefullyconducted from a chemical standpoint ; no doubt their peptone wasmixed with albumin ; they put t5is mixture into the stomach, andwithdrew i t after half-an-hour ; by that time the paptone had beenabsorbed, and the fluid, minus its peptone, was now able to keep thefrog's heart beating; whereas, their conclusion was that the peptone hadbeen converted into serum albumin.The question then arises, dothe ljmphojid cells or the epithelium cells of the stomach and intes-tinal walls produce this effect? The fact that the white bloodcorpuscles are not able t o effect the change when peptone is injectePHY SIOLOGICATA CHEXISTRY. 235into the blood stream is considered sufficient to refute the conclusionarrived at by others that the lymph cells are the active aKents ; infact, most physiologists are now pretty well agreed that it is theepithelial elements with which, in this connection, we have to reckon,and their dehydrating action on the peptones is comparable to that ofthe liver cells in converting sugar into glycogen.The question whether the liver cells have any action on peptone isan interesting one.In most animals, artificial circulation of fluidcontaining peptone through the recently-removed and still-livingorgan led to a negative result; but in the case of the rabbit, the livqrcells were found to possess the power seemingly limited in otheranimals to the columnar cells of the wall of the alimentary canal. Itcannot be, however, supposed that weighty conclusions can be drawnfrom an exceptional case; and even in the rabbit, the liver cellscannot normally fulfil this function, since the portal vein is alwaysfree from peptone, as in other animals.Such observations are alsoof importance in view of Seegen’s remarkable conclusion that theforma.tion of sugar in the liver occurs, not a t the expense of thehepatic glycogen, but of the peptone brought to the liver by theportal vein (Abstr., 1888, 172). Much of the present paper isdevoted t o an examination of Seegen’s work, and the general natureof the criticisms, and of the experiments performed to negative hisassertions, will be gathered from what has preceded this.Throughout this paper, great care is taken to point out the methodsto be adopted in the separation of peptones and albumoses from oneanother, and from other proteids, and the fallacious results obtainedbefore the time of the introduction of ammonium sulphate as areagent for this purpose.Among the points taken up, it is shownthat a so-called peptone described as existing in eggs (W. Fischel,Abstr., 2886, 166) is not a true peptone. The namepseudopeptone issuggested for it.Cystin in Pancreatic Digestion. By E. KULZ (Zeit. Biol., 27,415417).-The question, as to what becomes of the sulphur ofproteids during digestion has never been completely answered. In thepresent examination of the products of an artificial pancreatic diges-tion, no hydrogen sulphide was evolved. The insoluble productswere removed by filtration, and the filtrate concentrated ; during thisprocess, a precipitate formed, but after removal this was not found tocontain cystin.The final filtrate, after o, time, deposited 8 whiteprecipitate insoluble in water, but soluble in ammonia. The ammo-niacal solution was diluted with large quantities of water, and six-sided crystals separated, which, after purification by recrystallisation,gave all the reactions of cystin. Whether this is always the case,or if bacteria are concerned in the process, are questions that havestill to be settled. W. D. H.W. D. H.The so-called Liver of Helix pomatia. By M. LEVY (Zkit.BioE., 27, 398414).-The chief intestinal gland of the snail Eelixyomatia is a digestive gland, but is not analogous to any of theabdominal glands of the higher animals.The weight of its organicr 236 ABSTRACTS OF CHEDfICAL PAPERS.constituents is very constant, being the same in summer and winter,and in great measure they are the same in kind in all periods of theyear. The alcoholic extract of the gland shows the chlorophyllspectrum (MacMunn’s enterochlorophyll). The digestive fermentspresent are a diastatic, n peptic, but not a tryptic one. The pepticferment appears to be idantical with Krukenberg’s helicopepsin. Thediastatic ferment disappears during the winter sleep ; it is capable ofdigesting raw starch, but has no effect on cellulose. A fat emulsifyingaction is shown by the secretion in the summer time, but this alsodisappears during hibernation.The ferment by means of which this action is brought about is notidentical with the one described by Schmiedeberg (Arch.exper. Path.Pharm., 14) as histozyme. Histozyme, which was separated frompigs’ kidneys, is concerned in the splitting up of hippuric acid. Thesnail’s ferment has no such action.Glycogen with sinistrin was generally present in the organ, but alltests for bile gave a negative result.A list of the substances separable from the organ is as follows :-(1.) In the alcoholic extract : Chloropliyll, lecithin, oleic acid, fatty(2.) In the ethereal extract : A trace of fat.(3.) In the aqueous extract : Sugar, globulin (coagulating at 66”),glycogen, sinistrin, hypoxanthine, and other bases precipitable byphosphotungstic acid ; in the ash, potassium, sodium, calcium, magne-sium, iron (traces), manganese, chlorine, and phosphoric and sulphuricacids.Jecorin was also absent.acids, ash, chlorine, and phosphoric and sulphuric acids.In winter animals, silica was found in addition.W.D. H.Organic Basis of Various Shells. By W. ENGEL ( Z e d . Biol.,27, 374--385).-Numerons previous researches liave been directed t othe determination of the inorganic constituents of egg shells, b u tthose relating to their organic constituents are scanty.The shells of a number of snakes, which were preserved for micro-scopic purposcs in Kleinenberg’s solution, were freed from picricacid by prolonged washing with water, alcohol, and ammonia.Elementary analysis of their organic substratiim gave the followingpercentage results :-C, 54.68 ; N, 16.37 ; H, 7-24 ; 0, 21.1.Thesecoincide very well with the percentage composition of elastin, asworked out by previons investigators. The reactions of this sub-stance are, moreover, identical with those of elastin; Rome slightdifferences in solubility, especially in alkalis, are not considered suffi-cient to negative the general conclusion tbat the material in questionis elastin, since elastin prepared from various sources itself exhibitssimilar differences in solubility.The cover of the incubating cells of wasps was next investigated ;and although the quantity of material available was not sufficient forelementary analysis, the colonr tests and solubilities of the substanceare so like those of fibroin, with which it was carefully compared, thatthe conclusion is drawn that the material in question is fibro‘in.Lastly tbe egg shells of the Aplysia were examined; their organicconstituent ap2eared to be allied to keratin by its reactions, and iVEQETABLE PHYSIOLOGY AND AGRICULTURE. 237elementary analysis i t was found to be intermediate between conchiolinand elastin. The general conclusion drawn is that the substance inquestion is one of the keratins.Action of Yeast on the Animal and Human Organism. ByJ. NEUMAYER (Clrem. Centr., 1890, ii, 247-248; from Inaug. Diss.Miinchen. Hygien. Inst.) .-The author finds that the various yeastspass through the alimentary canal without suffering any change, andare not acted 09 by the gastric juice, and that they may be eatenwithout any harm to the aiiima.1, provided that all fermentable sub-stances aro absent, otherwise inflammation of the stomach ensues.This injurious action is not due to the yeasts, or the principal pro-ducts of their fermentive action, but to abnormal fermentation pro-ducts formed at the high temperature of the body; if the fermenta-tion proceeds at law temperatures, these injurious products are notformed a t all, or only in illsignificant amount. Subcutaneous injectionof the yeasts causes their destruction, without, however, producingany ill effects on the animal.W. D. H.J. W. L

ISSN:0368-1769    

DOI:10.1039/CA8916000233

出版商:RSC    

年代:1891

数据来源: RSC

摘要:

VEQETABLE PHYSIOLOGY AND AGRICULTURE. 237 Chemistry of Vegetable Physiology and Agriculture. The Antiseptic Properties of Podium Fluoride. By 0. HEWELKE (Chem. Centr., 1890, ii, 248; from Deut. 31d. Wiss., 16, 477478) .-The author experimented with alkaline sodium fluoride on the ferment, and the alkalino fermentation of urine. Torula cemvisce did not grow in the presence of 1 part of sodium fluoride in 100 to 300 parts of urine ; in presence of 1 : 60G to 3000 the fer- mentation was distinctly checked, and this was noticeable, although i n a minor degree, when the proportion of sodium fluoride was reduced t o 1 : 4000. In tho case of urine without any sodium fluoride, the fermentation commenced at the end of 3 to 5 days; the addition of 1 part to 2000 of urine prevented fermentation until the 14th-15th day.; -1 : 600 till the 60th day ; 1 : 100 over a month.Blood, with the addition of 1 part of sodium fluoride to $0-160, remained gsod for ti long period, and a disagreeable odour was first developed at the end of several weeks. In nutrient substances containing 1 of sodium fluoride : 150 to 200, neither pathogenic nor non-pathogenic organisms developed, and even when the proportion of the salt mas reduced to 1 : 600, evidences of a checked growth were observable. Some organisms proved more Susceptible t.han others, for instance 1 : 300 prevented the growth of Bacillus anthracis. In general, the pathogenic organisms proved the most susceptible. J. W. L. By 0. LOEW (Ber., 23, 3125-3126).-As, in all probability, the sulphur in albumino'ids is not present in the form of a sulphonic group, it must be assumed that hydrogen sulphide is formed from sulphates in the Catalytic Reduction of the Sulphonic Group.238 ABSTRACTS OF CHEMICAL PAPERS.vegetable organism, and that a t the moment of its formation it is further converted into an organic compound, that is to say, it takes part in the production of albuminoids. The most plausible explanation of this phenomenon is, that the intense atomic vibrations in the active albumin are communicated to the sulphates and t o the dissolved organic matter, causing them to act on oDe another in such a way that the oxygen of the sulpliuric acid acts on the organic matter, the hydrogen of the latter combining with the sulphur : in other words, it may be supposed that oxidation and reduction take place simultaneously under the influence of a catalytic action.Experiments which were made with various sulphates in presence of platinum black did not gire the expected results ; sodium hydroxy- methylenesulpbonate (formaldehyde sodium hydrogen snlphite), on the other hand, is reduced moderately easily. On warming a solution of this organic salt (5 grams) and crptalline sodium carbonate (10 grams) in water (100 grams) with platinurn black (16 grams), in a flask which is nlmost completely filled with the solution, an odour of leeks is observed after some hours, and the solution then gives the nitroprusside reaction for sulphides ; on acidifying with acetic acid, hydrogen sulphide is evolved, showing that sodium sulphide has been formed by reduction, whilst a corresponding quan- tity of the sodium hydroxmethylenesulphonate must have undergone oxidation.When the quantity of the organic sodium salt and platinum black is increased, the solution gives off an odour Tery like that of decomposing albuminojids, probably owing to the formation of methyl rnercaptan ; if platinum black is not added to the solution, reduction does not take place. The above reaction is not due to nascent hydrogen, as this gas is not evolved when a dilute solution of formaldehyde is warmed with platinum black and sodium carbon- ate. F. s. K. Chemical Composition of Vegetable Cell Membranes. By E. SCHULZE (Ber., 23, 3175; compare Abstr., 1890, 1456).-The author explains that he did not mean it to be inferred that cellulose is the only constihent of the cell envelope which is insoluble in dilute acids.J. B. T. Crystalline Constituents of the Seeds of Cataputize minoris. By Y. TAHARA (Ber., 23, 3347--3351).--The seeds are carefully freed from oil, extracted repeatedly with alcohol, the alcohol evaporated, the residae washed with ether, and boiled with alcohol ; on cooling the solution, brown crystals of ausculetol are deposited, which may be purified by treatment with lead acet.ate. If the oil is allowed to remain for some time in a closed flask, a substance separates which crystalIises from alcohol in colourless, odonrless prisms melting at 193" ; it is insoluble in water, alkalis, or acids, and bas not yet been further investigated. J. B. T. Kesso Oil. By J. BERTRAN and E.GILDEMEISTER (Arch. Pharm., 228,483492) .-Kesso is the Japanese name for Valeriana oficinalisVEQETABLE PHYSIOLOGY AND AORIOULTURE. 239 vur. nngustifo'olia ; the oil obtained by distilling the root of this plant with steam has a sp. gr. of 0.996, whilst the sp. gr. of oil of vderian is 0.945. A large quantity of kesso oil was divided into three portions by distillation with steam. The first portion was fractionated into six portions. 1. Up to 155", contained much acetic and valeric acids, but no formic acid. Probably some valeraldehyde was present, judging by the odour. 2. That boiling between 153" and 160" was relatively small in amount, and consisted of lavopinene, the rotation in Wild's apparatus, with a column 100 mm. long, being 55' 5' to the left.4. That boiling between 170" and 180" consisted of dipentene, as shown by the formation of its hydrochloride and hydrobromide. 5. That boiling between 180" and 200" is not given. 6. That boiling between 200" and 220' contsined terpinol, CloHn*OH. On shaking it up with a strong aqueous hydriodic acid solution, the compound C10H16,2HI was obtained, which melted at 76". The second portion, boiling between 220" and 290", yielded a fraction below 260", composed of borneol with acetic and isovaleric acids. The fraction boiling between 260' and 280" was a clear liquid, consisting, apparently, of sesquiterpene. The third portion of the distillate was heavier than water, and boiled about 300". This was saponified, and yielded acetic acid, ft bluish oil, whose composition has not yet been made out, and kessyl alcohol, C,rH2rOz.This alcohol is odourless, insoluble in water, easily soluble in alcohol, ether, chloroform, benzene, and light petroleum. It melts at 85", and boils under a pressure of I1 mm. between 155" and 156", and at the ordinary pressure at 300-302" without decom- position. A 10 per cent. solution in alcohol has a rotatory power of 3" 39' to the left in a column 100 mm. long. It readily forms well- shaped, rhombic crystals from i t s solution in alcohol or ether [a : 2, : c = 0.9936 : 1 : 0.43691. Kessyl alcohol alone, or dissolved in dry ether, in contact with acetic chloride or phosphorus penta- chloride, develops heat, evolves hydrogen chloride, and produces a splendid, dark, cherry-red solution. Kessy I acetate, C14H2302A~, was obtained by heating the alcohol with acetic anhydride and some anhydrous sodium acetate.It can also be obtained by fractional distillation of the kesso oil, but is impure when thus produced. The pure acetate is a thick, colourless oil, of very faint odour, which does not solidify at -20". It is insoluble in water, easily soluble in ether, alcohol, chloroform, and light petroleum. Its is laevorotatory to the extent of 70" 6' in u, column 100 mm. long. Oxidation products of kessyl alcohol have not yet been fully investigated. Poisonous Action of Hydrazine. By 0. LOEW ( B e y . , 23, 3203-3206) .-Hydrazine exerts an extremely poisonous action on organisms of the most varying description. In a solution containing, in addition to food substances, 0.2 gram of hydrazine sulpbate per litre, the shoots of the heliantlius and of barley were rapidly killed.Alpre, fission organisms, moulds, r3'chizoi7rycetes, and lower water organisms were also rapidly destroyed by its dilute solution. A dose 3. That boiling between 160" and 170" is not given. This fraction also contained borneol. J. T.240 ABSTRACTS OF OHEMICAL PAPERS. of 0.1 gram of hydrazine sulphate neutralised with sodium carbonate, and administered subcutaneously to a guinea-pig, caused death in 24 hours, and a doso of 0.5, gram, administered to a puppy in a similar Composition of Sorghum Seed. By H. W. WILEY (Bied. Centr., 1890, 678-680) .-The following is the mean percentage composition of 84 sa,mples sorghum seed, hulled and unhulled :- manner, brought about the same result in 24 hours.H. G. c. Unhulled. Moisture ..................... 9.93 Albuminoids. ................. 10.54 Ether extractive .............. 0.61 Absolute alcohol extractive .... 2.44 80 per cent. alcohol extractive . . 2.91 Fibre.. ...................... 3.17 Ash ......................... 2.05 Carbohydrates ................ 64.62 Light petroleum extractive .... 3.72 Hulled. 9.63 11-39 3-16 0.34 1.46 1.78 1.83 1.69 68.86 This seed, compared with wheat, maize, and oats, appears to be equal i n feeding value to maize and oats, and only rather poorer than wheat. The seed hulls contain n colonring matter which, however, is not harmful t o cattle, nor does it contain any tannin. E. W. P.VEQETABLE PHYSIOLOGY AND AGRICULTURE. 237Chemistry of Vegetable Physiology and Agriculture.The Antiseptic Properties of Podium Fluoride.By 0.HEWELKE (Chem. Centr., 1890, ii, 248; from Deut. 31d. Wiss., 16,477478) .-The author experimented with alkaline sodium fluorideon the ferment, and the alkalino fermentation of urine. Torulacemvisce did not grow in the presence of 1 part of sodium fluoride in100 to 300 parts of urine ; in presence of 1 : 60G to 3000 the fer-mentation was distinctly checked, and this was noticeable, althoughi n a minor degree, when the proportion of sodium fluoride was reducedt o 1 : 4000. In tho case of urine without any sodium fluoride, thefermentation commenced at the end of 3 to 5 days; the addition of1 part to 2000 of urine prevented fermentation until the 14th-15thday.; -1 : 600 till the 60th day ; 1 : 100 over a month.Blood, with theaddition of 1 part of sodium fluoride to $0-160, remained gsod for tilong period, and a disagreeable odour was first developed at the endof several weeks.In nutrient substances containing 1 of sodium fluoride : 150 to200, neither pathogenic nor non-pathogenic organisms developed, andeven when the proportion of the salt mas reduced to 1 : 600, evidencesof a checked growth were observable. Some organisms proved moreSusceptible t.han others, for instance 1 : 300 prevented the growth ofBacillus anthracis. In general, the pathogenic organisms proved themost susceptible. J. W. L.By 0. LOEW(Ber., 23, 3125-3126).-As, in all probability, the sulphur inalbumino'ids is not present in the form of a sulphonic group, it mustbe assumed that hydrogen sulphide is formed from sulphates in theCatalytic Reduction of the Sulphonic Group238 ABSTRACTS OF CHEMICAL PAPERS.vegetable organism, and that a t the moment of its formation it isfurther converted into an organic compound, that is to say, it takespart in the production of albuminoids.The most plausible explanation of this phenomenon is, that theintense atomic vibrations in the active albumin are communicated tothe sulphates and t o the dissolved organic matter, causing them toact on oDe another in such a way that the oxygen of the sulpliuricacid acts on the organic matter, the hydrogen of the latter combiningwith the sulphur : in other words, it may be supposed that oxidation andreduction take place simultaneously under the influence of a catalyticaction.Experiments which were made with various sulphates in presenceof platinum black did not gire the expected results ; sodium hydroxy-methylenesulpbonate (formaldehyde sodium hydrogen snlphite), onthe other hand, is reduced moderately easily.On warming a solutionof this organic salt (5 grams) and crptalline sodium carbonate(10 grams) in water (100 grams) with platinurn black (16 grams),in a flask which is nlmost completely filled with the solution, anodour of leeks is observed after some hours, and the solution thengives the nitroprusside reaction for sulphides ; on acidifying withacetic acid, hydrogen sulphide is evolved, showing that sodiumsulphide has been formed by reduction, whilst a corresponding quan-tity of the sodium hydroxmethylenesulphonate must have undergoneoxidation.When the quantity of the organic sodium salt andplatinum black is increased, the solution gives off an odour Tery likethat of decomposing albuminojids, probably owing to the formationof methyl rnercaptan ; if platinum black is not added to the solution,reduction does not take place. The above reaction is not due tonascent hydrogen, as this gas is not evolved when a dilute solutionof formaldehyde is warmed with platinum black and sodium carbon-ate. F. s. K.Chemical Composition of Vegetable Cell Membranes. ByE. SCHULZE (Ber., 23, 3175; compare Abstr., 1890, 1456).-Theauthor explains that he did not mean it to be inferred that celluloseis the only constihent of the cell envelope which is insoluble indilute acids.J. B. T.Crystalline Constituents of the Seeds of Cataputizeminoris. By Y. TAHARA (Ber., 23, 3347--3351).--The seeds arecarefully freed from oil, extracted repeatedly with alcohol, the alcoholevaporated, the residae washed with ether, and boiled with alcohol ;on cooling the solution, brown crystals of ausculetol are deposited,which may be purified by treatment with lead acet.ate.If the oil is allowed to remain for some time in a closed flask, asubstance separates which crystalIises from alcohol in colourless,odonrless prisms melting at 193" ; it is insoluble in water, alkalis, oracids, and bas not yet been further investigated. J. B. T.Kesso Oil.By J. BERTRAN and E. GILDEMEISTER (Arch. Pharm.,228,483492) .-Kesso is the Japanese name for Valeriana oficinaliVEQETABLE PHYSIOLOGY AND AORIOULTURE. 239vur. nngustifo'olia ; the oil obtained by distilling the root of this plantwith steam has a sp. gr. of 0.996, whilst the sp. gr. of oil of vderianis 0.945.A large quantity of kesso oil was divided into three portions bydistillation with steam. The first portion was fractionated intosix portions. 1. Up to 155", contained much acetic and valeric acids,but no formic acid. Probably some valeraldehyde was present,judging by the odour. 2. That boiling between 153" and 160" wasrelatively small in amount, and consisted of lavopinene, the rotationin Wild's apparatus, with a column 100 mm.long, being 55' 5' to theleft. 4. Thatboiling between 170" and 180" consisted of dipentene, as shown by theformation of its hydrochloride and hydrobromide. 5. That boilingbetween 180" and 200" is not given. 6. That boiling between 200"and 220' contsined terpinol, CloHn*OH. On shaking it up with astrong aqueous hydriodic acid solution, the compound C10H16,2HI wasobtained, which melted at 76".The second portion, boiling between 220" and 290", yielded afraction below 260", composed of borneol with acetic and isovalericacids. The fraction boiling between 260' and 280" was a clear liquid,consisting, apparently, of sesquiterpene.The third portion of the distillate was heavier than water, andboiled about 300". This was saponified, and yielded acetic acid, ftbluish oil, whose composition has not yet been made out, and kessylalcohol, C,rH2rOz.This alcohol is odourless, insoluble in water, easilysoluble in alcohol, ether, chloroform, benzene, and light petroleum.It melts at 85", and boils under a pressure of I1 mm. between 155"and 156", and at the ordinary pressure at 300-302" without decom-position. A 10 per cent. solution in alcohol has a rotatory power of3" 39' to the left in a column 100 mm. long. It readily forms well-shaped, rhombic crystals from i t s solution in alcohol or ether[a : 2, : c = 0.9936 : 1 : 0.43691. Kessyl alcohol alone, or dissolvedin dry ether, in contact with acetic chloride or phosphorus penta-chloride, develops heat, evolves hydrogen chloride, and produces asplendid, dark, cherry-red solution.Kessy I acetate, C14H2302A~, wasobtained by heating the alcohol with acetic anhydride and someanhydrous sodium acetate. It can also be obtained by fractionaldistillation of the kesso oil, but is impure when thus produced. Thepure acetate is a thick, colourless oil, of very faint odour, which doesnot solidify at -20". It is insoluble in water, easily soluble inether, alcohol, chloroform, and light petroleum. Its is laevorotatoryto the extent of 70" 6' in u, column 100 mm. long. Oxidation productsof kessyl alcohol have not yet been fully investigated.Poisonous Action of Hydrazine. By 0. LOEW ( B e y . , 23,3203-3206) .-Hydrazine exerts an extremely poisonous action onorganisms of the most varying description.In a solution containing,in addition to food substances, 0.2 gram of hydrazine sulpbate perlitre, the shoots of the heliantlius and of barley were rapidly killed.Alpre, fission organisms, moulds, r3'chizoi7rycetes, and lower waterorganisms were also rapidly destroyed by its dilute solution. A dose3. That boiling between 160" and 170" is not given.This fraction also contained borneol.J. T240 ABSTRACTS OF OHEMICAL PAPERS.of 0.1 gram of hydrazine sulphate neutralised with sodium carbonate,and administered subcutaneously to a guinea-pig, caused death in24 hours, and a doso of 0.5, gram, administered to a puppy in a similarComposition of Sorghum Seed. By H. W. WILEY (Bied. Centr.,1890, 678-680) .-The following is the mean percentage compositionof 84 sa,mples sorghum seed, hulled and unhulled :-manner, brought about the same result in 24 hours. H. G. c.Unhulled.Moisture ..................... 9.93Albuminoids. ................. 10.54Ether extractive .............. 0.61Absolute alcohol extractive .... 2.4480 per cent. alcohol extractive . . 2.91Fibre.. ...................... 3.17Ash ......................... 2.05Carbohydrates ................ 64.62Light petroleum extractive .... 3.72Hulled.9.6311-393-160.341.461.781.831.6968.86This seed, compared with wheat, maize, and oats, appears to beequal i n feeding value to maize and oats, and only rather poorer thanwheat.The seed hulls contain n colonring matter which, however, is notharmful t o cattle, nor does it contain any tannin. E. W. P

ISSN:0368-1769    

DOI:10.1039/CA8916000237

出版商:RSC    

年代:1891

数据来源: RSC

摘要:

240 ABSTRACTS OF OHEMICAL PAPERS. An a1 y t i c a1 C h e m i s t r y. Gas Apparatus, &c. By W. E. ADENEY (C'hem. News, 62, 196-199 ; 204--206).-1n this apparatus, the pressure and measur- ing tubes are placed some little distance apart, the latter only being surrounded by a, water-jacket: they are connected at their lower extremities (which are bent at right angles for the purpose, the measuring tube being likewise narrowed) by wired india-rubber tubing and ti glycerol joint. The pressure tube is furnished near the bend with a side tube connecting with the mercury reservoir, and termi- nates at the top with a Friedrich's patent glass stop-cock, so that it can be used either open or closed ; i t is 1000 mm. high. The measur- ing tube, 640 mm. long, is wide for about two-thirds of its length, but is narrower at the upper portion, to which a Friedrich stop-cock is attached, and this is connected with two capillary, double right- angled tubes, one of wider bore, for the admission of the gas to be examined, or other object; the second and narrower one passing to the laboratory vessel, which is furnished at the top with a cup, into which the tube fits, and is rendered air-tight by an indk-rubber collar.The laboratory vessel, which may be of any convenient capacity, is provided with plat-inum wires for explosions, and, moreover, termin- ates below in a narrow cylindrical portion, which may be usedANALYTICAL CHEMISTRY. 241 open, or be closed with a cork, and to which is attached side tnbe, connecting with an independent mercury reservoir to facilitate filling with mercury, transferences, &c.A suitably bent tube, with india- rubber attachment, is fitted to the cork, and serves for the admission of reagents. Behind the whole length of the pressure tube a long, narrow mirror, graduated in millimetres on an unsilvered portion, is fixed at such an angle as to reflect a good image of the mercury column and meniscus. The whole apparatus is mounted on a wooden support, with necessary clamps, attachments, &c. ; tbe mercurF reservoirs being placed behind. The apparatus serves for all kinds of gas measurements, as an air-pump, and for distillations under reduced pressure or in a vacuum. Lacmo'id. By 0. FORSTER (Zeit. ang. Chent., 1890, 163-167).- Commercial lacmoid is of very variable character.Some specimens are almost wholly insoluble in water, and are unsuitable as indicators. Others colour boiling water intensely blue, and are fit for use. To prepare the pure blue indicator, the finely-powdered crude material is extracted with boiling water, but stopping short of complete exhaustion, so as to avoid dissolving a sparingly soluble red substance. From fhe cooled and filtered blue solution, the colour is precipitated by feebly acidifying, and after some hours is collected on a filter and washed with cold water, then dried at a low temperature (since some decomposition takes place if it be dried at looo), or dissolved in alcohol, and the solution evaporated on the water-bath. Purified in this way, it gives, with pure distilled water, a blue solution, having a slight tendency to violet, and exceeds all other indicators in sbarp- ness.In wafer containing carbonic acid or au ammonium salt, it gires an exceedingly sharp change with a quantity of alkali, which has scarcely any efl'ect on litmus. To prepare blue lacmo'id paper, sulphuric acid is added to an alcoholic solution of lacruoi'd, until white paper dipped into the liquid is coloured red. This will become blue on drying. The depth of blue should be that of the forget-me-not. For red paper, the paper should be dipped in very dilute sulphuric acid and dried before staining. It must be preserved in well stoppered bottles, and is an extremely sensitive indicator for alkalis. A somewhat more ready mode of purification is as follows :- 8 parts of finely-powdered crude lacmo'id is gently warmed for a, quarter of an hoar with 100 parts of 20 per cent.alcohol, and the liquid filtered after cooling. After ascertaining the amount of matter in solution by evaporating a portion, there should be added an alcoholic solntion of 14 parts of malachite green t o 86 parts of the lacmoid. This addition does not impair the indication witb acids, whilst it increases enormously the sharpness of the change to blue with an alkali. The liquid is filtered from a, precipitate which forms, and is then mixed with an equal volume of absolute alcohol. It should be kept in black bottles. Estimation of Free Hydrochloric Acid in Stannous Chloride Solutions. By W. MINOR (Zeit. mag. Chenz., 1890, D. A. L. 11. J. S.242 ABSTRACTS OF CHEMIOAL PAPERS.25--26).-Precipitation as silver chloride cannot be resorted to i n consequence o€ the co-precipitation of tin compounds. A measured quantity (100 c.c.) of the solution is, therefore, satmated hot with hydrogen sulphide, and filtered into a litre flask. Half of the filtrate is boiled to expel hydrogen sulphide, and the total acid then titrated with standard alkali. The amount of tin is now ascertained by titration witb iodine, and the corresponding quantity of hydrochloric a i d deducted from the total. M. J. S. Detection of Hypochlorous Acid in Chlorine Water. By T. SALZER (Chern. Centr., 1890, ii, 472 ; from Pharm. Zeit., 35, 457). -The author recommends the method of Lunge and Naeff, devised for the determination of hypochlorous acid in the presence of chlorine, which depends on the fact that chlorine reacts with potassium iodide and hydrochloric acid, forming potassium chloride, iodine, and hydrochloric acid, whereas hypochlorous acid produces, under the same circumstances, no hydrochloric acid.If, therefore, the solution is first titrated with decinormal alkali and then with thiosulphate solution, the amount of the chlorine and hypochlorons acid may be calculated. Of neutral chloxine water, the author recommends 25 C.C. should be acidified with 10 C.C. of decinormal hydrochloric acid, 1 gram of potassium iodide added, and titrated with thiosulphate. Pure chlorine water should require exactly 10 C.C. of decinormal hydrochloric acid. Chlorine water, containing acid, is not to be recommended as an eye-mash.Detection of Traces of Iodine in the Presence of much Chlorine. By A. JOHKSTONE (Chem. News, 62, 153, 169).-The solution to be tested is treated with a saturated solution of silver nitrate in strong ammonia; a yellow precipitate indicates the presence of an iodide. To c0nfir.m this, add concentrated sulphuric acid, and agitate with carbon bisulphide ; the latter becomes coloui-ed by any liberated iodine. D. A. L. J. W. L. Separation and Estimation of Tellurium. By E. DONATH (Zeit. ang. Chem., 1890, 214-217 ).-Precipitation by sulphurous acid is complete but tedious. Kastner’s grape-sugar method (Abstr., 1876, 440) is accurate and expeditious. Precipitation by stannous chloride or an alkaline fitannite is not suitable, since the precipitate always contains tin.Tellurium is very rapidly precipitated from acid solutions by hyposulphurous acid. The yellow solution obtained by shaking scrap zinc with aqueous sulphurous acid is filtered, and added to the cold concentrated hydrochloric acid solution of the tellurium compound. Precipitation is complete in 15 minutes. The washed precipitate, which may contain some tellurium sulphide, is riused into a tared capsule, oxidised with strong nitric acid, and, after gentle ignitiol;, weighed as tellurium dioxide. For. the attack of ores containing tellurium, 3 or 4 grams of the impalpable powder is treated in a basin with small quantities of con- centrated nitric acid, and from the pasty mass obtained, the excess of acid is completely evaporated at a temperature which will not decom-ANALYTICAL CHEMISTRY.243 pose the metallic nitrates. The dry mass is powdered in the basin, moistened with strong soda solution, and digested for half an hour. Water is then added, the filtrate boiled for 20 minutes with pure grape- sugar, and the precipitated tellurium weighed as dioxide, as above. M. J. S. Estimation of Hypophosphorous, Phosphorous, and Hypo- phosphoric Acids. By L. AMAT (Conzpt. rend., 111,676-679).-1~ a warm acid solntion, hypophosphoric acid reduces mercuric chloride to the mercurous salt, and is itself completely converted into phosphoric acid, probably in consequence of an intermediate conversion into phosphorous and phosphoric acids. About 1 gram of the substance is mixed with 10 C.C. of concentrated hydrochloric acid, evaporated almost to dryness in order to promote the decomposition of the hypo- phosphoric acid, redissolved in a fimall quantity of water, and mixed with a solution containing 69 grams of mercuric chloride and 20 to 40 C.C.of concentrated hydrochloric acid per litre. The mixture is allowed to remain for 24 hours at 80°, and the mercurous chloride is collected and weighed. Potassium permanganate can be employed in the manner indicated by P. de St. Gilles, the substance being oxidised by excess of the permanganate and the excess determined by means of oxalic acid. The oxidation is more rapid, the more concentrated the solution, the greater the proportion of free acid, and the higher the temperature. At a high temperature, a small quantity of permanganate may be decomposed, and a t a low temperature, especially in dilute solutions, oxidation is incomplete ; careful attention to the conditions is there- fore necessary.The permanganate employed should be equivalent to a solution containing 63 grams of oxalic acid per iitre, and the quantity of sub- stance taken for analysis sbould reduce about 20 C.C. of the perman- ganate. The substance is dissolved in 20 C.C. of water, mixed with 3 C.C. of concentrated sulphuric acid, cooled, mixed with 35 C.C. OE per- manganate, and heated at 50" for half an hour. 20 C.C. of oxalic acid solution is then added, and after the liquid has become colourless and the brown precipitate has completely dissolved, the excess of osalic acid is determined by means of permsnganate. The method is applicable to phospbites, pyrophosphites, and hypophosphites.In the case of hhophosphates, the liquid is first heated with the sulphuric acid a t 80-100" for half an hour, and then cooled and mixed with the per- mangsnate. The mercuric chloride method, although the more tedious, is the more accurate of the two. C. H. B. The '6 Citrate Method" of Phosphoric Acid Estimation. By 0. REITNAIR (Zeit. any. Chem., 1890, 19-25, 196-210; continued from Abstr., l890,416).-Comparing the results yielded by the citrate method, under a great variety of conditions, with those furnished by precipitation by molybdate, the author has investigated the amount of the error of deficiency due to imperfect precipitation of the phos- phoric acid, and that of the error of excess due to conta.mination of the precipitate by impurities.His conclusions are as follows :-In244 ABSTRAOTS OF CHEMIOAL PAPERS. all modifications of the citrate method, the precipitation of the phos- phoric acid is incomplete, and with large proportions of citrate and a small amount of magnesia, it may be very seriously so. In the most faavowable cases, about 2 milligrams of magnesium pyrophosphate passes into the filtrate. On the other hand, when calcium, iron, aluminium, or manganese is present, a variable portion of those bases will always be found in the precipitate, and, if enough magnesia mix- ture has been used, a compensation of errors is possible. The use of & minimum quantity of ammonium citrate, in accordance with the pro- cedure of Brassier and Glaser (Abstr., 1885, 837), is not permissible ; an excess is always requisite, The quantity of magnesia mixture must, however, always be proportioned t,o the amount of citrate.The bases which chiefly contaminate the precipitate are calcium and manganese. Both are precipitated in the form of ammonio-phosphates, which aro converted into pyrophosphates on ignition. Of iron and aluminium, there are usually only traces precipitated ; the principal effect of these metah in the solution is to retard the precipitation of the magnesium ammonium phosphate. Grupe and Tollens have stated that magnesia, .or a basic magnesium salt, is precipitated together with the ammonio- phosphate. This is certainly true, since the ignited precipitate always shows the reaction of an orthophosphate with silver nitrate, but if the magnesia mixture has been added by drops to an ammoniacal solution (2.5 per cent.of ammonia), the magnesium oxide in the precipitate will be scarcely weighable. But, using nearly neutral solutions, and espe- cially when salts of sodium or potassium are present, the amount may be very considerable. The use of hydrochloric acid for dissolving phos- phates containing silica is disadvantageous ; the magnesium precipi- tate will always be st.rongly contaminated with silica, and the amount oE foreign bases precipitated will also be increased. Even when snlphuric acid is used, and the solution is consequently freer from silica, it is to be expected that about 1 milligram will be found in the precipitate. The presence of sulphates has, however, the tendency, other things being equal, to increase the error of deficiency.More- over, since the use of sulphuric acid removes a large part of the lime as sulphate, less ammonium citrate is needed than mould otherwise be the case. Using the process for estimating the phosphoric acid in the soluble portion of a superphosphate, and working upon 1 gram of substance, with 5 grams of citric acid, 25 C.C. of magnesia mixture, and ammonia equal to 2.5 per cent. of the solution, t~ loss of about 2 milligrams, equal t o 0.128 per cent. of phosphoric acid, may be assumed. On the other hand, when examining basic slag, or raw phosphates, the error will be in excess. If silica, and manganese are absent, the amount of the error may be small, but no estimate of its average magnitude can be formed.MI. J. S. Reduction of Arsenic Acid in Analysis. By F. A. GOOCH and P. E. BROWNING (Amer. J. Sci., 40, 66--71).-The authors endeavour to shorten fhe process of reduction of arsenic acid by employing hydriodic acid, instead of sulphurous acid, as the active agent. The process recommended may be snmmarised ab follows :-To the arsenateANALYTICAL OHEMISTRY. 245 in solution are t D be added potassium iodide in excess of the amount needed, according to the equation, to complete the reduction, and 10 C.C. of half and half sulphuric acid. The liquid is to be diluted to about 100 c.c., and boiled rapidly until the volume is decreased to 40 C.C. The colour of the free iodine is to be bleached by cautious additions of sulphurous acid, and the liquid immediately diluted with water and neutralised, first with normal potassium carbonate and after- wards with the hydrogen salt.. The whole is to be cooled and titrated with iodine in the usual manner, starch being used as an indicator.The advantage of this method is in the rapidity with which it may be executed, the whole opcration being completed in half an honr. The average error of the process amounts to 0.13 per cent. of the amount taken. B. H. B. Estimation of Peroxides of the Alkaline Earths. By G. KASSNER (Arch. Pharm., 228, 432435).-A weighed amount of the peroxide (0.2 in the case of the barium compound) is ground with a, little water and washed into a beaker ; then excess (about five times as much) of pure potassium ferricyanide is added. Oxygen is at once evolved, and the reaction is complete when the gas ceases to come off ; the reaction may be accelerated by gently warming the beaker. A considerable amount of water is now added, and excess of sulphuric acid ; the greenish colour which may now appear does not affect t h 0 result.The solution is finally titrated with potassium permanganate solution. Thus, 0.2 gram of peroxide required 15.2 C.C. of perman- ganate (1 C.C. = 0-00576 gram of Fe) ; hence the peroxide contained 74.7 per cent. of peroxide. The old direct process gave 75.13 per cent. The new process may prove useful in cases where an acid solution would be inadmissible ; it is only necessary to filter off an aliquot part of the solution before the acid is added, and then titrate and calculate. J. T. Estimation of Ferric Oxide and Alumina in Phosphatic Manures. By A.STUTZER (Zeit. my. Chem., 1890, 43--44).-Thc author, whilst admitting the superiority of Glaser’s method (Abstr , 1890,420) over that depending on the insolubility of the iron and aluminium phosphates in acetic acid, prefers to weigh the ferric oxide and alumina as such, and not as phosphates. To this end, the solu- tion of 1 gram of the phosphate in hydrochloric acid is made alkaline with ammonia, and then feebly acid with acetic acid. The precipitate is collected and partially washed ; the filter with its contents is re- turned to the same beaker, and digested with 150 C.C. of niolybdate solution. The solution filtered horn the yellow precipitate is made feebly alkaline with ammonia, and warmed for 10 minutes on the water-batb.The precipitate sometimes contains traces of molybdic acid, but if dissolved in hydrochloric acid and reprecipitated by ammonia, the ferric oxide and aluminn are obtained free from all impurities. Valuation of Pyrolusite by means of Hydrogen Dioxide. By A. BAUMANN (Zeit. ang, Chem., 1890, 72--79).-The reaction MnOz -i- HzO, = MnO + 02, which occurs in acid solutions, yields equally good results by gravirnetric, volumetric, or gasometric M. J. S.246 ABSTRACTS OF CHEMICAL PAPERS. methods. The last has already been employed by Lunge (Abstr., 1885, 1162). For accurate work, an ordinar7 50 C.C. nitrometer is scarcely large enough, since not more than 0.18 gram of manganese dioxide could be used, and an error of 0.1 C.C. in reading the volume of the gas would equal 0.2 per cent.in the result. The. eudiometer should be able to measure at least 100 C.C. of gas, and should be surrounded by a water-jacket, that the temperature may be kuown with exactness. Water may be used in the eudiometer instead of mercury. In case the pyrolusite should resist ahtack, the reaction flask may be warmed to 70". 1 C.C. of oxygen at 0" and 760 mm. is equal to 0*003885 gram of Mn02. Gravimetrically, the estimation may be made by weighing the oxygen evolved. Almost any of the forms of carbonic acid apparatus for the estimation by loss of weight may be used. From 2 to 6 grams of the pyrolusite, in impalpable powder, is placed in the reaction flask with 30 C.C. of sulphuric acid (1 part to 3 of water), and 40 C.C. of commercial hydrogen peroxide is placed in the inner tube.Warming should be avoided. For volumetric estimation, an acidified hydrogen peroxide (contain- ing about one-tenth of sulphuric acid) should be made of strength corresponding approximately with a standard permanganate (10 grams per litre). The relation of the solutions is accnrateiy found, and then 0.4 to 1 gram of the pyrolusite is treated with 50 C.C. of the hydrogen peroxide in the cold, and after half an hour with occasional shaking, the excess is titrated back with the permanganate. The presence of ferrous compounds in the pyrolusite leads to high results, since they consume hydrogen peroxide ; in Bunsen's and the ferrous sulphate processes, the error is in the opposite direction. Titration of Permanganate and of Bleaching Powder by Hydrogen Peroxide.By L. VANINO (Zeit. nag. Chern., 1890,SO-83). -To facilitate calculation of the results from the volume of oxygen evolved, tables are given of the weight of 1 C.C. of oxygen and of chlorine respectively, over a sufficiently wide range of temperature and pressure. The author's practice differs in three points from that of Lunge (Zeit. nng. Chem., 1890, 7) ; he prefers an azotometer to the nitrometer ; in the analysis of bleaching powder, he uses feebly acid, instead of alkaline, hydrogen peroxide ; and he compares his results with those of the iodometric method, rather than with Penot's, and finds a closer agreement than did Lunge with the latter. The titra- tiou by permanganate of the residual hydrogen peroxide gives unex- ceptionable results in the assay of bleaching powder.Dry Assay of Tin Ores. By H. 0. HOFFMANN (Chem. News, 62, 157-159 ; 169--170).-This section of the author's paper on the dry assay of tin ores deals with methods depending on fusion with potas- sium cyanide, of which various modifications have been investigated, with and without a salt cover, in chalk- or charcoal-lined crucibles, in porcelain crucibles, with charcoal intermixed with the cyanide, with various qualities of cyanide, &c. The chief source of error appears to be due to the tin, instead of forming a button, being disseminated through M. J. S. M. J. S.ANALP TlCAL CHEMISTRY. 247 the mass of slag, when it cannot subsequently be thoroughly sepa- rated. To obviate this, it is recommended to ram a lot of potassium cyanide into the bottom of the crucible before putting in the ore and flux, so as to form a fused mass for the tin to fall through and accu- mnlate beneath to form a button.As regards impurities, iron pabses into the cyanide, alkaline sulphates and carbonates cause low results owing to the formation of tin sulphides in the first case, and of stan- nates in the second. Impure cyanide gives low and irregular results. By A. ROSENHEIM (Bey., 23, 3208--3210).-The statement attributed to the author by Rothenbach (Bey., 23, 3050; and this vol., p. 18) that sulphurous acid is capable of reducing tungstic acid when present as phosphotungstic acid is incorrect, as he has shown (Abstr., 1889, 762) ihat no reducing action takes place. Rothenbach further states that the violet coloration produced when sulphurous acid is added to a mixture of phosphoric and vanadotungstic acids is not due to the re- duction of the tungstic acid, as vauadiurn tetroxide free from snlph- urous acid also yields the coloration with phosphotungststes.This fact, however, really proves the contrary of Rothenbach’s statement, for vanadium tetroxide, as shown by its action on ferric oxide and am- moniacal silver solutions is a reducing agent, and this is the compound which actually causes the reduction of the tungstic acid, as is shown by the fact that the intensity of the coloration is dependent on the quantity of tungstic acid present, and not on that of the vanadium tetroside. H. G. C . D. A. L. Estimation of Vanadic Acid in Vanadiotungstates.Estimation of Ferrocyanides. By R. ZALOZIECKI (Zeit. ang. ohem., 1890, 210--214).-When a solution of an alkaline ferrocyanide is treated with zinc carbonate and a stream of carbonic anhydride, the whole of the ferrocyanogen is precipitated in the form of a double salt of the alkali metal and zinc. If the operation is performed at the boiling temperature, the reaction takes place according to the equation 3h~t’~FeCy~ + 2ZnC03 = 2Zn2FeCy6,M’4PeCy6 + 4M‘2C03, and the amount of alkaline carbonate produced may be employed as a measure of the ferrocyanide originally present. The zinc carbonate should be prepared by the addition of sodium carbonate to a hot solution of zinc sulphate, as it then subsides and washes readily. It is preserved in the pasty state, and if the quantity added contains an amount of zinc approximately equal to the weight of alkaline ferrocyanide, i t will be amply in excess.The mixture is heated to boiling, and a stream of carbonic anhydride is passed through it for a half to one hour. It is then cooled, diluted to a known volume, filtered, and an aliquot part, of the filtrate is titrated with standard acid, using methyl-orange as indicator. If the original solution had contained alkaline carbonates or sulphides, the amount of these should be ascertained by titration, and the acid they consume deducted froni the total quantity required after treatment with zinc carbonate. Sulphates and chlorides have a disturbing influence, but this can be counteracted by the presence of an excess of alkaline carbonate; thiocyanates and the other con- stituents of prussiate “ metal ” are without influence.Id. J. s.248 ABSTRAOTS OF GHEMIOAL PAPERS. Estimation of Sugar in Blood. By J. SEEUEN (Chein. Centr., 1890, ii, 478-479 ; from Centr. Physiol., 4, 217--222).--The author has found that if, in the estimation of sugar in blood,the coagulum, caused by the addition of iron acetate, be not thoroughly and repeatedly pressed and washed, considerable quantities of sugar may be retained by it., although he has not found the error to be nearly so great as stated by Schenk and by Riihmann. In his first experiments, 5-8 per cent. was retained, and he considers that the sugar may be entirely washed from the coagulum independently of any choice of pre- cipitating agent.J. W. L. Examination of Oils, Fats, and Allied Substances. By T. T. P. B. WARREN (Chem. News, 62, 125; 179-lSO).-The sulphur chloride test recommended in various communications by the author indicates the character but not the probable quantity of the oils in a mixture ; it is, therefore, now suggested to ascertain the latter factor by taking the iodine absorptions, with Hubl's reagent, of the indi- vidual constituent oils as well as of the mixture, and from the data obtained to determine the proportions present, for which purpose methods of calculating are described. Estimation of Formic Acid in presence of Acetic and Butyric Acids. By A, SCALA (Gazzetta, 20,393-396).-The liquid containingthe formate is weighed out into a deep beaker, an excess of a saturated solution of corrosive sublimate added, the whole covered with a clock glass and heated for two hours on the water- bath.The precipitated calomel is collected on a weighed filter, washed with warm water, dried at loo", and weighed. When the acid is present in the free state, it is neutralised before proceeding as above. This metbod gives trustworthy results, and is very sensitive, formic acid precipitating more than 10 times its weight of calomel. S. B. A. A. D. A. L. Modification of Jaffe's Indican Test. By F. OBERMETER (Clzem. Centr., 1890, ii, 273-274 ; from Centr. PhysioZ., 4, 155).-The author precipita.tes the urine with plumbic acetate, avoiding too large an excess, filters through a dry filter, agitates the filtrate with an equal volume of fuming hydrochloric acid, in which 2 to 4 parts of ferric chloride are dissolved in 1000 parts, and extracts finally with chloro- form.The indigo produced by the oxidation of the indican may then be determined colorimetricallp in the chloroform solution. Ferric chloride has the great advantage over others, as an oxidising agent of indican, that it does not affect the indigo produced. J. W. L.240 ABSTRACTS OF OHEMICAL PAPERS.An a1 y t i c a1 C h e m i s t r y.Gas Apparatus, &c. By W. E. ADENEY (C'hem. News, 62,196-199 ; 204--206).-1n this apparatus, the pressure and measur-ing tubes are placed some little distance apart, the latter only beingsurrounded by a, water-jacket: they are connected at their lowerextremities (which are bent at right angles for the purpose, themeasuring tube being likewise narrowed) by wired india-rubber tubingand ti glycerol joint.The pressure tube is furnished near the bendwith a side tube connecting with the mercury reservoir, and termi-nates at the top with a Friedrich's patent glass stop-cock, so that itcan be used either open or closed ; i t is 1000 mm. high. The measur-ing tube, 640 mm. long, is wide for about two-thirds of its length,but is narrower at the upper portion, to which a Friedrich stop-cockis attached, and this is connected with two capillary, double right-angled tubes, one of wider bore, for the admission of the gas to beexamined, or other object; the second and narrower one passing tothe laboratory vessel, which is furnished at the top with a cup, intowhich the tube fits, and is rendered air-tight by an indk-rubber collar.The laboratory vessel, which may be of any convenient capacity, isprovided with plat-inum wires for explosions, and, moreover, termin-ates below in a narrow cylindrical portion, which may be useANALYTICAL CHEMISTRY.241open, or be closed with a cork, and to which is attached side tnbe,connecting with an independent mercury reservoir to facilitate fillingwith mercury, transferences, &c. A suitably bent tube, with india-rubber attachment, is fitted to the cork, and serves for the admissionof reagents. Behind the whole length of the pressure tube a long,narrow mirror, graduated in millimetres on an unsilvered portion, isfixed at such an angle as to reflect a good image of the mercurycolumn and meniscus.The whole apparatus is mounted on a woodensupport, with necessary clamps, attachments, &c. ; tbe mercurFreservoirs being placed behind. The apparatus serves for all kinds ofgas measurements, as an air-pump, and for distillations under reducedpressure or in a vacuum.Lacmo'id. By 0. FORSTER (Zeit. ang. Chent., 1890, 163-167).-Commercial lacmoid is of very variable character. Some specimensare almost wholly insoluble in water, and are unsuitable as indicators.Others colour boiling water intensely blue, and are fit for use. Toprepare the pure blue indicator, the finely-powdered crude materialis extracted with boiling water, but stopping short of completeexhaustion, so as to avoid dissolving a sparingly soluble red substance.From fhe cooled and filtered blue solution, the colour is precipitatedby feebly acidifying, and after some hours is collected on a filter andwashed with cold water, then dried at a low temperature (sincesome decomposition takes place if it be dried at looo), or dissolvedin alcohol, and the solution evaporated on the water-bath.Purifiedin this way, it gives, with pure distilled water, a blue solution, havinga slight tendency to violet, and exceeds all other indicators in sbarp-ness. In wafer containing carbonic acid or au ammonium salt, itgires an exceedingly sharp change with a quantity of alkali, whichhas scarcely any efl'ect on litmus. To prepare blue lacmo'id paper,sulphuric acid is added to an alcoholic solution of lacruoi'd, untilwhite paper dipped into the liquid is coloured red.This willbecome blue on drying. The depth of blue should be that of theforget-me-not. For red paper, the paper should be dipped in verydilute sulphuric acid and dried before staining. It must be preservedin well stoppered bottles, and is an extremely sensitive indicator foralkalis.A somewhat more ready mode of purification is as follows :-8 parts of finely-powdered crude lacmo'id is gently warmed for a,quarter of an hoar with 100 parts of 20 per cent. alcohol, and theliquid filtered after cooling. After ascertaining the amount of matterin solution by evaporating a portion, there should be added analcoholic solntion of 14 parts of malachite green t o 86 parts of thelacmoid.This addition does not impair the indication witb acids,whilst it increases enormously the sharpness of the change to bluewith an alkali. The liquid is filtered from a, precipitate which forms,and is then mixed with an equal volume of absolute alcohol. It shouldbe kept in black bottles.Estimation of Free Hydrochloric Acid in StannousChloride Solutions. By W. MINOR (Zeit. mag. Chenz., 1890,D. A. L.11. J. S242 ABSTRACTS OF CHEMIOAL PAPERS.25--26).-Precipitation as silver chloride cannot be resorted to i nconsequence o€ the co-precipitation of tin compounds. A measuredquantity (100 c.c.) of the solution is, therefore, satmated hot withhydrogen sulphide, and filtered into a litre flask. Half of the filtrateis boiled to expel hydrogen sulphide, and the total acid then titratedwith standard alkali.The amount of tin is now ascertained bytitration witb iodine, and the corresponding quantity of hydrochlorica i d deducted from the total. M. J. S.Detection of Hypochlorous Acid in Chlorine Water. ByT. SALZER (Chern. Centr., 1890, ii, 472 ; from Pharm. Zeit., 35, 457).-The author recommends the method of Lunge and Naeff, devisedfor the determination of hypochlorous acid in the presence of chlorine,which depends on the fact that chlorine reacts with potassiumiodide and hydrochloric acid, forming potassium chloride, iodine, andhydrochloric acid, whereas hypochlorous acid produces, under thesame circumstances, no hydrochloric acid. If, therefore, the solutionis first titrated with decinormal alkali and then with thiosulphatesolution, the amount of the chlorine and hypochlorons acid may becalculated. Of neutral chloxine water, the author recommends 25 C.C.should be acidified with 10 C.C.of decinormal hydrochloric acid,1 gram of potassium iodide added, and titrated with thiosulphate.Pure chlorine water should require exactly 10 C.C. of decinormalhydrochloric acid. Chlorine water, containing acid, is not to berecommended as an eye-mash.Detection of Traces of Iodine in the Presence of muchChlorine. By A. JOHKSTONE (Chem. News, 62, 153, 169).-Thesolution to be tested is treated with a saturated solution of silvernitrate in strong ammonia; a yellow precipitate indicates the presenceof an iodide. To c0nfir.m this, add concentrated sulphuric acid, andagitate with carbon bisulphide ; the latter becomes coloui-ed by anyliberated iodine.D. A. L.J. W. L.Separation and Estimation of Tellurium. By E. DONATH(Zeit. ang. Chem., 1890, 214-217 ).-Precipitation by sulphurousacid is complete but tedious. Kastner’s grape-sugar method (Abstr.,1876, 440) is accurate and expeditious. Precipitation by stannouschloride or an alkaline fitannite is not suitable, since the precipitatealways contains tin. Tellurium is very rapidly precipitated fromacid solutions by hyposulphurous acid. The yellow solution obtainedby shaking scrap zinc with aqueous sulphurous acid is filtered, andadded to the cold concentrated hydrochloric acid solution of thetellurium compound. Precipitation is complete in 15 minutes.Thewashed precipitate, which may contain some tellurium sulphide, isriused into a tared capsule, oxidised with strong nitric acid, and,after gentle ignitiol;, weighed as tellurium dioxide.For. the attack of ores containing tellurium, 3 or 4 grams of theimpalpable powder is treated in a basin with small quantities of con-centrated nitric acid, and from the pasty mass obtained, the excess ofacid is completely evaporated at a temperature which will not decomANALYTICAL CHEMISTRY. 243pose the metallic nitrates. The dry mass is powdered in the basin,moistened with strong soda solution, and digested for half an hour.Water is then added, the filtrate boiled for 20 minutes with pure grape-sugar, and the precipitated tellurium weighed as dioxide, as above.M.J. S.Estimation of Hypophosphorous, Phosphorous, and Hypo-phosphoric Acids. By L. AMAT (Conzpt. rend., 111,676-679).-1~ awarm acid solntion, hypophosphoric acid reduces mercuric chloride tothe mercurous salt, and is itself completely converted into phosphoricacid, probably in consequence of an intermediate conversion intophosphorous and phosphoric acids. About 1 gram of the substanceis mixed with 10 C.C. of concentrated hydrochloric acid, evaporatedalmost to dryness in order to promote the decomposition of the hypo-phosphoric acid, redissolved in a fimall quantity of water, and mixedwith a solution containing 69 grams of mercuric chloride and 20 to40 C.C. of concentrated hydrochloric acid per litre.The mixture isallowed to remain for 24 hours at 80°, and the mercurous chloride iscollected and weighed.Potassium permanganate can be employed in the manner indicatedby P. de St. Gilles, the substance being oxidised by excess of thepermanganate and the excess determined by means of oxalic acid.The oxidation is more rapid, the more concentrated the solution, thegreater the proportion of free acid, and the higher the temperature.At a high temperature, a small quantity of permanganate may bedecomposed, and a t a low temperature, especially in dilute solutions,oxidation is incomplete ; careful attention to the conditions is there-fore necessary.The permanganate employed should be equivalent to a solutioncontaining 63 grams of oxalic acid per iitre, and the quantity of sub-stance taken for analysis sbould reduce about 20 C.C.of the perman-ganate. The substance is dissolved in 20 C.C. of water, mixed with3 C.C. of concentrated sulphuric acid, cooled, mixed with 35 C.C. OE per-manganate, and heated at 50" for half an hour. 20 C.C. of oxalic acidsolution is then added, and after the liquid has become colourless andthe brown precipitate has completely dissolved, the excess of osalic acidis determined by means of permsnganate. The method is applicableto phospbites, pyrophosphites, and hypophosphites. In the case ofhhophosphates, the liquid is first heated with the sulphuric acid a t80-100" for half an hour, and then cooled and mixed with the per-mangsnate.The mercuric chloride method, although the more tedious, is themore accurate of the two.C. H. B.The '6 Citrate Method" of Phosphoric Acid Estimation. By0. REITNAIR (Zeit. any. Chem., 1890, 19-25, 196-210; continuedfrom Abstr., l890,416).-Comparing the results yielded by the citratemethod, under a great variety of conditions, with those furnished byprecipitation by molybdate, the author has investigated the amountof the error of deficiency due to imperfect precipitation of the phos-phoric acid, and that of the error of excess due to conta.mination ofthe precipitate by impurities. His conclusions are as follows :-I244 ABSTRAOTS OF CHEMIOAL PAPERS.all modifications of the citrate method, the precipitation of the phos-phoric acid is incomplete, and with large proportions of citrate and asmall amount of magnesia, it may be very seriously so.In the mostfaavowable cases, about 2 milligrams of magnesium pyrophosphatepasses into the filtrate. On the other hand, when calcium, iron,aluminium, or manganese is present, a variable portion of those baseswill always be found in the precipitate, and, if enough magnesia mix-ture has been used, a compensation of errors is possible. The use of &minimum quantity of ammonium citrate, in accordance with the pro-cedure of Brassier and Glaser (Abstr., 1885, 837), is not permissible ;an excess is always requisite, The quantity of magnesia mixture must,however, always be proportioned t,o the amount of citrate. The baseswhich chiefly contaminate the precipitate are calcium and manganese.Both are precipitated in the form of ammonio-phosphates, which aroconverted into pyrophosphates on ignition.Of iron and aluminium,there are usually only traces precipitated ; the principal effect of thesemetah in the solution is to retard the precipitation of the magnesiumammonium phosphate. Grupe and Tollens have stated that magnesia,.or a basic magnesium salt, is precipitated together with the ammonio-phosphate. This is certainly true, since the ignited precipitate alwaysshows the reaction of an orthophosphate with silver nitrate, but if themagnesia mixture has been added by drops to an ammoniacal solution(2.5 per cent. of ammonia), the magnesium oxide in the precipitate willbe scarcely weighable. But, using nearly neutral solutions, and espe-cially when salts of sodium or potassium are present, the amount maybe very considerable. The use of hydrochloric acid for dissolving phos-phates containing silica is disadvantageous ; the magnesium precipi-tate will always be st.rongly contaminated with silica, and the amountoE foreign bases precipitated will also be increased.Even whensnlphuric acid is used, and the solution is consequently freer fromsilica, it is to be expected that about 1 milligram will be found in theprecipitate. The presence of sulphates has, however, the tendency,other things being equal, to increase the error of deficiency. More-over, since the use of sulphuric acid removes a large part of the limeas sulphate, less ammonium citrate is needed than mould otherwise bethe case.Using the process for estimating the phosphoric acid in the solubleportion of a superphosphate, and working upon 1 gram of substance,with 5 grams of citric acid, 25 C.C.of magnesia mixture, and ammoniaequal to 2.5 per cent. of the solution, t~ loss of about 2 milligrams,equal t o 0.128 per cent. of phosphoric acid, may be assumed. On theother hand, when examining basic slag, or raw phosphates, the errorwill be in excess. If silica, and manganese are absent, the amount ofthe error may be small, but no estimate of its average magnitude canbe formed. MI. J. S.Reduction of Arsenic Acid in Analysis. By F. A. GOOCH andP. E. BROWNING (Amer. J. Sci., 40, 66--71).-The authors endeavourto shorten fhe process of reduction of arsenic acid by employinghydriodic acid, instead of sulphurous acid, as the active agent.Theprocess recommended may be snmmarised ab follows :-To the arsenatANALYTICAL OHEMISTRY. 245in solution are t D be added potassium iodide in excess of the amountneeded, according to the equation, to complete the reduction, and10 C.C. of half and half sulphuric acid. The liquid is to be diluted toabout 100 c.c., and boiled rapidly until the volume is decreased to40 C.C. The colour of the free iodine is to be bleached by cautiousadditions of sulphurous acid, and the liquid immediately diluted withwater and neutralised, first with normal potassium carbonate and after-wards with the hydrogen salt.. The whole is to be cooled and titratedwith iodine in the usual manner, starch being used as an indicator.The advantage of this method is in the rapidity with which it maybe executed, the whole opcration being completed in half an honr.The average error of the process amounts to 0.13 per cent.of theamount taken. B. H. B.Estimation of Peroxides of the Alkaline Earths. By G.KASSNER (Arch. Pharm., 228, 432435).-A weighed amount of theperoxide (0.2 in the case of the barium compound) is ground with a,little water and washed into a beaker ; then excess (about five timesas much) of pure potassium ferricyanide is added. Oxygen is at onceevolved, and the reaction is complete when the gas ceases to come off ;the reaction may be accelerated by gently warming the beaker. Aconsiderable amount of water is now added, and excess of sulphuricacid ; the greenish colour which may now appear does not affect t h 0result.The solution is finally titrated with potassium permanganatesolution. Thus, 0.2 gram of peroxide required 15.2 C.C. of perman-ganate (1 C.C. = 0-00576 gram of Fe) ; hence the peroxide contained74.7 per cent. of peroxide. The old direct process gave 75.13 percent. The new process may prove useful in cases where an acid solutionwould be inadmissible ; it is only necessary to filter off an aliquot part ofthe solution before the acid is added, and then titrate and calculate.J. T.Estimation of Ferric Oxide and Alumina in PhosphaticManures. By A. STUTZER (Zeit. my. Chem., 1890, 43--44).-Thcauthor, whilst admitting the superiority of Glaser’s method (Abstr ,1890,420) over that depending on the insolubility of the iron andaluminium phosphates in acetic acid, prefers to weigh the ferric oxideand alumina as such, and not as phosphates.To this end, the solu-tion of 1 gram of the phosphate in hydrochloric acid is made alkalinewith ammonia, and then feebly acid with acetic acid. The precipitateis collected and partially washed ; the filter with its contents is re-turned to the same beaker, and digested with 150 C.C. of niolybdatesolution. The solution filtered horn the yellow precipitate is made feeblyalkaline with ammonia, and warmed for 10 minutes on the water-batb.The precipitate sometimes contains traces of molybdic acid, but ifdissolved in hydrochloric acid and reprecipitated by ammonia, theferric oxide and aluminn are obtained free from all impurities.Valuation of Pyrolusite by means of Hydrogen Dioxide.By A.BAUMANN (Zeit. ang, Chem., 1890, 72--79).-The reactionMnOz -i- HzO, = MnO + 02, which occurs in acid solutions, yieldsequally good results by gravirnetric, volumetric, or gasometricM. J. S246 ABSTRACTS OF CHEMICAL PAPERS.methods. The last has already been employed by Lunge (Abstr.,1885, 1162). For accurate work, an ordinar7 50 C.C. nitrometer isscarcely large enough, since not more than 0.18 gram of manganesedioxide could be used, and an error of 0.1 C.C. in reading the volumeof the gas would equal 0.2 per cent. in the result. The. eudiometershould be able to measure at least 100 C.C. of gas, and should besurrounded by a water-jacket, that the temperature may be kuownwith exactness.Water may be used in the eudiometer instead ofmercury. In case the pyrolusite should resist ahtack, the reactionflask may be warmed to 70". 1 C.C. of oxygen at 0" and 760 mm. isequal to 0*003885 gram of Mn02.Gravimetrically, the estimation may be made by weighing theoxygen evolved. Almost any of the forms of carbonic acid apparatusfor the estimation by loss of weight may be used. From 2 to 6 gramsof the pyrolusite, in impalpable powder, is placed in the reactionflask with 30 C.C. of sulphuric acid (1 part to 3 of water), and 40 C.C.of commercial hydrogen peroxide is placed in the inner tube. Warmingshould be avoided.For volumetric estimation, an acidified hydrogen peroxide (contain-ing about one-tenth of sulphuric acid) should be made of strengthcorresponding approximately with a standard permanganate (10 gramsper litre).The relation of the solutions is accnrateiy found, and then0.4 to 1 gram of the pyrolusite is treated with 50 C.C. of the hydrogenperoxide in the cold, and after half an hour with occasional shaking,the excess is titrated back with the permanganate. The presence offerrous compounds in the pyrolusite leads to high results, since theyconsume hydrogen peroxide ; in Bunsen's and the ferrous sulphateprocesses, the error is in the opposite direction.Titration of Permanganate and of Bleaching Powder byHydrogen Peroxide. By L. VANINO (Zeit. nag. Chern., 1890,SO-83).-To facilitate calculation of the results from the volume of oxygenevolved, tables are given of the weight of 1 C.C.of oxygen and ofchlorine respectively, over a sufficiently wide range of temperatureand pressure. The author's practice differs in three points from thatof Lunge (Zeit. nng. Chem., 1890, 7) ; he prefers an azotometer to thenitrometer ; in the analysis of bleaching powder, he uses feebly acid,instead of alkaline, hydrogen peroxide ; and he compares his resultswith those of the iodometric method, rather than with Penot's, andfinds a closer agreement than did Lunge with the latter. The titra-tiou by permanganate of the residual hydrogen peroxide gives unex-ceptionable results in the assay of bleaching powder.Dry Assay of Tin Ores. By H.0. HOFFMANN (Chem. News, 62,157-159 ; 169--170).-This section of the author's paper on the dryassay of tin ores deals with methods depending on fusion with potas-sium cyanide, of which various modifications have been investigated,with and without a salt cover, in chalk- or charcoal-lined crucibles, inporcelain crucibles, with charcoal intermixed with the cyanide, withvarious qualities of cyanide, &c. The chief source of error appears to bedue to the tin, instead of forming a button, being disseminated throughM. J. S.M. J. SANALP TlCAL CHEMISTRY. 247the mass of slag, when it cannot subsequently be thoroughly sepa-rated. To obviate this, it is recommended to ram a lot of potassiumcyanide into the bottom of the crucible before putting in the ore andflux, so as to form a fused mass for the tin to fall through and accu-mnlate beneath to form a button.As regards impurities, iron pabsesinto the cyanide, alkaline sulphates and carbonates cause low resultsowing to the formation of tin sulphides in the first case, and of stan-nates in the second. Impure cyanide gives low and irregular results.By A.ROSENHEIM (Bey., 23, 3208--3210).-The statement attributed to theauthor by Rothenbach (Bey., 23, 3050; and this vol., p. 18) thatsulphurous acid is capable of reducing tungstic acid when present asphosphotungstic acid is incorrect, as he has shown (Abstr., 1889, 762)ihat no reducing action takes place. Rothenbach further states thatthe violet coloration produced when sulphurous acid is added to amixture of phosphoric and vanadotungstic acids is not due to the re-duction of the tungstic acid, as vauadiurn tetroxide free from snlph-urous acid also yields the coloration with phosphotungststes.Thisfact, however, really proves the contrary of Rothenbach’s statement,for vanadium tetroxide, as shown by its action on ferric oxide and am-moniacal silver solutions is a reducing agent, and this is the compoundwhich actually causes the reduction of the tungstic acid, as is shownby the fact that the intensity of the coloration is dependent on thequantity of tungstic acid present, and not on that of the vanadiumtetroside. H. G. C .D. A. L.Estimation of Vanadic Acid in Vanadiotungstates.Estimation of Ferrocyanides. By R. ZALOZIECKI (Zeit.ang.ohem., 1890, 210--214).-When a solution of an alkaline ferrocyanideis treated with zinc carbonate and a stream of carbonic anhydride, thewhole of the ferrocyanogen is precipitated in the form of a double saltof the alkali metal and zinc. If the operation is performed at theboiling temperature, the reaction takes place according to the equation3h~t’~FeCy~ + 2ZnC03 = 2Zn2FeCy6,M’4PeCy6 + 4M‘2C03, and theamount of alkaline carbonate produced may be employed as a measureof the ferrocyanide originally present. The zinc carbonate should beprepared by the addition of sodium carbonate to a hot solution of zincsulphate, as it then subsides and washes readily. It is preserved inthe pasty state, and if the quantity added contains an amount of zincapproximately equal to the weight of alkaline ferrocyanide, i t will beamply in excess.The mixture is heated to boiling, and a stream ofcarbonic anhydride is passed through it for a half to one hour. It isthen cooled, diluted to a known volume, filtered, and an aliquot part,of the filtrate is titrated with standard acid, using methyl-orange asindicator. If the original solution had contained alkaline carbonatesor sulphides, the amount of these should be ascertained by titration,and the acid they consume deducted froni the total quantity requiredafter treatment with zinc carbonate. Sulphates and chlorides have adisturbing influence, but this can be counteracted by the presence ofan excess of alkaline carbonate; thiocyanates and the other con-stituents of prussiate “ metal ” are without influence.Id. J. s248 ABSTRAOTS OF GHEMIOAL PAPERS.Estimation of Sugar in Blood. By J. SEEUEN (Chein. Centr.,1890, ii, 478-479 ; from Centr. Physiol., 4, 217--222).--The authorhas found that if, in the estimation of sugar in blood,the coagulum,caused by the addition of iron acetate, be not thoroughly and repeatedlypressed and washed, considerable quantities of sugar may be retainedby it., although he has not found the error to be nearly so great asstated by Schenk and by Riihmann. In his first experiments, 5-8 percent. was retained, and he considers that the sugar may be entirelywashed from the coagulum independently of any choice of pre-cipitating agent. J. W. L.Examination of Oils, Fats, and Allied Substances. By T. T.P. B. WARREN (Chem. News, 62, 125; 179-lSO).-The sulphurchloride test recommended in various communications by the authorindicates the character but not the probable quantity of the oils in amixture ; it is, therefore, now suggested to ascertain the latter factorby taking the iodine absorptions, with Hubl's reagent, of the indi-vidual constituent oils as well as of the mixture, and from the dataobtained to determine the proportions present, for which purposemethods of calculating are described.Estimation of Formic Acid in presence of Acetic andButyric Acids. By A, SCALA (Gazzetta, 20,393-396).-The liquidcontainingthe formate is weighed out into a deep beaker, an excessof a saturated solution of corrosive sublimate added, the wholecovered with a clock glass and heated for two hours on the water-bath. The precipitated calomel is collected on a weighed filter,washed with warm water, dried at loo", and weighed. When theacid is present in the free state, it is neutralised before proceeding asabove. This metbod gives trustworthy results, and is very sensitive,formic acid precipitating more than 10 times its weight of calomel.S. B. A. A.D. A. L.Modification of Jaffe's Indican Test. By F. OBERMETER (Clzem.Centr., 1890, ii, 273-274 ; from Centr. PhysioZ., 4, 155).-The authorprecipita.tes the urine with plumbic acetate, avoiding too large anexcess, filters through a dry filter, agitates the filtrate with an equalvolume of fuming hydrochloric acid, in which 2 to 4 parts of ferricchloride are dissolved in 1000 parts, and extracts finally with chloro-form. The indigo produced by the oxidation of the indican may thenbe determined colorimetricallp in the chloroform solution. Ferricchloride has the great advantage over others, as an oxidising agent ofindican, that it does not affect the indigo produced. J. W. L

ISSN:0368-1769    

DOI:10.1039/CA8916000240

出版商:RSC    

年代:1891

数据来源: RSC

摘要:

249 General and P h y s i c a l Chemistry. Circular Polarisation of certain Tartrate Solutions. By J. R. LONG (Amer. J . Sci. [3], 40, 275-283 ; compare Sbstr., 1890, Sl;J).-The specific rotation of potassium antimony tartrate is con- siderably reduced hy the admixture of carbonates, borates, phosphates, or acetates in amounts insufficient to produce immediate precipitation. Investigation of 1 his behaviour leads to the coriclusicn that on mix- ing solutions of alkaline phosphates, acetates, carbonates, or borates wit.h the tartrate in the cold, there is probably first formed a, tern- porarily stable mtimony salt, with a corresponding amount of alkaline tartrate. 'I'he obsiwed rotation is due to this plus that of the iinchanged potassi L i r n antimony tartrate. The specific rotation of potassium ammonium tartrate is but slightly affectod hy the presence of ammonium or potassium salts, but is considerably diminished by the addition of a sodium salt.This behaviour may also be explained on the general hypothesis of replacement in the tartrate niolecule by excess of inactive salts. Phosphorescence of Lithium Compounds in Vacua, and Spectra of Coated Terminals. By E. E. BROOKS (Chem. News, 62, 239).-Vnrious lithium salts and minerals exhibited the following phosphorescence phenomena and continuous spectra showing a con- centration of light in certain parts, when examined by Crooked method in the negative discharge in a vacuum :-Sulphate, a bright lilac-blue ; phosphate, bright, light Cambridge blue, when fused with sodium carbonate the colour became bright emerald-green, and, unlike the other cases, the glow was prolonged for a second or t w o after the cii-cuit was broken : chloride, moderately brilliant, pale lavender- blue ; fluoride.moderately brilliant, very light flesh-colour ; silico- fluoride, deep blue with darker spots, not ho brilliant as the sulphate ; spodumene, golden-+yellow ; lepitiolite, very brilliant, deep-red, with .Lt.aces o€ blue ; petalile, very brilliant, rich yellow ; amblggonite, trace of white glow ; the nitrate, carbonate, hydroxide, and rubellite arid indicollite did not phosphoresce ; but the nitrate, fused in a glass tube, produced an opFtque, enamel-like appearance at surfaces of con- tact, by which the inherent yellowish phosphorescence of the German glass became -jellower. By coating with, or simply placing 011, aluminium or platinum negative terminals, lithium, thallium, sodium, calcium, or barium salts, and submitting them to a discliarge in a racuiim of moderate tenuity, the flame spectra of the respective metals were obtained; other metals gave very taint spectra, or even none, with the 1-inch- spark coil employed, H.C . These spectra disappear in high vacua. I) A. L. Crystalline Liquids. By 0. LERMAXN (Ann. Phys. Chern., 41, 525--537).--The author has drawn attention to the fact tba$ certain VOL. LX. 6250 ABSTKACTS Ot“ CHEMICAL PAPERS. liquids exist which behave optically as if they had a crystalline struc- ture (Abstr., 1890, 106). These liquids are chemically homogeneous, rlnd the anisotropy is not produced by exteimd force.He now asks the question whether isotropic liquids are non-crystalline, or whether. they belong to the regular system, and concludes that in view of the very general miscibili t.y of liquids they are non-crystalline, for other- wise they would onlyhave tl:e power of mixing with isomorphous substances. This conclusion lie supports by experiments on the miscibility of crystalline lifpids with each other and with solid crjsta1c;l. Liquid crystals, when heated between cover glasses slightly above the point, where they pass into ordinary liquids, retHin oil cooling the origin;il direction of their optical axes, owing probably to condensation and consequent higher “ melting ” point of a layer on the surface of the glass. Isomorphous liquid crystals exhibit the pheuomena of diffusion, and thus the capability of solids to form mixed crystals appears to correspond exwctlv with the process of mixing or diffusion in liqiiids (compare van’t HofT, Abstr., 1890, 104 k).J. W. Passive State of Iron and Steel. Hy T. ANDREW‘S (PIWC. Roy: Soc., 48, 116--12S).--Steel magnetised by hand or by it coil exhibits a small E.M.F., almost always p )sit,ive with respect to lion-mftpnetised steel, when both are immersed in nitric acid of sp. gr. 1.42 at the ordinary temperature. As the temperntnre is r A i s d , the E.M.F. varies somewhat, but remains small, riot exceeding 0.03 volt. ,4t about 90”, however, the magnctised steel is attacked violently by the acid, and the E.M.F. rises suddenly to as much as 0.3 volt,. Effect of Pressure on the Electrical Conductivity of Liquids.By C. BARUS (Amer. J . Sci. [ S ] , 40, 219-222).--Por commercial iuercnry subjected to pressnres between 10 anci 400 atmos. isotliei*- tnally, -6rt/tt = 30 x 10-sSP, where SR/R is the decrement of the specific electrical resistance R, corresponding with the pressure incre- ment SP. If v i R the volume, tlien from the results of Gras:;i and others, - & j / t ’ = 8 x lG-SSP, and hence 6R/R = 106z-/v. If 0 be tlie symbol of temperature, the following approximate results apr)ly, i-opiestically, at ordinary temperatures nnd pressiires: i?R’/R’ = 800 x 10-680, and 6c/o = 180 x 10-6d0. Hence 6R/R’ = 4.4 &/v, where XI’ refers GO electrical resistance considered in its thermal relations. l+”or a conce-rtrated solution of zinc sulphate subjeched to pressnres from 10 to 400 atmos., similar expres3ioas apply with somewhat less a :curacy.Expressing the results graphically, the pressures in atmospheres or volume decrements per unit of volume are found to be linear functions of the corresponding decrements or increments of electrical resisttmce per unit of r4staiice. The cuwes for thermal change of resistairce Slt’/R coordinated with volume aecrement are also recti- linear. In order to bring the compression loci into coincidence with the thermal loci, the former must be rotated in each case around the origin in a direction contrary to tho hands of a watch. The angle of rotation is coneiderably greater for zinc sulpliate solution tliun it, i s J. W.GENERAL AND PHYSlCAL CHEMISTRY.251 for mercury. From this, follows the remarkable result that, both it1 the case of the metal and of the electrolyte, the effect of isothermal compression is a decrement of resistance nearly proportional to pres- sure, and by deduction, that the immediate electrical effect of rise of temperature, &R'/R - sR/R, is a decrement of specitic resistance, both in the case of the metal and of the electrolyte. This points out, an inberent similarity betweeu the metallic and the electroljtic conduc- tion in this instance. H. C. Electrical Conductivity of Boric Acid Solutions in Presence of Dulcitol. By G. MAGNAMNL (Gazzetta, 20, 44148).-'l'he author has applied his new met-hod of studying the constitution of solutions (see Sbztr., 1890, 1357) to the investigation of the mole- cular composition of the compounds existing in solutions of bwic acid aad dulcitol.The variations of the molecular conductivity of boric acid solutions in presence of dulcitol are precisely of the same character as those which occur in presence of mannitol, with this dif- ference, however, that from the observed values of the conductivity in the case of dulcitol, no simple relation for the m3lecnlar composition of the electrolytic compound or compounds can be calculated. This renders it probable that several compounds of boric acid and dulcitol exist together in the solution. S. B. A. A. Determination of BDiling and Freezing Points by means of the Platinum Thermometer. By E. H. ORIFFLTHS (PTOC. Roy. SOC., 48, 220-225) .-Eight thermometers, varying somewhat in con- struction, were compared.The best form was found to be the follow- ing:-A coil of fine platinum wire is wound on a roll of asbestos paper, and slipped into a thin tube of hard glass. Thick platiuum wit-es run from this coil to the top of the instrument, and fhe unimmersed portion of the stem is surrounded by the outcr tube of a condenser, throiigh which tap-water is kept flowing. The diameter is less than 3/!.6ths of an inch, and the 1eng:Gh about 18 inches. Tho instruments were graduated at the boiling points of water, naphtha- lene, benzophenone, and salphur, and the freezing point of wtiter. From the determina$ions of the boiling points of rarious substances, it was found that although the curves for the different thermometers varv considembl v in form.intermediate temtwratnres deduced from t,h& are in prackcal agrekent (less than 0.1') up to 500". J. W. Heat of Combustion of Organic Compounds. By F. STOH- MAWN (Zeit. physikal. Chent., 6, 334--35i).--In this paper are collected and systematically arranged the heats of combustion of over 400 organic compounds. The tables include all the determinations made from 1852 until Augnat, 1890, with the exception of t,he experi- ments of Frankland, Ramsay, von Rechenberg, and Danileflski. Many hitherto unpublished determinations by the author and his pupils are also included. In the various columns are given the heat of combustion per gram in small calories; the heat of combustion per gram-molecu!ar weight i n grcat calories (both at constant pressure 8 2252 ABSTRAO'J'P OF CHEMIOAL PAPERS.9.5 5.7 8 . 5 2 . 8 3 . 3 6 ' 4 1.0 4.2 and conRtant volume) ; the heat of formation in great calories ; tho observer ; and the reference to the original source. In calculating the heats of formrttion, tho author assumes the following heats of combnation:-C, 94 Cal.; H f , 69 Cal.; and S, 69.3 Cal. J. W. 0*09300 0*12100 0'02870 0-10200 0.00867 0.00286 0.02040 0*00678 Relations of the Heats of Combustion of Solid Bibasic Acids to those of the Gaseous Hydrocarbons. BV F. STOHMANN ( J . pr. Chem. [2], 42. 248-259; compare Abstr., 1889, 1096, and Abstr., 1890, loo).-lf A is the heat of combustion of any bibasic acid, and B that of the gaseous hydrocarbon frcm which it is derived, then the ratio A/B is practically a constant. A mean value for this constant obtained from the determinations of the heats of combustion of 22 different acids is 0.97692.Hence, if the heat of combustiori of a molecule of a gaseons hydrocarlion is tnkeii as unity, that of the corresponding bibasic acid will be 0.97698, or the heat of combustion of the hydrocarbon is obtained by dividing tltrtt of the acid by 097692. A comparison between numbers thus calculated and those observed shows a very srttisfactor-y agreement. The dieerence B - A is equal to the sum of two numbers x and y, the first of which is the loss of heat i n the passage of the bydro- carbon from the gaseous to the solid condition, and the second tbc? heat evohed in the conversion of the solid hydrocarbor, into the corresponding acid. I n some cases x is already known, and for others it may be calculated without serious error on the assumption that the heats of fusion and vaporisation of unit weight of all hydrocarbons are the same.The value of x being known? y the heat, of formation of the acid from the hydrocarbon is theu easily calculated. The following table gives values of y for different acids calculated by the above method :- Malonic acid ......... Dimethylmalonic acid.. Succinic acid ......... Et~h~lsuccinic acid. .... Glutaric acid.. ....... Piinelic acid.. ........ Adipic acid. .......... Male'ic acid .......... Methylmalonic acid.. .. Ethylmalonic acid. .... Metbylsuccinic acid ... - Ye Cal. - 2 *5 1 -7 5 '5 8-1 9.7 8 '2 7.4 6 *2 8.1 10-7 3 3 K. -- 0 -17100 0 -08700 0 *12700 0.07';OO 0 -00665 0 Q0860 0 *00860 0 90475 0 -00357 0 00371 1 -17oOO ---- Fumavic acid ........Phtlialic acid ........ Isophthalic acid.. .... Salicylic acid ........ Met aliydroxjbenzoic acid .............. Purahydruxy benzoic acid .............. a-Nnphthoic acid ..... /3-Naphthoic acid. .... --- In the second colurrin of the table, are giren the values of Ostwa,ld's affinity coefficients, between which and the heats of formation there is an evident, relation, for acids of similar constitution the affinity coefficient being smaller the greater the heat of forma4tion. Methyl- malonic acid occupies an exceptional position i n the malonic acid series. By analogy with the cther acids of t.his series, the heat ofQENERAL AND PHYSICAL OHEMISTRY. 253 formation should be between 2.5 Cal.and 5.5 Cal., and the affinity coefficient between 0.171 and 0.127. Instead of this, the numbers are 1.7 Cal. and 0.087. H. C. Compressibility of Mixture8 of Air and Carbonic Anhydride. By U. LALA (Conzpt. rend., 111, 819--82i).-The author has investi- gated the compressibility of mixtures of air and carbonic anhydride containing 11 to 56.92 per cent. of the latter, n t pressures extending to 1613.96 cm. of mei.cui:y. When the proportion of carbonic anhydride does not exceed 22 per cent., the compressibility lies between that of air and carbonic anhydride, and is, at first, nearer too that of air, but approaches more closelv to that of carbonic anhydride as the pressure increases. The greater the proportion of carbonic amhydride, the lower the pressnre at which the cornpressihility becomes equal to that of carbonic anhydride alone.As the proportion of this gas increases, the compressibility becomes greater than it would he it' no air were present, but beyond a, certain point it decreases aiid tends to revert-to tho cotnpressibility of pure carbonic anhydride. C. H. B. Experiments on Vapour Density. By E. P. PERMAY (PTCC. Roy. h'oc., 48, 45-59) .-This investigation was undertaken mainly to ascertain if bromine dissociates at low pressures and moderate temperatures. The apparatus employed is figured in the accom- panying cut. A is a glass globe of known capacity (abont f litrej blowti inside a larger globc, B. The liquid which produces the vapour-jacket is boiled in C, and condensed in D, which ma.y be specially cooled if noccssary.P is a tube containing a liquid to absorb the bromine vaponr, a few drops being also introduced into254 ABSTRACTS OF CHEMIOAL PAPERS. the bulb-tube G. M is an air reservoir, and 0 a pressure gauge, the tube P being attached to a water-pump. A is first exhausted, and then there is introduced into i t a, little liquid bromine, air being excluded. The tube ahore E is fused on to F, the liquid in C boiled, and the bromine allowed gradually to blow ont over the potash solution in F. The tube above tho globe must, be heated gently with a Bunaen flame. Tbe apparatus is now exhausted as far as possible, the stopcock E turned off, the tube above cracked and removed, triore bromine admitted as a t first, tlrs tube fused together again, m d the bromine driven out as before until the vapqur in A has the atmospheric pressure at hhe temperature of ;the boiling liquid in C.The absorption-tube F is then filled witli strong solution of potassium iodide, anit the whole apparatus connected up as in the tigure. M is exhausted to the requisite degree, and tho pump cut off by the screw-clip R. Bromine vapour is allowed to eeoape from A by cautious mallipulation of the stopcock E until equilibrium is attained. The pressure is then rend off, the stopcock L closed, and the contents of the absorption-tube washed into a stoppered bottle to be afterwards titrated with thiosulphate. The experiment is then repeated at lower pressures until the series is complete. By adding together the residual quantity of bromine and the quantities removed, the weight of bromine in the globe-at each pressure is found, and as the volume occupied is already known, all data required are availa ble.It was found that at. temperatnres ranging from 15" to 280", and nt pressures from 15 mm. to 760 mm., bromine vapour exhibited the normal density withoat any indication of dissociation. Iodine, when vaporised in a similar apparatus, did not yield constant results, so experiments with it were conducted by means of an apparatus for determining the speed of sound in the vapour. Finely-divided precipitated silica was used to ascertain the wave- lengtb. The density of the saturated vapour a t 132" was found to be normal. The author finds (in contradiction to J. J. Thomson, Abstr., 1887, 1013) that the passage of electric sparks through the vapour does not alter its density.A few experiments were made with tho vapour of sulphuric anhydride. Tbe author considers that his results prove the formula of this substance to be SO, and not S,O,. The vapour density of aqueous hydrochloric acid shows that the acid and water do not combine at the temperature eniployed (132"). Variation of the Density with the Concentration of Weak Aqueous Solutions of Certain Salts. By J. G. MACGREGOR (Chew. N e w , 62,223-224,252-234).-The densities of the various solutions were, in these experiments, determined in a specific gibavity bottle a t 20°, and, us a rule, at least two solutions of differrnt strengths of each salt were prepared from weighed quantities of the recrystalked pure crj stalline salt, of commerce and weighed quantities of water, the intermediate solutions being obtained by dilution.With ferrous sulphate, hoaewr, a11 solutions were made directly from the salt and J. W.GENERAL AND PHSSICAL UHEIJISTRY. 255 wat,er; in this case, also, air was eliminated from the water as thr a8 possible by boiling. In all the Ealts tested, in concentrations varjing from 1 per cent. to about 5 per cent. of anhjdrous salt, the excess of densitgof a solution over that of water a t the same temperatare is directly pro- portional to the percentago of salt in the solution, aud may be represented symbolically by the equt tion Dt = di + kp, in which Dt and di are the densities at the same temperature t of a, solution and of water respectively, p the percentage of anhydrous salt in the solution, arid k a constant ior all sufficit.utly dilnte sollitions of any one salt.Uata are furnished showing the close agreement between the numbers calculated from the formula and those obtained from actual observations. In the following table, the value of k is given, and the maximum observed concentration up to which it holds good for each salt. Salt. ZUSO, .......... M gw,. ......... hl gso, ......... FedO, .......... CdSO, .......... C'USO~ .......... A I?(SO,)a ....... AlK(SO& ...... &SO, .......... P$lO,. ......... Ntr,YO, ......... Na$04 ......... KHO .......... NaHO.. ........ - t. - 20 '0° 20 '0 23 *o 20 .o 18 0 18 ,o 12 ' 5 20 *o 15 .O 12.5 15 *o 15-0 18 .O 18 .O k. 0.01039 I 8 0' 0106321 0 0098176 0 40994u6 0 '0097329 0 '0098427 0 * OO93083 0 '009518',' 0 *0081600 0 9085950 0 -0091878 0.0091267 0 e0093717 0.0145630 Maximum concen- trtlthn per cent-.3 .o 2 .o betweell 2 .O and 2 . 5 above 2 -6 ahout 3 -0 below 2 0 2 -5 f at leust 1 *7 '1 posaihly 2 .5 } 2.6 2 . 5 4'0 4 0 o\*er 5 -0 about 2 -0 Observer. MacGregor. Schiff. MacGregor. Grot rim. Gerlnch. Ha$senfrutx. MacGrcgor. Gerlach. Ha8se;if i.atz. Ostwsl;:. Gerlach. Thornsen. Thornsen. 97 The formula seldom applies to concentrations below 1 per cent., exceptions beiiig magnesium, copper, and potassium alumiilium sulphates. D. A. L. Dissociation Hypothesis of Arrhenius. By J. TRAC'BE (Ber., 23, 3519--;353U).-'l'lie author raises a number of objec:tioris to the hypothesis of Arrhenius OF the dissociation of electroljtes in diluts aqiieous solution (Abstr., 1888, 896).The byputhesis contmdicts our ordinary conceptions of chemica.1 affinity, since even tho most stable compounds are assumed to dissocia.te when dissolved in water. All explanations of reactions in solution based on the assumption of it so-called nascent, condition become impossible under the new hypo- thesis. To explain the fact t h a t the ions which are assumed to exist in the free state in aqueous solutions cannot, be separated from one aiiotiier b j diffusion, the furlher assumption is made thst; the ions are256 ABSTRAOTS OF OHBMlCAL PAPERS. endowed with charges of opposite sign, and are, in conseluence, so dependent one on another that thev cannot be sepal-ated without the application of energy fkom the oubside. This is, however, to assnme a dissociation where none redly occurs.According to the Irypothesis, the colour of any particular ion i n solution sliould always be the mme, whereits an atom of iron in the thiocynnate is red, in Prrissian blue is blue, i n ferrous sulphate is green, ttnd in ferric chloride is yellow. The additive properties of dilute solution<, which Arrhonius rega,rdR aq of so much importance in support of the tiypothesis, are rather to be looked on a s a weak point. For were the hypothesis correct, all the proper.ties of dilute solutions would be of an additive nature, and this is by no means the case. The freezing point redaction OE a mixed solution i s either equal to or less than the sum of those of its constituonts, according as there is no action between the salts or the formation o f a double salt.On the dissociation hypothesis, the former only would he the case. The hypothesis also contraJictIs in every way the hydrate theory, ignoring the fnct that from the properties of solutions the existence of bydrates has been predicted which have subsequeritly been obtained in the free state. We should be compelled to assume t h t oven in solutions of 10 per cent. to 15 per cent. concentration, salts exist in a dissociated condition, and if we accept the Arrheniw reasoning, that in a 65 per cent. solubion of silver nitrat: tbis salt is completely dissociated. Ostwald (Abstr., 1888, 102U, 1141) applies the laws of gaseous dissociation to electrolytes, hut the forinula lie obtains, m2/(1 - m)o = C, which should be applicable to all binary elcctro- lytes, only liolda for organic acids of low conductivity. Altliouph, therefore, the formula holds for some hurtdreds of acids, there are an equally large nurnber of compounds to which it is absolutely in- applicable.The application of the gaseous l a w s by Arrheuius to electrolytes leads to the conclusion that the dissociation is attended in some cases with a development of heat, a result which cannot be reconciled tvdth the idea that energy i.; required to separate the ioiis fram one another. The phenomena of electrolytic conduction are opposed to the dissociation hypothesis. For since many indifferent organic compounds have a, moleculnr conductivity, which like that of the acids decrzases with the concentration, it wonld be necessary t o assume for these also an electrolytic dissociation, whicb, however, is impossible. In rhe same way, all the abnormal results for the osmotic pressure, and lowering of the freezing point of organic compounds, would have to be taken as iirdicatiug that these also undergo electro- lytic dissociation.Objections tire raised to Arrhenius' method of calculating the value of i from the conductivity (Zoc. cit.). The values of a are calculated for solutions containing 1 gram of the dissolvcd substance in R litre O E water. The freezitig poitit determinations, on the other liand, apply to normal or half-normal solutions. The error, therefore, i n the latter series of numbers must be at leest 20 per cent. The value a = 0 is assumed for non-electrolytes, but the author cannot Ree any rewon why the law of Kohlransc5 X = u + v shoulil ho applied at all to non-electrolytes.H. C .GEXERAL AND PHYSICAL CHEMISTRY. 257 Surface Tension of the Halogens. By A. A. TRUSSE~VITSCH (Zed. physikul. Chem., 6, 360--361).-The author, in this prelimina~y comniunication, gives the results he obtained from measurement of the capillary clevntion of bromine and liquid chlorine. He finds for bromine pi = 4.11, and for chlorine y = 2.72. Influence of Mass on Chemical Processes. By F. RI..HRMANN ( J . p ~ . Cltsm. [el, 42, 13&142).--The author gives some further instances in support of the view that he put forward in a former paper (Abstr., 1890, 484), that not only the laws of chemical affinity, but also the atoubic or molecular weight of the replacing atom o r radicle dominates or directs the position which it takes up in any compound. The above assnmpiio~ serves to explain the fact t h , t many compounds, such n s henzilcdioxime, are capable of existing in stereochemically different forms, whererts other compounds of ana- logous constitution, such as diacetyloxime, exist only in one form.Afflnity Constants of Organic Acids, &c. By R. BADER (Zeit. yhysikal. Chern.. a, 289 -318).--The aiithor, i n tbis paper, communicates his det,erminatioris of the dissociation constants of some 60 organic substances of acid character. The chief vompouiids investigated are the hydroxybenzenes, their derivatives, and certain cyanamide corn- pou ti d s. The mono- and poly- liydroxyhenzenes are extremely feeble acids, so much 60 that, it is impossible to obtain a constant for them at all.When alkyl rrtdicles, Ibowcver, are introduced into the benzene nucleus, the acid properties increase rnni-kedly, the cresols, for ex- ample, giving definite though still very small constants. The intro- duction of a chlorine atom exerts no great influence on the phenols ; the nitro-gronp, on the otlier h m d , is extremely active, nitrophenol and tho dinitrophenols being moderately etrong acids. The position of the substituent groups w i t h regard to the hydroxyl here p l a p a great part in determining the strength of the compound. Tri- nitrophenol (picric acid) is quite comparable to the mineral acids. Nitrodihydroxy-derivatives are sti-ouger than the corresponding nit1 0- monohydroxy-compounds, but are still dissociated only as monobasic acids.Cyanamide in aqueous solution scar.ce1-y conducts electricity at all, is thus feebly dissociat,erl, and shows no diatinct acid properties. Its derivatives of the type CNeNHK’, where R’ is tt univalent acid radicle, are, however, in many cases strong acids, being nsuaily much more powerful than the corresponding carboxylic acids themselves. Thus, whilst acetic acid has the constant K = 0.0018, acetylcjanamide, CN*NH(C,H,O), has K = 0.015. When the substituting radicle is that of a sulphonic acid, the resulting substance, though acid, is by no means so powerful a s the correspondii’g compound derived from a carboxglic acid: for example, we have for CN*NH(C,H,*CO), K = 0.186 ; but for CX*NHI(C6H,.SO,), K = 0.0013.The replaceability of the hydrogen atom of t,he imido-group is evidently conditioned by the simultaneous presence of the cyanogen group and an acid radicle in the molecule. An acid radicle ftlono is insufficient to impart J. W. H. C.258 ABSTRACTS OF OHEMICAL PAPERS. >NH, HiCO cu2*co strongly acid properties to the group NH ; succinimide, for instrance, being practically a non-conductor of electricity in aqneous solution. Other acids irivestigated were /3-nnphthoic acid and its reduction products ; a-t hiophenic acid (stronger than benzoic acid) ; tetrahydro- a-thiophenic acid ; phenylglyoxylic acid (very powerful) and its ketoxime ; isocinnam ic acid (much stronger than ordinary cinnamic acid) ; dimethylglutaric acid ; ond 3 ~ - and ytruxillic acids.J. w. Coefacient of Mineral Condensation in Chemistry. By T. S. HUNT (Arner. C'hent. J., 12, 565-585) --Solid or liquid mineral species (including under the designation of minerals all distinct forms of unorganised matter) are formed by intrinsic conclensn tion or poly- merisation from simpler chemical species, often themselves ,ameon:;. There ia at present no metshod of fixing the amount, or, in other words, of determining the coeficientf, of the condensation, often very con- siderable, which results in the production of such mineral species. The author proposes, however, to do this by assumiitg that for all species, whether gaseous, liquid, or solid, t.he molcculw weight varies as the density, taking that of hydrogen under normal conditions as the unit.Dealing with solids atid liqaids, the density of which is referred to water as unity, it will be necesswy to multiply thiH density by about 11400, the number expressing the densit'y of liquid water with respect to hydrogen, in order to obtain t h e molecular weigtt of H substance in the solid or liquid state. Dividing the number so obtained by the ordinarily accepted molecular weight, deduced chemically or from the gaseous density, we get the coefficient of mineral condensation. Thus for quartz, SiO, = 60, the density oC which is 2.65, the coefficient of mineral condensation will be 2-65 x 2140C/60 = 945 approximately, and for other substances it may be calculated in like manner. The coefficient of mineral condensation expresses the degree of polymerisation necessary in the conversion of the simple gaseous chemical species into the liquid or solid mineral species.The author quotes a number of facts in favour of the view that solid molecules are built up by condensation from the gaseous molecules, and that the above reasoning is therefore perfectlg jnstifiable. All the facts that have up to the present been ascertaiiicd with regard to the rnolecules of solid substances point to their being of great complexity, as would be the case if the views above explained are correct. H. C. Reactions at High Temperatures and Pressures. By W. HEMPEL (Ber., 23, 3388--33Y'L).-l'he author describes an apparatus consisting of a steel cylinder A, containing a porcelain tube G i l l which the substance under examination is placed. Dowtr the middle of the tube, a thin rod of cirrhon F pawm and t i t s into a carbon block F; it may be heated by t'he electric current, passed by means of the copper wires D and K ; the head B of the steel cylitider screws on a i r - tight, and provision is made for pumping in gas through the valvc C,WNEIIAL AND PHYSICAL CHEMISTRY.259 until the desired pressure is obtained. Experiments with this ap- paratus show that the quantity of cyanides obtained from carbon, nitrogen, and alkaline oxides increases ns the pressure becomes greater, potassium cyanide being much more readily formed than barium cyanide. The production of boron nitride from boric anhydride, carbon, and nitrogen follows the same rulc. By H. SCHULZ (Her., 23, 3568--3570).--'l'he apprtrat us described in this p p e r resembles in many respects that recently described by H.Wislicenus (this vol., p. 146), but differs from it, inasmuch a8 the bell-jar covering t h o vessels for the collection of the distillate is the part which i s made to rotate. It is very simple in construction, and can readilj be made of any size, and is, therefore, suitable for technical purposes. H. G. C. Error in the Principle of the Ordinary Exsiccator. By W. HEMPEL (Rer., 23, 3566--3568).--Zn the ordinary exsiccntors, the material used for absorbing the moisture is always placed at the bottom, the result of which is that diffusion of dry air takes placs very slowly, owing to the fact t8ha.t dry air i s heavier than moist n.ir at. the same temperature. If the drying material be placed above the J.B. T. Apparatus for Fractional Distillation in a Vacuum.260 ABSTRACTS OF CHENICAL PAPERG. slibstance which is t.0 be dried, a much more rapid evaporation will Lake place, the dried air falling to the bottom, and thus causing rapid currents witahin the apparatus. To dcterrnine the difference in the desiccating action, two dishes, each containing 10 C.C. of water, were placed in two similar exsiccators, the one being above and the other below the dish containing the sulpburic acid. In the first case, the watw took nine days to evaporate, and in the second only three days. The author recommends the employment, of Rn ordinary bell-jar exsiccator, in which the dish of drying material is fixed as high as possible on an iron tripod, and the substance to be dried placed underneath.If snlphuric acid is employcd, it is advisable to place in the liquid largo pieces of glass, porcelain, or pumice stone. The hat named substance must previously be boiled with sulphuric acid to remove the chlorides i t contains. The drying action may he further increased by cooling the highest poi*tion of the bell-jar with a freezing mixture, which causes the fortriatiou of' stronger currents inside the exsiccator. Notwithstanding the presence of the sulphuric acid, the moisture separates out a t the coolest places i n the form of snow. By W. CAMERER (Zeit. anal. Chem., 1890, 576).-This material is a very advantageous sub- stitnte for the porons clay and plaster of Paris plates hitherto used for drying precipitates, dic.A c o a h g of cellulose gives (t smoother surface. M. J. S. H. G. C. Absorption Plates of Wood Wool.249General and P h y s i c a l Chemistry.Circular Polarisation of certain Tartrate Solutions. By J.R. LONG (Amer. J . Sci. [3], 40, 275-283 ; compare Sbstr., 1890,Sl;J).-The specific rotation of potassium antimony tartrate is con-siderably reduced hy the admixture of carbonates, borates, phosphates,or acetates in amounts insufficient to produce immediate precipitation.Investigation of 1 his behaviour leads to the coriclusicn that on mix-ing solutions of alkaline phosphates, acetates, carbonates, or borateswit.h the tartrate in the cold, there is probably first formed a, tern-porarily stable mtimony salt, with a corresponding amount of alkalinetartrate.'I'he obsiwed rotation is due to this plus that of theiinchanged potassi L i r n antimony tartrate.The specific rotation of potassium ammonium tartrate is butslightly affectod hy the presence of ammonium or potassium salts,but is considerably diminished by the addition of a sodium salt.This behaviour may also be explained on the general hypothesis ofreplacement in the tartrate niolecule by excess of inactive salts.Phosphorescence of Lithium Compounds in Vacua, andSpectra of Coated Terminals. By E. E. BROOKS (Chem. News, 62,239).-Vnrious lithium salts and minerals exhibited the followingphosphorescence phenomena and continuous spectra showing a con-centration of light in certain parts, when examined by Crookedmethod in the negative discharge in a vacuum :-Sulphate, a brightlilac-blue ; phosphate, bright, light Cambridge blue, when fused withsodium carbonate the colour became bright emerald-green, and, unlikethe other cases, the glow was prolonged for a second or t w o after thecii-cuit was broken : chloride, moderately brilliant, pale lavender-blue ; fluoride. moderately brilliant, very light flesh-colour ; silico-fluoride, deep blue with darker spots, not ho brilliant as the sulphate ;spodumene, golden-+yellow ; lepitiolite, very brilliant, deep-red, with.Lt.aces o€ blue ; petalile, very brilliant, rich yellow ; amblggonite,trace of white glow ; the nitrate, carbonate, hydroxide, and rubellitearid indicollite did not phosphoresce ; but the nitrate, fused in a glasstube, produced an opFtque, enamel-like appearance at surfaces of con-tact, by which the inherent yellowish phosphorescence of the Germanglass became -jellower.By coating with, or simply placing 011, aluminium or platinumnegative terminals, lithium, thallium, sodium, calcium, or bariumsalts, and submitting them to a discliarge in a racuiim of moderatetenuity, the flame spectra of the respective metals were obtained;other metals gave very taint spectra, or even none, with the 1-inch-spark coil employed,H.C .These spectra disappear in high vacua.I) A. L.Crystalline Liquids. By 0. LERMAXN (Ann. Phys. Chern., 41,525--537).--The author has drawn attention to the fact tba$ certainVOL. LX. 250 ABSTKACTS Ot“ CHEMICAL PAPERS.liquids exist which behave optically as if they had a crystalline struc-ture (Abstr., 1890, 106).These liquids are chemically homogeneous,rlnd the anisotropy is not produced by exteimd force. He now asksthe question whether isotropic liquids are non-crystalline, or whether.they belong to the regular system, and concludes that in view of thevery general miscibili t.y of liquids they are non-crystalline, for other-wise they would onlyhave tl:e power of mixing with isomorphoussubstances. This conclusion lie supports by experiments on themiscibility of crystalline lifpids with each other and with solidcrjsta1c;l. Liquid crystals, when heated between cover glasses slightlyabove the point, where they pass into ordinary liquids, retHin oilcooling the origin;il direction of their optical axes, owing probably tocondensation and consequent higher “ melting ” point of a layer onthe surface of the glass.Isomorphous liquid crystals exhibit thepheuomena of diffusion, and thus the capability of solids to formmixed crystals appears to correspond exwctlv with the process ofmixing or diffusion in liqiiids (compare van’t HofT, Abstr., 1890,104 k). J. W.Passive State of Iron and Steel. Hy T. ANDREW‘S (PIWC.Roy: Soc., 48, 116--12S).--Steel magnetised by hand or by it coilexhibits a small E.M.F., almost always p )sit,ive with respect tolion-mftpnetised steel, when both are immersed in nitric acid of sp. gr.1.42 at the ordinary temperature. As the temperntnre is r A i s d , theE.M.F. varies somewhat, but remains small, riot exceeding 0.03 volt.,4t about 90”, however, the magnctised steel is attacked violently bythe acid, and the E.M.F.rises suddenly to as much as 0.3 volt,.Effect of Pressure on the Electrical Conductivity of Liquids.By C. BARUS (Amer. J . Sci. [ S ] , 40, 219-222).--Por commercialiuercnry subjected to pressnres between 10 anci 400 atmos. isotliei*-tnally, -6rt/tt = 30 x 10-sSP, where SR/R is the decrement of thespecific electrical resistance R, corresponding with the pressure incre-ment SP. If v i R the volume, tlien from the results of Gras:;i andothers, - & j / t ’ = 8 x lG-SSP, and hence 6R/R = 106z-/v. If 0 be tliesymbol of temperature, the following approximate results apr)ly,i-opiestically, at ordinary temperatures nnd pressiires: i?R’/R’ = 800 x10-680, and 6c/o = 180 x 10-6d0.Hence 6R/R’ = 4.4 &/v, whereXI’ refers GO electrical resistance considered in its thermal relations.l+”or a conce-rtrated solution of zinc sulphate subjeched to pressnresfrom 10 to 400 atmos., similar expres3ioas apply with somewhat lessa :curacy.Expressing the results graphically, the pressures in atmospheres orvolume decrements per unit of volume are found to be linearfunctions of the corresponding decrements or increments of electricalresisttmce per unit of r4staiice. The cuwes for thermal change ofresistairce Slt’/R coordinated with volume aecrement are also recti-linear. In order to bring the compression loci into coincidence withthe thermal loci, the former must be rotated in each case around theorigin in a direction contrary to tho hands of a watch.The angle ofrotation is coneiderably greater for zinc sulpliate solution tliun it, i sJ. WGENERAL AND PHYSlCAL CHEMISTRY. 251for mercury. From this, follows the remarkable result that, bothit1 the case of the metal and of the electrolyte, the effect of isothermalcompression is a decrement of resistance nearly proportional to pres-sure, and by deduction, that the immediate electrical effect of rise oftemperature, &R'/R - sR/R, is a decrement of specitic resistance, bothin the case of the metal and of the electrolyte. This points out, aninberent similarity betweeu the metallic and the electroljtic conduc-tion in this instance. H. C.Electrical Conductivity of Boric Acid Solutions in Presenceof Dulcitol.By G. MAGNAMNL (Gazzetta, 20, 44148).-'l'heauthor has applied his new met-hod of studying the constitution ofsolutions (see Sbztr., 1890, 1357) to the investigation of the mole-cular composition of the compounds existing in solutions of bwicacid aad dulcitol. The variations of the molecular conductivity ofboric acid solutions in presence of dulcitol are precisely of the samecharacter as those which occur in presence of mannitol, with this dif-ference, however, that from the observed values of the conductivity inthe case of dulcitol, no simple relation for the m3lecnlar compositionof the electrolytic compound or compounds can be calculated. Thisrenders it probable that several compounds of boric acid and dulcitolexist together in the solution.S. B. A. A.Determination of BDiling and Freezing Points by means ofthe Platinum Thermometer. By E. H. ORIFFLTHS (PTOC. Roy. SOC.,48, 220-225) .-Eight thermometers, varying somewhat in con-struction, were compared. The best form was found to be the follow-ing:-A coil of fine platinum wire is wound on a roll of asbestospaper, and slipped into a thin tube of hard glass. Thick platiuumwit-es run from this coil to the top of the instrument, and fheunimmersed portion of the stem is surrounded by the outcr tube of acondenser, throiigh which tap-water is kept flowing. The diameteris less than 3/!.6ths of an inch, and the 1eng:Gh about 18 inches. Thoinstruments were graduated at the boiling points of water, naphtha-lene, benzophenone, and salphur, and the freezing point of wtiter.From the determina$ions of the boiling points of rarious substances,it was found that although the curves for the different thermometersvarv considembl v in form. intermediate temtwratnres deduced fromt,h& are in prackcal agrekent (less than 0.1') up to 500".J.W.Heat of Combustion of Organic Compounds. By F. STOH-MAWN (Zeit. physikal. Chent., 6, 334--35i).--In this paper are collectedand systematically arranged the heats of combustion of over400 organic compounds. The tables include all the determinationsmade from 1852 until Augnat, 1890, with the exception of t,he experi-ments of Frankland, Ramsay, von Rechenberg, and Danileflski.Many hitherto unpublished determinations by the author and hispupils are also included.In the various columns are given the heatof combustion per gram in small calories; the heat of combustionper gram-molecu!ar weight i n grcat calories (both at constant pressure8 252 ABSTRAO'J'P OF CHEMIOAL PAPERS.9.55.78 . 52 . 83 . 36 ' 41.04.2and conRtant volume) ; the heat of formation in great calories ; thoobserver ; and the reference to the original source. In calculatingthe heats of formrttion, tho author assumes the following heats ofcombnation:-C, 94 Cal.; H f , 69 Cal.; and S, 69.3 Cal. J. W.0*093000*121000'028700-102000.008670.002860.020400*00678Relations of the Heats of Combustion of Solid BibasicAcids to those of the Gaseous Hydrocarbons.BV F. STOHMANN( J . pr. Chem. [2], 42. 248-259; compare Abstr., 1889, 1096, andAbstr., 1890, loo).-lf A is the heat of combustion of any bibasicacid, and B that of the gaseous hydrocarbon frcm which it is derived,then the ratio A/B is practically a constant. A mean value for thisconstant obtained from the determinations of the heats of combustionof 22 different acids is 0.97692. Hence, if the heat of combustioriof a molecule of a gaseons hydrocarlion is tnkeii as unity, that of thecorresponding bibasic acid will be 0.97698, or the heat of combustionof the hydrocarbon is obtained by dividing tltrtt of the acid by097692. A comparison between numbers thus calculated and thoseobserved shows a very srttisfactor-y agreement.The dieerence B - A is equal to the sum of two numbers x and y,the first of which is the loss of heat i n the passage of the bydro-carbon from the gaseous to the solid condition, and the second tbc?heat evohed in the conversion of the solid hydrocarbor, into thecorresponding acid.I n some cases x is already known, and for othersit may be calculated without serious error on the assumption that theheats of fusion and vaporisation of unit weight of all hydrocarbonsare the same. The value of x being known? y the heat, of formationof the acid from the hydrocarbon is theu easily calculated.The following table gives values of y for different acids calculatedby the above method :-Malonic acid .........Dimethylmalonic acid..Succinic acid .........Et~h~lsuccinic acid.....Glutaric acid.. .......Piinelic acid.. ........Adipic acid. ..........Male'ic acid ..........Methylmalonic acid.. ..Ethylmalonic acid. ....Metbylsuccinic acid ...-YeCal. -2 *51 -75 '58-19.78 '27.46 *28.110-73 3K.--0 -171000 -087000 *127000.07';OO0 -006650 Q08600 *008600 904750 -003570 003711 -17oOO----Fumavic acid ........Phtlialic acid ........Isophthalic acid.. ....Salicylic acid ........Met aliydroxjbenzoicacid ..............Purahydruxy benzoicacid ..............a-Nnphthoic acid ...../3-Naphthoic acid. ....---In the second colurrin of the table, are giren the values of Ostwa,ld'saffinity coefficients, between which and the heats of formation thereis an evident, relation, for acids of similar constitution the affinitycoefficient being smaller the greater the heat of forma4tion. Methyl-malonic acid occupies an exceptional position i n the malonic acidseries. By analogy with the cther acids of t.his series, the heat oQENERAL AND PHYSICAL OHEMISTRY.253formation should be between 2.5 Cal. and 5.5 Cal., and the affinitycoefficient between 0.171 and 0.127. Instead of this, the numbersare 1.7 Cal. and 0.087. H. C.Compressibility of Mixture8 of Air and Carbonic Anhydride.By U. LALA (Conzpt. rend., 111, 819--82i).-The author has investi-gated the compressibility of mixtures of air and carbonic anhydridecontaining 11 to 56.92 per cent. of the latter, n t pressures extendingto 1613.96 cm.of mei.cui:y. When the proportion of carbonicanhydride does not exceed 22 per cent., the compressibility liesbetween that of air and carbonic anhydride, and is, at first, nearer toothat of air, but approaches more closelv to that of carbonic anhydrideas the pressure increases. The greater the proportion of carbonicamhydride, the lower the pressnre at which the cornpressihility becomesequal to that of carbonic anhydride alone. As the proportion ofthis gas increases, the compressibility becomes greater than it wouldhe it' no air were present, but beyond a, certain point it decreasesaiid tends to revert-to tho cotnpressibility of pure carbonic anhydride.C. H. B.Experiments on Vapour Density. By E. P. PERMAY (PTCC.Roy. h'oc., 48, 45-59) .-This investigation was undertaken mainlyto ascertain if bromine dissociates at low pressures and moderatetemperatures.The apparatus employed is figured in the accom-panying cut. A is a glass globe of known capacity (abont f litrejblowti inside a larger globc, B. The liquid which produces thevapour-jacket is boiled in C, and condensed in D, which ma.y bespecially cooled if noccssary. P is a tube containing a liquid toabsorb the bromine vaponr, a few drops being also introduced int254 ABSTRACTS OF CHEMIOAL PAPERS.the bulb-tube G. M is an air reservoir, and 0 a pressure gauge, thetube P being attached to a water-pump.A is first exhausted, and then there is introduced into i t a, littleliquid bromine, air being excluded. The tube ahore E is fused on toF, the liquid in C boiled, and the bromine allowed gradually to blowont over the potash solution in F.The tube above tho globe must,be heated gently with a Bunaen flame. Tbe apparatus is nowexhausted as far as possible, the stopcock E turned off, the tubeabove cracked and removed, triore bromine admitted as a t first, tlrstube fused together again, m d the bromine driven out as before untilthe vapqur in A has the atmospheric pressure at hhe temperature of;the boiling liquid in C. The absorption-tube F is then filled witlistrong solution of potassium iodide, anit the whole apparatus connectedup as in the tigure. M is exhausted to the requisite degree, and thopump cut off by the screw-clip R. Bromine vapour is allowed toeeoape from A by cautious mallipulation of the stopcock E untilequilibrium is attained.The pressure is then rend off, the stopcockL closed, and the contents of the absorption-tube washed into astoppered bottle to be afterwards titrated with thiosulphate. Theexperiment is then repeated at lower pressures until the series iscomplete.By adding together the residual quantity of bromine and thequantities removed, the weight of bromine in the globe-at eachpressure is found, and as the volume occupied is already known, alldata required are availa ble.It was found that at. temperatnres ranging from 15" to 280", and ntpressures from 15 mm. to 760 mm., bromine vapour exhibited thenormal density withoat any indication of dissociation.Iodine, when vaporised in a similar apparatus, did not yield constantresults, so experiments with it were conducted by means of anapparatus for determining the speed of sound in the vapour.Finely-divided precipitated silica was used to ascertain the wave-lengtb.The density of the saturated vapour a t 132" was found tobe normal. The author finds (in contradiction to J. J. Thomson,Abstr., 1887, 1013) that the passage of electric sparks through thevapour does not alter its density.A few experiments were made with tho vapour of sulphuricanhydride. Tbe author considers that his results prove the formulaof this substance to be SO, and not S,O,.The vapour density of aqueous hydrochloric acid shows that theacid and water do not combine at the temperature eniployed (132").Variation of the Density with the Concentration of WeakAqueous Solutions of Certain Salts.By J. G. MACGREGOR (Chew.N e w , 62,223-224,252-234).-The densities of the various solutionswere, in these experiments, determined in a specific gibavity bottle a t20°, and, us a rule, at least two solutions of differrnt strengths ofeach salt were prepared from weighed quantities of the recrystalkedpure crj stalline salt, of commerce and weighed quantities of water,the intermediate solutions being obtained by dilution. With ferroussulphate, hoaewr, a11 solutions were made directly from the salt andJ. WGENERAL AND PHSSICAL UHEIJISTRY. 255wat,er; in this case, also, air was eliminated from the water as thra8 possible by boiling.In all the Ealts tested, in concentrations varjing from 1 per cent.to about 5 per cent.of anhjdrous salt, the excess of densitgof asolution over that of water a t the same temperatare is directly pro-portional to the percentago of salt in the solution, aud may berepresented symbolically by the equt tionDt = di + kp,in which Dt and di are the densities at the same temperature t of a,solution and of water respectively, p the percentage of anhydroussalt in the solution, arid k a constant ior all sufficit.utly dilnte sollitionsof any one salt. Uata are furnished showing the close agreementbetween the numbers calculated from the formula and those obtainedfrom actual observations. In the following table, the value of k isgiven, and the maximum observed concentration up to which it holdsgood for each salt.Salt.ZUSO, ..........M gw,..........hl gso, .........FedO, ..........CdSO, ..........C'USO~ ..........A I?(SO,)a .......AlK(SO& ......&SO, ..........P$lO,. .........Ntr,YO, .........Na$04 .........KHO ..........NaHO.. ........-t.-20 '0°20 '023 *o20 .o18 018 ,o12 ' 520 *o15 .O12.515 *o15-018 .O18 .Ok.0.01039 I 80' 01063210 00981760 40994u60 '00973290 '00984270 * OO930830 '009518','0 *00816000 90859500 -00918780.00912670 e00937170.0145630Maximum concen-trtlthn per cent-.3 .o2 .obetweell 2 .O and 2 . 5above 2 -6ahout 3 -0below 2 02 -5f at leust 1 *7'1 posaihly 2 .5 } 2.62 . 54'04 0o\*er 5 -0about 2 -0Observer.MacGregor.Schiff.MacGregor.Grot rim.Gerlnch.Ha$senfrutx.MacGrcgor.Gerlach.Ha8se;if i.atz.Ostwsl;:.Gerlach.Thornsen.Thornsen.97The formula seldom applies to concentrations below 1 per cent.,exceptions beiiig magnesium, copper, and potassium alumiiliumsulphates.D. A. L.Dissociation Hypothesis of Arrhenius. By J. TRAC'BE (Ber.,23, 3519--;353U).-'l'lie author raises a number of objec:tioris to thehypothesis of Arrhenius OF the dissociation of electroljtes in dilutsaqiieous solution (Abstr., 1888, 896). The byputhesis contmdictsour ordinary conceptions of chemica.1 affinity, since even tho moststable compounds are assumed to dissocia.te when dissolved in water.All explanations of reactions in solution based on the assumption ofit so-called nascent, condition become impossible under the new hypo-thesis.To explain the fact t h a t the ions which are assumed to existin the free state in aqueous solutions cannot, be separated from oneaiiotiier b j diffusion, the furlher assumption is made thst; the ions ar256 ABSTRAOTS OF OHBMlCAL PAPERS.endowed with charges of opposite sign, and are, in conseluence, sodependent one on another that thev cannot be sepal-ated without theapplication of energy fkom the oubside. This is, however, to assnmea dissociation where none redly occurs. According to the Irypothesis,the colour of any particular ion i n solution sliould always be themme, whereits an atom of iron in the thiocynnate is red, in Prrissianblue is blue, i n ferrous sulphate is green, ttnd in ferric chloride isyellow.The additive properties of dilute solution<, which Arrhoniusrega,rdR aq of so much importance in support of the tiypothesis, arerather to be looked on a s a weak point. For were the hypothesis correct,all the proper.ties of dilute solutions would be of an additive nature,and this is by no means the case. The freezing point redaction OE amixed solution i s either equal to or less than the sum of those of itsconstituonts, according as there is no action between the salts or theformation o f a double salt. On the dissociation hypothesis, theformer only would he the case. The hypothesis also contraJictIs inevery way the hydrate theory, ignoring the fnct that from theproperties of solutions the existence of bydrates has been predictedwhich have subsequeritly been obtained in the free state.We shouldbe compelled to assume t h t oven in solutions of 10 per cent. to15 per cent. concentration, salts exist in a dissociated condition, andif we accept the Arrheniw reasoning, that in a 65 per cent. solubionof silver nitrat: tbis salt is completely dissociated.Ostwald (Abstr., 1888, 102U, 1141) applies the laws of gaseousdissociation to electrolytes, hut the forinula lie obtains,m2/(1 - m)o = C, which should be applicable to all binary elcctro-lytes, only liolda for organic acids of low conductivity. Altliouph,therefore, the formula holds for some hurtdreds of acids, there are anequally large nurnber of compounds to which it is absolutely in-applicable.The application of the gaseous l a w s by Arrheuius toelectrolytes leads to the conclusion that the dissociation is attendedin some cases with a development of heat, a result which cannot bereconciled tvdth the idea that energy i.; required to separate the ioiisfram one another. The phenomena of electrolytic conduction areopposed to the dissociation hypothesis. For since many indifferentorganic compounds have a, moleculnr conductivity, which like that ofthe acids decrzases with the concentration, it wonld be necessary t oassume for these also an electrolytic dissociation, whicb, however, isimpossible. In rhe same way, all the abnormal results for the osmoticpressure, and lowering of the freezing point of organic compounds,would have to be taken as iirdicatiug that these also undergo electro-lytic dissociation.Objections tire raised to Arrhenius' method of calculating thevalue of i from the conductivity (Zoc.cit.). The values of a arecalculated for solutions containing 1 gram of the dissolvcd substancein R litre O E water. The freezitig poitit determinations, on the otherliand, apply to normal or half-normal solutions. The error, therefore,i n the latter series of numbers must be at leest 20 per cent. Thevalue a = 0 is assumed for non-electrolytes, but the author cannotRee any rewon why the law of Kohlransc5 X = u + v shoulil hoapplied at all to non-electrolytes. H. C GEXERAL AND PHYSICAL CHEMISTRY. 257Surface Tension of the Halogens. By A.A. TRUSSE~VITSCH(Zed. physikul. Chem., 6, 360--361).-The author, in this prelimina~ycomniunication, gives the results he obtained from measurement of thecapillary clevntion of bromine and liquid chlorine. He finds forbromine pi = 4.11, and for chlorine y = 2.72.Influence of Mass on Chemical Processes. By F. RI..HRMANN( J . p ~ . Cltsm. [el, 42, 13&142).--The author gives some furtherinstances in support of the view that he put forward in a formerpaper (Abstr., 1890, 484), that not only the laws of chemical affinity,but also the atoubic or molecular weight of the replacing atom o rradicle dominates or directs the position which it takes up in anycompound. The above assnmpiio~ serves to explain the fact t h , tmany compounds, such n s henzilcdioxime, are capable of existing instereochemically different forms, whererts other compounds of ana-logous constitution, such as diacetyloxime, exist only in one form.Afflnity Constants of Organic Acids, &c.By R. BADER (Zeit.yhysikal. Chern.. a, 289 -318).--The aiithor, i n tbis paper, communicateshis det,erminatioris of the dissociation constants of some 60 organicsubstances of acid character. The chief vompouiids investigated arethe hydroxybenzenes, their derivatives, and certain cyanamide corn-pou ti d s.The mono- and poly- liydroxyhenzenes are extremely feeble acids,so much 60 that, it is impossible to obtain a constant for them at all.When alkyl rrtdicles, Ibowcver, are introduced into the benzenenucleus, the acid properties increase rnni-kedly, the cresols, for ex-ample, giving definite though still very small constants.The intro-duction of a chlorine atom exerts no great influence on the phenols ;the nitro-gronp, on the otlier h m d , is extremely active, nitrophenoland tho dinitrophenols being moderately etrong acids. The positionof the substituent groups w i t h regard to the hydroxyl here p l a p agreat part in determining the strength of the compound. Tri-nitrophenol (picric acid) is quite comparable to the mineral acids.Nitrodihydroxy-derivatives are sti-ouger than the corresponding nit1 0-monohydroxy-compounds, but are still dissociated only as monobasicacids.Cyanamide in aqueous solution scar.ce1-y conducts electricity at all,is thus feebly dissociat,erl, and shows no diatinct acid properties.Itsderivatives of the type CNeNHK’, where R’ is tt univalent acid radicle,are, however, in many cases strong acids, being nsuaily much morepowerful than the corresponding carboxylic acids themselves. Thus,whilst acetic acid has the constant K = 0.0018, acetylcjanamide,CN*NH(C,H,O), has K = 0.015. When the substituting radicle isthat of a sulphonic acid, the resulting substance, though acid, is by nomeans so powerful a s the correspondii’g compound derived from acarboxglic acid: for example, we have for CN*NH(C,H,*CO), K =0.186 ; but for CX*NHI(C6H,.SO,), K = 0.0013. The replaceabilityof the hydrogen atom of t,he imido-group is evidently conditioned bythe simultaneous presence of the cyanogen group and an acid radiclein the molecule.An acid radicle ftlono is insufficient to impartJ. W.H. C258 ABSTRACTS OF OHEMICAL PAPERS.>NH,HiCOcu2*co strongly acid properties to the group NH ; succinimide,for instrance, being practically a non-conductor of electricity inaqneous solution.Other acids irivestigated were /3-nnphthoic acid and its reductionproducts ; a-t hiophenic acid (stronger than benzoic acid) ; tetrahydro-a-thiophenic acid ; phenylglyoxylic acid (very powerful) and itsketoxime ; isocinnam ic acid (much stronger than ordinary cinnamicacid) ; dimethylglutaric acid ; ond 3 ~ - and ytruxillic acids.J. w.Coefacient of Mineral Condensation in Chemistry. By T.S. HUNT (Arner. C'hent. J., 12, 565-585) --Solid or liquid mineralspecies (including under the designation of minerals all distinct formsof unorganised matter) are formed by intrinsic conclensn tion or poly-merisation from simpler chemical species, often themselves ,ameon:;.There ia at present no metshod of fixing the amount, or, in other words,of determining the coeficientf, of the condensation, often very con-siderable, which results in the production of such mineral species.The author proposes, however, to do this by assumiitg that for allspecies, whether gaseous, liquid, or solid, t.he molcculw weight variesas the density, taking that of hydrogen under normal conditions asthe unit.Dealing with solids atid liqaids, the density of which isreferred to water as unity, it will be necesswy to multiply thiHdensity by about 11400, the number expressing the densit'y of liquidwater with respect to hydrogen, in order to obtain t h e molecularweigtt of H substance in the solid or liquid state. Dividing thenumber so obtained by the ordinarily accepted molecular weight,deduced chemically or from the gaseous density, we get the coefficientof mineral condensation.Thus for quartz, SiO, = 60, the density oCwhich is 2.65, the coefficient of mineral condensation will be 2-65 x2140C/60 = 945 approximately, and for other substances it may becalculated in like manner.The coefficient of mineral condensation expresses the degree ofpolymerisation necessary in the conversion of the simple gaseouschemical species into the liquid or solid mineral species.The authorquotes a number of facts in favour of the view that solid moleculesare built up by condensation from the gaseous molecules, and thatthe above reasoning is therefore perfectlg jnstifiable. All the factsthat have up to the present been ascertaiiicd with regard to thernolecules of solid substances point to their being of great complexity,as would be the case if the views above explained are correct.H. C.Reactions at High Temperatures and Pressures. By W.HEMPEL (Ber., 23, 3388--33Y'L).-l'he author describes an apparatusconsisting of a steel cylinder A, containing a porcelain tube G i l lwhich the substance under examination is placed. Dowtr the middle ofthe tube, a thin rod of cirrhon F pawm and t i t s into a carbon block F;it may be heated by t'he electric current, passed by means of the copperwires D and K ; the head B of the steel cylitider screws on a i r -tight, and provision is made for pumping in gas through the valvc CWNEIIAL AND PHYSICAL CHEMISTRY.259until the desired pressure is obtained. Experiments with this ap-paratus show that the quantity of cyanides obtained from carbon,nitrogen, and alkaline oxides increases ns the pressure becomes greater,potassium cyanide being much more readily formed than bariumcyanide. The production of boron nitride from boric anhydride,carbon, and nitrogen follows the same rulc.ByH. SCHULZ (Her., 23, 3568--3570).--'l'he apprtrat us described in thisp p e r resembles in many respects that recently described by H.Wislicenus (this vol., p. 146), but differs from it, inasmuch a8 thebell-jar covering t h o vessels for the collection of the distillate is thepart which i s made to rotate. It is very simple in construction, andcan readilj be made of any size, and is, therefore, suitable for technicalpurposes. H. G. C.Error in the Principle of the Ordinary Exsiccator. By W.HEMPEL (Rer., 23, 3566--3568).--Zn the ordinary exsiccntors, thematerial used for absorbing the moisture is always placed at thebottom, the result of which is that diffusion of dry air takes placsvery slowly, owing to the fact t8ha.t dry air i s heavier than moist n.irat. the same temperature. If the drying material be placed above theJ. B. T.Apparatus for Fractional Distillation in a Vacuum260 ABSTRACTS OF CHENICAL PAPERG.slibstance which is t.0 be dried, a much more rapid evaporation willLake place, the dried air falling to the bottom, and thus causing rapidcurrents witahin the apparatus. To dcterrnine the difference in thedesiccating action, two dishes, each containing 10 C.C. of water, wereplaced in two similar exsiccators, the one being above and the otherbelow the dish containing the sulpburic acid. In the first case, thewatw took nine days to evaporate, and in the second only threedays.The author recommends the employment, of Rn ordinary bell-jarexsiccator, in which the dish of drying material is fixed as high aspossible on an iron tripod, and the substance to be dried placedunderneath. If snlphuric acid is employcd, it is advisable to place inthe liquid largo pieces of glass, porcelain, or pumice stone. Thehat named substance must previously be boiled with sulphuric acid toremove the chlorides i t contains.The drying action may he further increased by cooling the highestpoi*tion of the bell-jar with a freezing mixture, which causes thefortriatiou of' stronger currents inside the exsiccator. Notwithstandingthe presence of the sulphuric acid, the moisture separates out a t thecoolest places i n the form of snow.By W. CAMERER (Zeit.anal. Chem., 1890, 576).-This material is a very advantageous sub-stitnte for the porons clay and plaster of Paris plates hitherto usedfor drying precipitates, dic. A c o a h g of cellulose gives (t smoothersurface. M. J. S.H. G. C.Absorption Plates of Wood Wool

ISSN:0368-1769    

DOI:10.1039/CA8916000249

出版商:RSC    

年代:1891

数据来源: RSC

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260 ABSTRACTS OF CHENICAL PAPERG. I n o r g a n i c Chemistry. Molecular Weights of Sulphur, Phospb.orus, and Iodine in Solution. By J. HERTZ (Zcit. phpikul. C!ht?t~., 6, 35$--359).-Phos- phorus dissolved in benzene gives a depression of the freezing point corresponding with the formula P,. The numbers obtained with sulphur dissolved in nnph thalene point to the exishence of molecules S8, i n accordance with the results obtained by Beckmann, who em- ployed carbon bisulpbide as solvent (Abstr., 189C, 447). The red solution of iodine in naphthalene yields numbers corresponding with the molecule I,. J. W. Action of Metals on Sulphuric Acid. By A. DITTE (Ann. Chim. Phys. [S], 19, 68-92).--The author has investigated the action of a iinmber of metals on sulphuric acid of different degrees of concentra- tion and a t rarious temperatures ; the following general conclusions may be drawn from the results of the experiments :- The metals attacked by sulphuric mid can bo classed in two groups.The one contains those metals which are acted on only when theINORGANIC CHE3lIS'l RY. 261 acid is concentrated and hot ; the reaction i s very regular in all cases, and sulphurous anhydride alone is evolved, no secondary reactions taking place. To this class belong silver, mercury, copper, lead, and bismuth. The second group embraces those metals which are acted on more or less readily by sulphuric acid of all degrees of concentration. The most constant product of the reaction is hydrogen, this gas being always evolved in the cold, and almost always at a high temperature also; when the temperatnre is not very high, hydrogen is the sole gaseous prodiict, whatever the degree of concentration of the sulphuric acid employed.Sulphurous anhydride is only produced when the acid is hot and concentrated ; the temperahme at which the evolution of sulphurous anhydride conimences varies with the metal employed, and, generally speaking, its quantity iirmenses in proportion to the rise of temperature, the quantity of hydrogen decrcasing to a pro- portionate extent, and sometimes, when tho temperature is very high, disappearing t l l together. When the concentration of the sulphum: acid decreases, the formation of sulphurous anhydride also decreases, 80 that, even at a high temperature, i t is not obtained free froni hydrogen ; when a certain degree of dilution of the acid is reached, salphurous anhjdride ceases to be formed.Between certain limits of temperature and concentration, which vary with the nature of the metal employed, the action of sulphuric acid gives rise to a mixture of hydrogen and suiphurous anhydride, SO that by choosiiig IL suitnble temperature and an acid of suitable strength, a mixture of the two gases, in any required proportion, could be obtainecl, This is true in the case of metals, like magncsiuni, which only yield hydrogen when treated with siilphurous acid, as the reducing action of the hydrogen on the sulphurous acid under the conditions of the experiment may be neglected. When, however, the nietal em- ployed decomposes sulphurous acid, yielding a sulphide, secondary reactions set in, and hydrogen sulphide is formed: i n mch cases, larger or smaller quantities of ihis gas are formed according as the action of the metal on the sulphurous acid is rapid or RIOW, and according as the sulphide produced is readily or slowly acted on by the sulphuric acid.poses, and is itself decomposed by, some of the sulphurous acid, and ~t also reduces the 5ulphuric acid causing a deposition of sulphur, which, in its turn, acts on the sulphiiric acid. When, however, t h o metal is treated with sulphuric acid under such condition8 that sulphurous acid is not produced, the forniat,iori of hydrogen sulphide and other secondary reactions cease, and pure hydrogen is evolved. 'Po the second of these two groups belong magnesium, manganese, nickel, cobalt, iron, zinc, cadmium, aluminium, tin, thallium, find probably also the alkali metals.I n the case of the last natned, it was only possible to study the behavioiir with snlpburic acid in the cold, and under these conditions hydrogen is evolved, but, considering the close relationship bztween the alkaline metals and thallium, it is very probable that, like the latter, they wonld yield sulphurous anhydride on treatment with sulphuric acid at a high temperature. F. S. K. The hydrogen sulphide t h u s produced262 ABSTRACTS OF CHEXIOAL PAPERS. Selenites. By BOUTZOUREANO (Arm. Chim. Pl2y8, [6], 18, 280- 351).-'l'he author has prepared the following selenites :- s EL EN~TES 0 F RIVAL E N ' ~ MEfrALs.-Basic selen ites :--2 c u 0, Se02, clinorhombic.Normal selenites :-MgO,SeOz + 6H20, cubic. MpO,SeO, + 2Hz0, clinorhombic. ZnG,SeOz, orthorhom bic. CdO,SeOz, orthorbombic. 3( CuO,SeOa) + H20, clinorhombic. 3(CoO,SeO,) + HzO, clinorhombic. 2(Ni0,Se02) + H20, ortho- rhombic. Acid selenites :-MgO,SSeO,, rhombohcdric. Zn0,2Se02 + 3&0, clinorhombic. ;!CdO,SSeOz + H20, clinot-hombic. Cd0,SSe02, ort>horhombic. Cu0,2Se02 + H20, clinorhombic. Cu0,2Se02 + 2H,O, clinorhombic. CuO,BSeO2 + 4H20, clinorliombic. 2( Mn0,2Se02) + H20, clinorhombic. Mu0,2Se02 + 5H,O. CoO,ZSeO, + 3H20, clinorhombic. SELENITES OF QVADRI VAL ICNT METALS. --Busic: selenites : --Mn?O,,BSeO?, clinorhombic. Fe2O3,2SeOZ, clinorhombic. NormaE seEenites :-- Fe,03,3Se02 + 10H,O, clinorhombic. Fez03,3Se02 + 3H20, cubic. Pe203,3Se02 + H20, clinorhombic.A1203,Se0, + 7H20, hexagonal. A1,OJ, 3Se0, + 3H20, cubic. U2O3,SeOz, cubic. Acid seZenites:- Fe203,4Se02 + HzO, orthorhorn bic. Fe203,GSe02 + 2H20, clino- rhombic. A1,0,,4Se02 + 3B,O, orthorhombic. AI2O3,6Se0, + 2H20, clinorhombic. AMMONIACAL S E LE N ifr m.-Zn0,Se02,NH,, orthorh Dmbic. C d 0, SeO,.N H3, orth orhom bic. C u 0, SeO,, N H3 + HzO, tricl in i c. Ag,O,SeO,,NH, tricliaic. With 8, few exceptions, the compounds given in the above list have not hitherto been prepared. The most. siicwssful methods for preparing the salts and obtaining them in well-defined ~ r y s t ~ a ~ l s were found to be (1) heating the Hmorphous or crystalline compounds in sealed tubes at 130-270" \vith water, or with a solntiori OF seleniocs anhydride, or adding se- lenious anhydride to a solut:on of a salt already prepared and heating the mixture in sealed tube..; ; and (2) dissolving metallic carbonates in selenious acid and evnporating the solution.The ammoniacal selenites were prepared by dissolviiig the selenites in ammoiiirt arid evspomting the solutions a t the ordinary tempera.- ture or at 100". I n estimating the selenium irr the salts, except in the case of the srtits of the sesquioxides, t,he best method was found to be the reduc- tion of the seleniou3 acid with Rodium hydrogen sulphite in hydro- chloric acid solution ; t.he results are very satisfactory when care is taken to prevent the volrttilisation of the selenious anhydride, and to cnsure complete reduction. 111 the case of the selenites of the sesquioxides, attempts were made tu detei-mine the selenium by Rose's method, but as the results were riot satisfact,ory, the salts were first boiled with a concenti-nted solution of sodium carbonate, and the beleniouu acid in the tiltered solution eshnated by reduction with sodium hydrogen sulphite as before.Reparation of the Nitrogen Hydride N,H . By E. J. MAUMEN~ !fit& SOC. CILirn. [3], 4? 179-180; compare Abstr., 1889, lP).--Rg the dry distillation of ammonium platiuochloride, the chloridu CoO,SSeO,, olinorhombic. 2( U,O,) ,3Se02 + 7 HzO, clinorhombic. F. S. K.1SORGANIC CHEMISTRY. 263 N,H,Cl, is obtained in six-sided, orthorhombic crystals which condense on the walls of the ret,ort. T. G. N. Hydrazine Hydrate and Haloid Salta (Halogen Diammonium Compounds). By 1'.CURTIUS and H. SCHULZ ( J . p-. Chem. [2], 42, 521-549 ; compare Abstr., 1889, 340).-Hydrazine sulphate forins rliqmbic crystals, 5 : b : c = 0*7_P538 : 1 : 0.82825 ; observed faces mPm, OP, Pw, Pa, d . 2 , 2P2; crystals tabular across w,Pm, colourless and clear; cryoscopic determination of its niolwular weight, in water, gave 69.16, 628i1, ttnd 60.i05 rsspectiT-ely. Hydrazine hydrate is best prepared by distilling a mixtnre of hydrazine snlphate (100 grams), potassium hydroxide (100 grams), and water (25 J grams) in a silver retort provided with a silver con- densing tube. The distillation is continued (5-6 hours) until the last drop has passed over, and the distillate (250 c.c.) i s then frac- tionated, the fractions being best divided into brlow 101", 101-104", 104-1li"~ ll7"-constrtrit boiling point.After four fractionationq, the hydraeine hydrate (36 grams) boils constantly at 119". Most of the properties of hydraline hytllate have been already detailed (Abstr., 1889, 340) ; it is hygroscopic, and nbsorl~s carboiiic anhydride ; it can be kept in c h e d vessels iinchanged ; it dissolves in water and alcohol, but not in ether, chloroform, or benzene; i t solidi6efi in solid carbonic anhydride and ether, but melts again below -40'; it boils (739.5 mm.) atl 118.5"; its sp. gr. at 21" is 1.0305 ; in its reactions with indicators i t resembles ammonia. De- twniination of the vapoui. density of hydraziue hydrate, made by Hofinann's method a t lWo, show that its molecule, under these coii- clitions, is X2H4,H20 ; those made by Victor Meyer's method at l i O o , and at atmospheric pressure, show that the molecule is dissociated under these couditions into N2H4 Rnd HzO ; cryoscopic determinations b h W that the molecular weight of hydrazine hycliate in water is 68, agreeing with the t'ormula N2H4,iLH20.Hydraziue hydrate which has been redistilled over barium oxide fulues In the air mure strongly than tha pure liquid, showing that it, contains free hydrszine dissolved in itl. When the hydrate is heated in tt sealed tube with barium oxide at 170", and the tube is subse- yncntlg opened, hydrazine (dianiide) escapes as a white fume ; ex- yeritiients in this dircction are still in progress. The hydrszine haloid salts are prepared either by mixing aqueous solutions of bydrazine hydrate and the haIogen acid and evaporating, or by additig the acid to an alcoholic solution OE tbe hydrazine hydrate, and subsequentlg adding ether, whereby the salt is precipi- tated.When hydrofluorir: and hIdrocliloric acids are used, tlie salts N2H,,BHR are obtained by both methods ; with hjdrobromic acid, the first method yields the salt N2H4,BBBr, and the second method the salt. K2H4,HBr; with hydriodic acid, both methods yield the salt N2H4,HI. The salts N2H4,BHR crystallise in the regular system, and are isotropic in polarised light; t,hey dissolve easily in water, but arc) nearly iusoluble in alcohol. The salt4 N2H4,Hlt are easily soluble in water and in warm alcohol, from which they cr~stallise well. Both classes are insoluble i n ether, benzene, &c.264 ABSTRACTS OF CHEMICAL PAPERS.Hydrazine dihydrqfltmde (dia.mmonium d{fiuoricEe), N,H4,2HF, melts at 105", and sublimes undec omposcd in presence of excesp of the salt. Hydrazine dihydrochloride has been already described (Abstr., 1887, 715); it can also be obtained by passing chlorine into hydrtaine hydrate. Hjldrasine dihydrobromide, NzH4,2HBr, niel ts at 195" : it can also be obtained by decomposing bsnsalazine (Abstr., 1889, 393) with hydrobromic acid. Hydt-azine dihydriodide, N?H4,ZH 1, can only be obtained by decomposing benzalazine with fuming hydriodic acid ; it is very hygroscopic, becomes brown on exposure to light, and melts at 220". Hydraziiie monhydrochloride has already been described (Abstr., 1869, 340). Hydmzine monhydrobromide, N,H4,HBr, ifr mepared by adding bromine to hgdrtlzine hydrate suspended in chloroform ; i t forms large, anisotropic, colnmnar crystals and melts a t 80".Hydr- m i n e mon,hydriodic?e, N2H4,HI, may be obtirined by adding iodine to an alcoholic solutionof hydrazine hydrate; it melts at 127" and then explodes. T&hydraaine dihyd&ditJe, N6HI2,2HI, is obtlained when iodine is added to a solution of hydrrlzine hydrahe in H little alcohol until white cteystals separate ; i t dissolws easily in water, and crystallises from rtlcohol i n large, white needles which melt at 90" and are optically hiaxial ; wben i k s aqueous solution is evaporated with hydriodic acid, i t yields hydrazine monhydriodide. Cryoscopic determinations of the molecular weiyli ts of the above salts show that in aqueous solution :-(1) the salts N.,H4,HR have molecular weiqhis which are halr those expressed by their formula, ; (2) trihydrazine dihydriodide has a molecular weight which is one- fifth of that expressed by its formula; (3) the salts NzH4,2HR have molecnlar weights which are one-fourth of those expressed by their formnlse (except that of NzH4,2HF, which is one-half that expressed by the formula).With regard t9 hydrazine sulphate, see above. These phenomena are to he explained by the dissociation of the salts in cases (1) and (3) into free molecules of N2H4 and Hlt, and in case (3) into molecules of NH, and R. The author concludes with some specnlations fts to the constitution of hydrazine hydrate and trihydrazine dihydriodide. A. G. B. Phosphorus Trifluoride.By H. MOISSAN ( A n n . Chiin. Phys. [S], 19, 286-288 ; compare Abstr., 1885, 15 and 482).-Phosphoros tri- fluoride can be prepared by gradually adding phosphorus hibromide to zinc fluoride which is gent'ly heated ; the gas is washed with water, dried with pumice moistened with a little sulphuric acid, and collected over mercury. F. S. K. Preparation of Phosphorus Oxyfluoride. By H. MOISSAN (BUZZ. Soc. ChinL. [3], 4, 260-262; compare Trans., 1889, 759).- Ziuc carbonate is dissolved in excess of hydrofluoric mid, the solution is evaporated, and the zinc fluoride dried at 300" and placed in a braas h h e , to which ft bromine bnrette, conhining slight excess of the cal- culated quantity of phosphorus oxjchloride, and tl lcaden deliveryIKORQANIC CE EMISTRY.265 tube are adapted by a paraffined cork. The leaden tube is connected to a brass tube cooled bya freezing mixture to -220",and this leads to another tube contailring zinc fluoride, which removes any traces of escaping oxychloride from the oxyfluoride. The phosphorus oxp chloride is dropped slowly on to the zinc fluoride, the ensuing reavtion being assisted by warming carefully at 40-50", and the evolved gas is collected over mercury in glass vessels. Tbe author determined the phosphorus contained ii? the gas in three instances as 29.2, 29.4, and 29-95 per cent., theory requiring 29.8 per cent., and the vapour density as 3.68, 3.69, and 3.71, theory requiring 3.63. Arsenic Fluoride. By H. MOISSAN (Aria. Chim. Phys. [6], 19, 280-286 ; cornpare Abstr., 1885,12l).-Arsenic trifluotide is formed * when arsenious anhydride is treated with anhydrous hjdrogen fluoride, and when arsenic chloride is warmed with lead or silver fluoride, but it is best prepared by heating a mixture of arsenious anhydride and calcium fluoride with excess of mlphuric acid, as described by L)umas (Ann.Chim. Yhys. [ S ] , 31,433). Arsenic fluoride boils at 63" (750 mm.), and its density is 2.73 (compare MacIvor, Chem. News, 30, 169, and 32,232). It solidifies n t -8.5" to a mass of crystals. When exposed to a dull red hest, in a glass vessel free from air, it is decomposed, yielding arsenious anhydride and silicon tetratluoride. Action of Hydrogen Sulphide on the Ortharsenates of the Alkali Metals. By W. MCCAY (Amer. Chent. J., 12, 347-55s ; compare Branner and Tomibek, Trans., 1888, 53, 145).- The author finds that arsenic peutasulphide may be prepared by the decomposition of a strong solution of an alkali amenate with hjdrogen sulphide, and subsequent precipitation by the addition of a mineral acid, according to the metbod proposed by Beizelins; but that the operation is successful only under the following definite conditions :- In the case of dihgdrogen alkali arsenates, the solution must be properly diluted and kept hot, and the hydrdgen sulphide passed in 1axcess and for a long time.In the case of the di- and tri-alkali ttisenates, the hydrogen sulphide must be kept present in such large excess and passed for such length of time that there is no chance of the pohssiutn thioxyarsenate, which is always formed in passing, in the wet, way, from arsenic acid to thioarsenic acid, to split up into potas- sium arsenite and sulphur, or to escape subsequent conversion itih the thio-salt.G. T. M. Certain Forms of Carbon. By P. SCH~TZENRERGER and L. SCH~TZKNRERGER (Compt. rend. 111, 774-778).-W hen pure and dry cyanogen is passed through a porcelain tube at a cherry-red heat, i t is only partially decomposed, and even a t a bright-red heat the de- composition is very limited, the interior of the tube being covered with a thin, brilliant, blackish-grey coating, m ith a sub-metallic lustre resembling that of polished graphite. If, however, there is placed in the hot part of the tube some gas carbon with powdered cryclite sprinkled over the surface, tohe cyanogen decornpoaes completely iu to carbon and nitrogen, even at a cherry-red heat.The carbon separates T. G. N. B. S. K. VOL. LX. t266 ABSTRACTS OF CHEMICAL PAPERS. in a bulky mass of very slender filaments, and, after a time, stops up the tube. Those portiotis in contact with the walls of t h e tube are more compact and somewhat elastic. It is friable, and leaves on paper a mark resembling that made by graphite, but not so bright. When a piece of aluminium was placed amongst the ga.8 carbon, the carbon separated round it in noti-elastic filaments, which could be compressed between the fingem into a mass resembling graphite. The carbon deposited at a cherry-red heat was treated with nitric acid and potassium chlorate at 20-25" for 24 hours. The insoluble residue, after being washed and dried, forms a deep maroon-brown powder, which decomposes suddenly when heated, becoming incan- descent and evolving carbonic anhydride and water.The proper1 ies of this product are not materially affected by a second treatment ~ i t h acid and chlorate in the cold, but if the mixture is heated at 50-60" for several hours, a somewhat pale brownish-yellow powder is oh- tained, which deflagrates energetically when heatcd. A portion of tbe product is soluble in water, and repented treatment with the oxidisiig mixture convei*ts the whole of it into yellow, soluble com- pounds. The pale brownish-yellow, insoluble product has the corn- position, C, 36.2 ; H, 2.5 ; 0, 41 *3 = 100 ; arid its formula is CllH606, that of Rrodie's graphitic acid being CllH,O,. The maroon-brown product obtained at 20-25" has the composition of graphitic acid.The carbon obtained in presence of aluminium yields similar pro- ducts. The filamentous carbon obtained by the decomposition of cynnopen is not identical with any of the established forms of graphite or carbon, and may be taken as a new moditication. Gas carbon, when treated two or three times in the cold with a mixture of potassinm chlornte and nitric acid, yields a blackish powder which deflaptes on heating. At 45-50", i t yields products similar to those obtained from cyanogen carbon. It follows that, the property of yielding hydroxides which deflagrate when heated is n o t peculiar to graphite, but is shared by some forms of amorphous carbon. The authors consider that t h e term carbon hydroxide is preferable to such terms as graphitic acid or graphitic oxide.Allotropic Silver. By A. J. A. PRANGE (Rec. Tmv. Chint., 9, 121--133).-With the object of ascertaining the existence of argentous compounds, the author has examined the solutio~s of silver, and the silver dissolved therein, as described by Carey Lea (Abstr., 2890, 210), and confirms this ~Eserver'~ results. The red solution is obtained by treating with water the blne- black precipitate formed by the interaction of dilnto solutions of ferrous sulphate, sodium citrate, and of silver nitrate. This solu- tion deposits a black powder in a few days, but when more dilute, remains free from precipitate for many weeks. I n either case, when freshly prepared, the solutions are perfectly transparent to both inci- dent and reflected light, whilst an intense ray of light passed through the solution undergoes no polarisation, thus proving the ahsence of suspended matter.Exposure to diffused light or to solar light causes decolorisntion and precipitation of t~ black substance, and C. H. B.INORGANIC CHEMISTRY. 267 a similar effect is brought about by the addition to the 8olution of acids, alkalis, and neutral salts. As finely-powdered quartz or graphite also effects the precipitntion, the author supposed a colloidal silver to be present, and on di:rlysis of the solution no silver passed the mcmbrane, but a deposit was thrown down thereon. Alternate freezing and thawing of the liquid causes decolorisation and formation of a precipitate. The soliltion has very great ahsorp- tive pomer ; a layer 1 C.C.thick, containing 0.7 gram silver per litre, allows no light to pass through. A solution containing 4.75 qrams silver per litre was of ft syrupy consistence, the colour of bromine, very nnstable, and contzined much iron salt associated with the dissolved silver. The heat of clissolution for 1 gram Ag in 2.179 litres of water = + 250.8 cal., and for 1 gram Ap in 0.2258 litre of water = +126*73 cal. From the solution, the silver was obtainrd by adding ammonium nitrate, and, after the blue-black precipitate thus obtained had been well washed with water, containing suficient ammonium nitrnte to prevent rediasolution, until the tracos of iron salts were removed as far as possihle, it was treated with alcohol, to remove adhering ammonium nitrate, and dried over suiphuric wid for several days ; a11 these operations must, be carried out in darkness, or Carey Lea's golden modification (Zoc. cit.) is obtained, instead of a heavy, deep, lilue- black substance, which, on compression, assumes a metallic Inat.re and is easily powdered.This is quite insoluble in water, but dilute mineral acids and acetic acid dissolve it readily. When spread in the inoisb condition on glass or paper and dried, a beautiful mirror is obtained. Careful analysis proved it to be free from combined oxygen, but traces of iron are a constant ini3urity. The heat of transformation to ordinary silver was calculatcd as i 6 0 cal. per gram. T. G. N. Ternary Alloys. By C. R. A. WRIGHT and C. THOMPSON (Proc.Roy. Xoc., 48, 25--45).--The authors iu this paper give an account of their experiments with mixtures of lead, zinc, and tin at high temperatures, and with mixtures of lead, zinc, and silver. Their general conclusions are as follows :- A mixture of tbree metals, A, B, and C, of which A and B are each miscible in all proportions with C, but not with each other, will in general, when allowed to remain molten for rt sufticient length of time a t constaut temperature, divide into two ternary alloys of unequal density, if the proportion of C present falls below a certain amount; but if the quafitity of C present is above this limit, no separation takes place, and a homogeneous alloy results. Under ordinary circumstances, the different alloys thus formed are respectively a saturated solution of A in a mixture of B and C, and one of B in a mixture of A and C, the solubilities being such that the greater the proportion of C present, the more of A (or B) is dissolved. Certain metals, however, appear to be capable of forming compounds in atomic proportions (for example, AgZn5 and Ag4Zn5), in which case the quantity of A (or B) dissolved does not alwayg vary directly with the amount of C present. The effect of temperature on diflerent mixtures t 22 (it) ABSTRACTS OF CHEMICAL PAPERS.is very variable, but usually a rise of temperature increages the solubility of A in BC, arid of B in AC, in sorrie cahes to a very con- siderable extent. The manner in mhhich C divides itfielf between the two alloys depends on the nature and proportions of the metals present.The numerical results me presented in numerous tables and curves. So-called Ammoniacal Mercury Compounds. By L. PESCI (Gazzetta, 20, 485-504; compare Abstr., 1889, 347 ; 1890, 1211).- Rammelsberg and Kane have shown that a number of the complex compounds of mercury and ammonia may be regarded as containing the radicle ( Hg2N)’, mwcwrummt~n‘I:7mn. Tbe author has nlso found (Abstr., 1890, 121 1) trhat compounds containing t h i s group are decomposed by the halo‘id iirnmonium salts, and has described a method of quantitatively determining the “ mercurammoniacd ” nitrogen in compounds containing the radicle. I t consists in placing under a bell-jar a mixture of the compound with a saturated aqueous solution of ammonium bromide coloured by litmus, and a vessel containing a known quantity of normal oxalic acid.The whole is left until the bromide solution acquires a clear purple colour. One fourth of the nitrogen in the ammonia absorbed by the acid is derived from the mercurammoninm group in the componnd, the reaction proceeding according to one of the following equations :- J. W. I. HgZNX + 3NH4X = 2HgX2 + 4NH3. TI. Hg2NR’ + 4NH4X = 2HgX2 + NH,R’ f 4NH3. 111. (HgJ!J)&‘‘ + 8NHJ = 4H,EX2 + (NH4)ZR’ + 8NH3 (X = C1, Br, I ; R’ = N03, BrO?, &c. ; R” = SOp, C03, &c.). This method has been applied by the author to the elucidation of the constitution of the compound nitrates, sulphates, arid iodides of mercury and ammonia, with the following results. (1). Nitrates.-Six coinpounds are described by Gmelin, namely :- CC.NH2( Hg302)N03 ; b. NH,(Hg20)N03 ; C. NH,(Ha.lO)NO,,NH*HgNO, ; e. 2NH3,2Hg(N0,)2; d. 2[ NHg(H~302)NO3],Hg(NO,X ; f. XHZ( H~g20)N 03,2NH,N O,,H,O. a WRS prepared by Pagenstecher by supersaturating a solntion of mercuric nitrate with ammonia, filtering, and allowing to evaporate ; i he author confirms Meyer’s observation, that under these conditioris the compound e only is formed. b was prepared by Ksne and Soubeiron by precipitating a dilute solution of mercuric nitrate with R slight excess of amtmnia, and washing the precipitate with boiling water. The author’s annlyses show that this compound is nothing but, mercurammoninm ni tinate, (Hg2N)N03. c, prepared by precipi- tating a neutral solution of mercuric nitrate with the necessary quantity of dilute ammonia, has the composition It evolves ammonia when heated with caustic potash (contxary to Kane’s stntement).and it is converted into mercurtlmmonium nitrate b~ the action of boiling water. d was prepared by Hirzel, by digesting (3Hg2Y)NO3,NH,NO3 + 2HzO.INORGANIC CHEMISTRY. 2G9 yelIow oxide of mercury with a moderately concentrated solutiou of animonium nitrate. By following Himel's directions, tbe author was only able to obtain mercurammonium nitrate. e, obtained as described under u, has the constitution ( HgzN)N0,,NH4N0,,H,0. On treatment with boiling water, i t loses ammonium nitrate and is converted into mercurammonium nitrate. j, prepared by Kane by dissolving c in a boiling 20 per cent. solution of ammonium nitrate and filtering, has the consti tutioii (Hg2N)N03,2NH4N03,2H,0.It loses 1 mol. H,O at 110-115". It is decomposed by boiling water into mercurammonium nitrafe and ammonium nitrate. g. (HgzN)NO~SNH4NO3.-This is a new conipound which i s formed when a boiling 50 per cent. solution of ammouiuin nitrate is used in the preparatiun of the preceding compound. It may also be prepared by treating a concentrated solution of the basic nitrate, Hg20(N03)?, with a 50 per cent. solution of ammonium nitrate. It crystallises in colourless, transparent needles which become almost opaque after exposure to the air tbr some time. Cold water abstracts ammonium nitrate from it, leaving the compoiind c ; boiling water converts it into mercturammoaium nitrate. It dissolves in ammonia, and on slowly evaporating the solutim the compound e crjstalliaes out in octahedra.SuZphutes.-Gtuelin describes the compounds- h. 2NH3,3Hg0,S03; i. 2NH3,2H,aO,SO3 ; j . 2NH,,HgO,SO, ; h, i, and j were prepared by Millon by saturating 100,70, and 40 C.C. respectively of concentrated ammonia witoh mercuric sulphate, allowing the solution to evaporate over quicklime i n an atmosphere of gaseous ammonia, and collecting the first crop of crystals in the first two caws, bnt evaporating to dryness to obtain the compound j. The author finds that whether 100 or 70 C.C. of ammonia are used, the first crop of crystals consist of octahedra baving the composition ( Hg,N)2S04,'LH,0 ; the crystals subsequently deposited have no con- stant composition. The product j is obtained in the manner described, but it is doubtful whether it is not a mixture of several substsnces.I;, prepared by Schmieder by saturating a cold 20 per cent. solution of ammonium sulphate with yellow oxide of mercury and evaporating, has the composition (Hg,N),S04,3( NH4)2SOa,4H,0. It is converted by cold water into the compound I, and by boiling water ultimately into mercurammonium sulphate. I iA obtained by treating the pre- ceding compound with cold water. It has the composition 7( Hg,N),S04,(NH4),S0,,12Hz0. It loses the whole of its water at 113". m was obtained by Schrnieder by dissolving k in dilute siilph- uric acid and precipitatirig the solution with potash, b u t under these conditions the author could only obtain mercurammoniurn sulphate. n. 5(Hg2N),S0,,14(NH~),S0,,16H,0.-This compound is formed when a mixture of a saturated solution of mercuric sulphate in ammonia (sp.gr. = 0.906) with an equal volume of a solution of ammonia satiirated a t 0" is allowed to remain for 24 hours. It crystallises in rectangular prisms which become opaque on drying in k. 2NH3,Hg0,S03H20 ; 1. 3[(NH:,,HgzO)zSO4],NHzHgSO4 ; m. NH,(H~~02),NH,Hg,O,S01.2'70 AlISTRACTS OF CHEMICAL PAPERS. the air. It is readily soluble i n ammonia, and the soluhn, when exposcd to the air in presence of sulphuric acid, deposits crystals of mercurammouium sul phate. Iodides.-Besides the compound NH2( Hg2O)T, shown by Rmnmels- berg to be the hydrate of mercurammonium iodide, namely, Hg2NI,H20, Gmelin describes the compounds 0, NH3Hg12, and p , 2iUH3HgI,. The former is considered by Rammelsberg to have the composicic;n Hg(NH31), + HgI,, but the author's results lead to the formnla 3Hg2NI,4HgT2,8NH,I ; p is regarded by Rammelsberg as Hg(NH,I), ; the author f i r d s , however, that it is formed when ammonia is added tto a solution of mercuric iodide in ammonium iodide, and this renders it probnble that its composition may be represented by the formula Hg2NT,3NH41, since ammonia precipitates " fusible white precipitate," Hg2NC1,3N H4C1, from solutions of mercuric chloride in ammonium chloride, and the compound Hg2NBr,3NH1Br from solutions of mercuric bromide in ammonium bromide (Abstr., 1890, 1211).Manganese Oxides. By A. GORGEU (Bull. SOC. Chim. [3], 4, 16-30; compare Abstr., 1889, 829; 1890, 260).-The author has prepared and examined specimens of hydrated manganese dioxide by a11 the known methods, and gives aualytical data respecting the sever91 products.' h e best yield is obtained by the action of dilute solutions of manganese nitrate acd potassium permangsnate on each other in presence of some free nitric: acid. As crystals of manganese nitrate when heated melt in their water of cryst~nllisation, and then decompose a t 125-143" to form manga- nese manganites, and at 150-165" to form manganese dioxide, the following method may be used for the production of anhydrous manganese dioxide :-600 to 800 grams of manganese nitratle crystals are warmed in a flask until red fumes appear, when the flask is to be removed from the flame, and the clear liquid decanted from the manganese manqanites, and maintained at 150-160" for 40-60 hours, when a black, crystalline precipitate containing 99 --lo0 per cent. of manganese dioxide is obtained, which is identical with polianite.The several hydrated manganese dioxides differ in the amount of water of hydration they contain, according to the reactions by which they are formed, and to the experimental conditions, and it appears impossible t o prepare a hydrated oxide by the wet method which &hall correspond with an oxide of the formula &ln02, on account of the te~deiicy existing i n this substance to combine with manganous oxide at the moment of liberation. The hydtated oxides prepared below 105" redden litmus, neu- tralise definite quantities of solutions of the alkaline hydroxides, and give a brown solutiori in water which is transparent to direct light, wbereas those prepared above 120", together with the anhydrous dioxides and the miiiei als pyrolusite and polianite, do not ; but even tlie last mentioned combine with hydrated manganons oxides to form manganese manganites, when left, in contact under water for soine days, and the reaction is accelerated by heat.It is converted by cold water into the compound 1. S. B. A. A.INORGANIC CHEMISTRY. 271 The hydrated oxides combine more readily with manganons oxide. the rate of action varying directly with their amount of water of hydration. Both bydmted and anhydrous manganese dioxides evolve ox-j-gen at 400”. When hydrated manganese dioxide, prepared as above described, is left for some time in contact with very dilute solutions of metallic salts, corresponding manganites are formed, the cobalt and copper rnanganites corresponding with lanpadite aiid asbolite respectively.Potassium permangarial e is rapidly reduced to manganate by boiling a solution of the salt containing 20 per cent. of potassium hydroxide witb an equivalent quantity of potassium manganite, produced by the action of carbonic anhydride on an alkaline solution of potassium perman gnna te. Violet Chromium Fluoride. By G. FARRIS (Gazzetta, 20, S82-5849.-W hen violet chromium snlphate is heated with an excem of normal ammonium fluoride, the green, crystalline precipitate formed has the composition CrF9,3NH4F. When the reaction is allowed to proceed in the cold, the hydrated fluoride, CrF3 + 9H20, is obtained.This compound is best prepared by adding the ammo- nium fluoride gradiially to a cold solution of the chromiutn sulphate. It IS insoluble in alcohol and in ammonium fluoride, and only very sparingly soluble in water ; it dissolves in hydrochloric acid and i n potasli, forming violet and green solutions respectively. When heated in the air it loses its water, turns greeu, and is ultimately converted into chromium sesquioxide. 8. B. A. A. Artificial Production of a Chromium Blue. Bg J. GARNTER (Gompt. rend., 111, 7Yl).-Potassium chromate, 48.62 parts, calcium fluoride, 65 parts, and silica, 157 parts, are fused in a brasqued crucible. A blue glass is obtained, surrounded by a pelliole of metallic ch rom i um. C. H. B. T. G. N. Action of Ammonia on Solutions of Normal Ammonium Titanofluoride.By A. PICCINI (Chem. Centr., 1890, ii, 544 ; Rend. Acad. Lincei, 6, i, 568--5;1).-1f ail excess of ammonia is added t o a solution of ammonium titanofluoride, TiF4.2KH4tc’, the whole of the titanic acid is precipitated. I f , however, ammonia is added drcp by drop to the warm solution of the fluoride, the white precipitate which first forms redissolves later, until at a certain point the liquid has merely an opalescent appearance : if now allowed t o remain, a white, crystalline precipitate setqles out. It is completely soluble in a solution of ammonium titanofluoride, but is decomposed by water, titanic acid being precipitated. The author ascribes to it the formula 3 ( TiF4,2 N H, F) ,2’l’i 0,,3NH4 B . J. W. L. Atomic Weight Of Bismuth.By R. SCHWEIDER (J. pr. Chern. [2 3, 42, 553-565) -In this paper, the author criticises Classen’s memoir on this subject (Abstr., 1890, 706). He complains that the consideration of Marignac’s work is dismissed too summarily by2 72 ABSTRAOTS OF OHEMIOAL PAPERS. Clamen, and that the criticisms thereon are not valid. The amma- tion against the bismuth which the author and hlarignac used, of containing lead, is t'rivial ; for even if it contained as much as 0.25 per cent. of lead, which is practically impossible, the atomic weight would otily be raised 0.17, an amount which i s well within the limits of variation in the determinations. The author criticises Classen's apparatus and concludes that his atomic weight, 208.9 (0 = 16), is less likely to be correct than 208.07.Action of Hydrogen Sulphide on certain Metallamines. By E. F. SMITH and H. F. KELLER (Ba-., 23, 33?3-3375).-0n passing pure hydrogen sul phide over yalladio-ammonium chloi-ide a t 70--8V0, the salt becomes black, and st higher temperatures am- monium chloride volatilises ; tlhe residue is insoluble in any one aciti, but dissolves sparingly in aqua regia, and probably has the formula Pd S. Pu rpureocobalt chloride, roseocobalt sulp hate, and luteocobalt chloride react in a similar manner with hydrogen sulphide a t ordi- nary temperatures, whilst purpureochromium chloride requires to be heated almost to the dissociation temperature of hydrogen sulphide before any uhauge occurs. A. G. B. J. B. T.260 ABSTRACTS OF CHENICAL PAPERG.I n o r g a n i c Chemistry.Molecular Weights of Sulphur, Phospb.orus, and Iodine inSolution. By J.HERTZ (Zcit. phpikul. C!ht?t~., 6, 35$--359).-Phos-phorus dissolved in benzene gives a depression of the freezing pointcorresponding with the formula P,. The numbers obtained withsulphur dissolved in nnph thalene point to the exishence of moleculesS8, i n accordance with the results obtained by Beckmann, who em-ployed carbon bisulpbide as solvent (Abstr., 189C, 447). The redsolution of iodine in naphthalene yields numbers corresponding withthe molecule I,. J. W.Action of Metals on Sulphuric Acid. By A. DITTE (Ann. Chim.Phys. [S], 19, 68-92).--The author has investigated the action of aiinmber of metals on sulphuric acid of different degrees of concentra-tion and a t rarious temperatures ; the following general conclusionsmay be drawn from the results of the experiments :-The metals attacked by sulphuric mid can bo classed in twogroups.The one contains those metals which are acted on only when thINORGANIC CHE3lIS'l RY.261acid is concentrated and hot ; the reaction i s very regular in all cases,and sulphurous anhydride alone is evolved, no secondary reactionstaking place. To this class belong silver, mercury, copper, lead, andbismuth.The second group embraces those metals which are acted on moreor less readily by sulphuric acid of all degrees of concentration. Themost constant product of the reaction is hydrogen, this gas beingalways evolved in the cold, and almost always at a high temperaturealso; when the temperatnre is not very high, hydrogen is the solegaseous prodiict, whatever the degree of concentration of the sulphuricacid employed.Sulphurous anhydride is only produced when theacid is hot and concentrated ; the temperahme at which the evolutionof sulphurous anhydride conimences varies with the metal employed,and, generally speaking, its quantity iirmenses in proportion to therise of temperature, the quantity of hydrogen decrcasing to a pro-portionate extent, and sometimes, when tho temperature is very high,disappearing t l l together. When the concentration of the sulphum:acid decreases, the formation of sulphurous anhydride also decreases,80 that, even at a high temperature, i t is not obtained free fronihydrogen ; when a certain degree of dilution of the acid is reached,salphurous anhjdride ceases to be formed.Between certain limitsof temperature and concentration, which vary with the nature of themetal employed, the action of sulphuric acid gives rise to a mixtureof hydrogen and suiphurous anhydride, SO that by choosiiig IL suitnbletemperature and an acid of suitable strength, a mixture of the twogases, in any required proportion, could be obtainecl,This is true in the case of metals, like magncsiuni, which onlyyield hydrogen when treated with siilphurous acid, as the reducingaction of the hydrogen on the sulphurous acid under the conditions ofthe experiment may be neglected. When, however, the nietal em-ployed decomposes sulphurous acid, yielding a sulphide, secondaryreactions set in, and hydrogen sulphide is formed: i n mch cases,larger or smaller quantities of ihis gas are formed according as theaction of the metal on the sulphurous acid is rapid or RIOW, andaccording as the sulphide produced is readily or slowly acted on bythe sulphuric acid.poses, and is itself decomposed by, some of the sulphurous acid, and~t also reduces the 5ulphuric acid causing a deposition of sulphur,which, in its turn, acts on the sulphiiric acid.When, however, t h ometal is treated with sulphuric acid under such condition8 thatsulphurous acid is not produced, the forniat,iori of hydrogen sulphideand other secondary reactions cease, and pure hydrogen is evolved.'Po the second of these two groups belong magnesium, manganese,nickel, cobalt, iron, zinc, cadmium, aluminium, tin, thallium, findprobably also the alkali metals.I n the case of the last natned, itwas only possible to study the behavioiir with snlpburic acid in thecold, and under these conditions hydrogen is evolved, but, consideringthe close relationship bztween the alkaline metals and thallium, it isvery probable that, like the latter, they wonld yield sulphurousanhydride on treatment with sulphuric acid at a high temperature.F. S. K.The hydrogen sulphide t h u s produce262 ABSTRACTS OF CHEXIOAL PAPERS.Selenites. By BOUTZOUREANO (Arm. Chim. Pl2y8, [6], 18, 280-351).-'l'he author has prepared the following selenites :- s EL EN~TES 0 F RIVAL E N ' ~ MEfrALs.-Basic selen ites :--2 c u 0, Se02,clinorhombic.Normal selenites :-MgO,SeOz + 6H20, cubic.MpO,SeO, + 2Hz0, clinorhombic. ZnG,SeOz, orthorhom bic.CdO,SeOz, orthorbombic. 3( CuO,SeOa) + H20, clinorhombic.3(CoO,SeO,) + HzO, clinorhombic. 2(Ni0,Se02) + H20, ortho-rhombic. Acid selenites :-MgO,SSeO,, rhombohcdric. Zn0,2Se02 +3&0, clinorhombic. ;!CdO,SSeOz + H20, clinot-hombic. Cd0,SSe02,ort>horhombic. Cu0,2Se02 + H20, clinorhombic. Cu0,2Se02 +2H,O, clinorhombic. CuO,BSeO2 + 4H20, clinorliombic.2( Mn0,2Se02) + H20, clinorhombic. Mu0,2Se02 + 5H,O.CoO,ZSeO, + 3H20, clinorhombic.SELENITES OF QVADRI VAL ICNT METALS. --Busic: selenites : --Mn?O,,BSeO?,clinorhombic. Fe2O3,2SeOZ, clinorhombic. NormaE seEenites :--Fe,03,3Se02 + 10H,O, clinorhombic.Fez03,3Se02 + 3H20, cubic.Pe203,3Se02 + H20, clinorhombic. A1203,Se0, + 7H20, hexagonal.A1,OJ, 3Se0, + 3H20, cubic. U2O3,SeOz, cubic. Acid seZenites:-Fe203,4Se02 + HzO, orthorhorn bic. Fe203,GSe02 + 2H20, clino-rhombic. A1,0,,4Se02 + 3B,O, orthorhombic. AI2O3,6Se0, +2H20, clinorhombic.AMMONIACAL S E LE N ifr m.-Zn0,Se02,NH,, orthorh Dmbic.C d 0, SeO,.N H3, orth orhom bic. C u 0, SeO,, N H3 + HzO, tricl in i c.Ag,O,SeO,,NH, tricliaic.With 8, few exceptions, the compounds given in the above list havenot hitherto been prepared.The most. siicwssful methods for preparing the salts and obtainingthem in well-defined ~ r y s t ~ a ~ l s were found to be (1) heating theHmorphous or crystalline compounds in sealed tubes at 130-270"\vith water, or with a solntiori OF seleniocs anhydride, or adding se-lenious anhydride to a solut:on of a salt already prepared and heatingthe mixture in sealed tube..; ; and (2) dissolving metallic carbonatesin selenious acid and evnporating the solution.The ammoniacal selenites were prepared by dissolviiig the selenitesin ammoiiirt arid evspomting the solutions a t the ordinary tempera.-ture or at 100".I n estimating the selenium irr the salts, except in the case of thesrtits of the sesquioxides, t,he best method was found to be the reduc-tion of the seleniou3 acid with Rodium hydrogen sulphite in hydro-chloric acid solution ; t.he results are very satisfactory when care istaken to prevent the volrttilisation of the selenious anhydride, and tocnsure complete reduction.111 the case of the selenites of thesesquioxides, attempts were made tu detei-mine the selenium by Rose'smethod, but as the results were riot satisfact,ory, the salts were firstboiled with a concenti-nted solution of sodium carbonate, and thebeleniouu acid in the tiltered solution eshnated by reduction withsodium hydrogen sulphite as before.Reparation of the Nitrogen Hydride N,H . By E. J. MAUMEN~!fit& SOC. CILirn. [3], 4? 179-180; compare Abstr., 1889, lP).--Rgthe dry distillation of ammonium platiuochloride, the chloriduCoO,SSeO,, olinorhombic.2( U,O,) ,3Se02 + 7 HzO, clinorhombic.F. S. K1SORGANIC CHEMISTRY. 263N,H,Cl, is obtained in six-sided, orthorhombic crystals which condenseon the walls of the ret,ort. T. G.N.Hydrazine Hydrate and Haloid Salta (Halogen DiammoniumCompounds). By 1'. CURTIUS and H. SCHULZ ( J . p-. Chem. [2], 42,521-549 ; compare Abstr., 1889, 340).-Hydrazine sulphate forinsrliqmbic crystals, 5 : b : c = 0*7_P538 : 1 : 0.82825 ; observed facesmPm, OP, Pw, Pa, d . 2 , 2P2; crystals tabular across w,Pm,colourless and clear; cryoscopic determination of its niolwular weight,in water, gave 69.16, 628i1, ttnd 60.i05 rsspectiT-ely.Hydrazine hydrate is best prepared by distilling a mixtnre ofhydrazine snlphate (100 grams), potassium hydroxide (100 grams),and water (25 J grams) in a silver retort provided with a silver con-densing tube. The distillation is continued (5-6 hours) until thelast drop has passed over, and the distillate (250 c.c.) i s then frac-tionated, the fractions being best divided into brlow 101", 101-104",104-1li"~ ll7"-constrtrit boiling point.After four fractionationq,the hydraeine hydrate (36 grams) boils constantly at 119".Most of the properties of hydraline hytllate have been alreadydetailed (Abstr., 1889, 340) ; it is hygroscopic, and nbsorl~s carboiiicanhydride ; it can be kept in c h e d vessels iinchanged ; it dissolves inwater and alcohol, but not in ether, chloroform, or benzene; i tsolidi6efi in solid carbonic anhydride and ether, but melts againbelow -40'; it boils (739.5 mm.) atl 118.5"; its sp. gr. at 21" is1.0305 ; in its reactions with indicators i t resembles ammonia. De-twniination of the vapoui. density of hydraziue hydrate, made byHofinann's method a t lWo, show that its molecule, under these coii-clitions, is X2H4,H20 ; those made by Victor Meyer's method at l i O o ,and at atmospheric pressure, show that the molecule is dissociatedunder these couditions into N2H4 Rnd HzO ; cryoscopic determinationsb h W that the molecular weight of hydrazine hycliate in water is 68,agreeing with the t'ormula N2H4,iLH20.Hydraziue hydrate which has been redistilled over barium oxidefulues In the air mure strongly than tha pure liquid, showing that it,contains free hydrszine dissolved in itl.When the hydrate is heatedin tt sealed tube with barium oxide at 170", and the tube is subse-yncntlg opened, hydrazine (dianiide) escapes as a white fume ; ex-yeritiients in this dircction are still in progress.The hydrszine haloid salts are prepared either by mixing aqueoussolutions of bydrazine hydrate and the haIogen acid and evaporating,or by additig the acid to an alcoholic solution OE tbe hydrazinehydrate, and subsequentlg adding ether, whereby the salt is precipi-tated.When hydrofluorir: and hIdrocliloric acids are used, tlie saltsN2H,,BHR are obtained by both methods ; with hjdrobromic acid, thefirst method yields the salt N2H4,BBBr, and the second method the salt.K2H4,HBr; with hydriodic acid, both methods yield the salt N2H4,HI.The salts N2H4,BHR crystallise in the regular system, and areisotropic in polarised light; t,hey dissolve easily in water, but arc)nearly iusoluble in alcohol. The salt4 N2H4,Hlt are easily soluble inwater and in warm alcohol, from which they cr~stallise well.Bothclasses are insoluble i n ether, benzene, &c264 ABSTRACTS OF CHEMICAL PAPERS.Hydrazine dihydrqfltmde (dia.mmonium d{fiuoricEe), N,H4,2HF, meltsat 105", and sublimes undec omposcd in presence of excesp of the salt.Hydrazine dihydrochloride has been already described (Abstr., 1887,715); it can also be obtained by passing chlorine into hydrtainehydrate. Hjldrasine dihydrobromide, NzH4,2HBr, niel ts at 195" : itcan also be obtained by decomposing bsnsalazine (Abstr., 1889, 393)with hydrobromic acid. Hydt-azine dihydriodide, N?H4,ZH 1, can onlybe obtained by decomposing benzalazine with fuming hydriodic acid ;it is very hygroscopic, becomes brown on exposure to light, and meltsat 220".Hydraziiie monhydrochloride has already been described (Abstr.,1869, 340).Hydmzine monhydrobromide, N,H4,HBr, ifr mepared byadding bromine to hgdrtlzine hydrate suspended in chloroform ; i tforms large, anisotropic, colnmnar crystals and melts a t 80". Hydr-m i n e mon,hydriodic?e, N2H4,HI, may be obtirined by adding iodine toan alcoholic solutionof hydrazine hydrate; it melts at 127" and thenexplodes.T&hydraaine dihyd&ditJe, N6HI2,2HI, is obtlained when iodine isadded to a solution of hydrrlzine hydrahe in H little alcohol until whitecteystals separate ; i t dissolws easily in water, and crystallises fromrtlcohol i n large, white needles which melt at 90" and are opticallyhiaxial ; wben i k s aqueous solution is evaporated with hydriodic acid,i t yields hydrazine monhydriodide.Cryoscopic determinations of the molecular weiyli ts of the abovesalts show that in aqueous solution :-(1) the salts N.,H4,HR havemolecular weiqhis which are halr those expressed by their formula, ;(2) trihydrazine dihydriodide has a molecular weight which is one-fifth of that expressed by its formula; (3) the salts NzH4,2HR havemolecnlar weights which are one-fourth of those expressed by theirformnlse (except that of NzH4,2HF, which is one-half that expressedby the formula).With regard t9 hydrazine sulphate, see above.These phenomena are to he explained by the dissociation of the saltsin cases (1) and (3) into free molecules of N2H4 and Hlt, and in case(3) into molecules of NH, and R.The author concludes with some specnlations fts to the constitutionof hydrazine hydrate and trihydrazine dihydriodide. A.G. B.Phosphorus Trifluoride. By H. MOISSAN ( A n n . Chiin. Phys. [S],19, 286-288 ; compare Abstr., 1885, 15 and 482).-Phosphoros tri-fluoride can be prepared by gradually adding phosphorus hibromideto zinc fluoride which is gent'ly heated ; the gas is washed with water,dried with pumice moistened with a little sulphuric acid, and collectedover mercury. F. S. K.Preparation of Phosphorus Oxyfluoride. By H. MOISSAN(BUZZ. Soc. ChinL. [3], 4, 260-262; compare Trans., 1889, 759).-Ziuc carbonate is dissolved in excess of hydrofluoric mid, the solutionis evaporated, and the zinc fluoride dried at 300" and placed in a braash h e , to which ft bromine bnrette, conhining slight excess of the cal-culated quantity of phosphorus oxjchloride, and tl lcaden deliverIKORQANIC CE EMISTRY.265tube are adapted by a paraffined cork. The leaden tube is connectedto a brass tube cooled bya freezing mixture to -220",and this leads toanother tube contailring zinc fluoride, which removes any traces ofescaping oxychloride from the oxyfluoride. The phosphorus oxpchloride is dropped slowly on to the zinc fluoride, the ensuing reavtionbeing assisted by warming carefully at 40-50", and the evolved gasis collected over mercury in glass vessels. Tbe author determinedthe phosphorus contained ii? the gas in three instances as 29.2, 29.4,and 29-95 per cent., theory requiring 29.8 per cent., and the vapourdensity as 3.68, 3.69, and 3.71, theory requiring 3.63.Arsenic Fluoride.By H. MOISSAN (Aria. Chim. Phys. [6], 19,280-286 ; cornpare Abstr., 1885,12l).-Arsenic trifluotide is formed *when arsenious anhydride is treated with anhydrous hjdrogen fluoride,and when arsenic chloride is warmed with lead or silver fluoride, butit is best prepared by heating a mixture of arsenious anhydride andcalcium fluoride with excess of mlphuric acid, as described by L)umas(Ann. Chim. Yhys. [ S ] , 31,433).Arsenic fluoride boils at 63" (750 mm.), and its density is 2.73(compare MacIvor, Chem. News, 30, 169, and 32,232). It solidifiesn t -8.5" to a mass of crystals. When exposed to a dull red hest, ina glass vessel free from air, it is decomposed, yielding arseniousanhydride and silicon tetratluoride.Action of Hydrogen Sulphide on the Ortharsenates ofthe Alkali Metals.By W. MCCAY (Amer. Chent. J., 12,347-55s ; compare Branner and Tomibek, Trans., 1888, 53, 145).-The author finds that arsenic peutasulphide may be prepared by thedecomposition of a strong solution of an alkali amenate with hjdrogensulphide, and subsequent precipitation by the addition of a mineralacid, according to the metbod proposed by Beizelins; but that theoperation is successful only under the following definite conditions :-In the case of dihgdrogen alkali arsenates, the solution must beproperly diluted and kept hot, and the hydrdgen sulphide passed in1axcess and for a long time. In the case of the di- and tri-alkalittisenates, the hydrogen sulphide must be kept present in such largeexcess and passed for such length of time that there is no chance of thepohssiutn thioxyarsenate, which is always formed in passing, in thewet, way, from arsenic acid to thioarsenic acid, to split up into potas-sium arsenite and sulphur, or to escape subsequent conversion itihthe thio-salt. G.T. M.Certain Forms of Carbon. By P. SCH~TZENRERGER and L.SCH~TZKNRERGER (Compt. rend. 111, 774-778).-W hen pure and drycyanogen is passed through a porcelain tube at a cherry-red heat, i tis only partially decomposed, and even a t a bright-red heat the de-composition is very limited, the interior of the tube being coveredwith a thin, brilliant, blackish-grey coating, m ith a sub-metallic lustreresembling that of polished graphite.If, however, there is placed inthe hot part of the tube some gas carbon with powdered cryclitesprinkled over the surface, tohe cyanogen decornpoaes completely iu tocarbon and nitrogen, even at a cherry-red heat. The carbon separatesT. G. N.B. S. K.VOL. LX. 266 ABSTRACTS OF CHEMICAL PAPERS.in a bulky mass of very slender filaments, and, after a time, stops upthe tube. Those portiotis in contact with the walls of t h e tube aremore compact and somewhat elastic. It is friable, and leaves onpaper a mark resembling that made by graphite, but not so bright.When a piece of aluminium was placed amongst the ga.8 carbon, thecarbon separated round it in noti-elastic filaments, which could becompressed between the fingem into a mass resembling graphite.The carbon deposited at a cherry-red heat was treated with nitricacid and potassium chlorate at 20-25" for 24 hours.The insolubleresidue, after being washed and dried, forms a deep maroon-brownpowder, which decomposes suddenly when heated, becoming incan-descent and evolving carbonic anhydride and water. The proper1 iesof this product are not materially affected by a second treatment ~ i t hacid and chlorate in the cold, but if the mixture is heated at 50-60"for several hours, a somewhat pale brownish-yellow powder is oh-tained, which deflagrates energetically when heatcd. A portion oftbe product is soluble in water, and repented treatment with theoxidisiig mixture convei*ts the whole of it into yellow, soluble com-pounds.The pale brownish-yellow, insoluble product has the corn-position, C, 36.2 ; H, 2.5 ; 0, 41 *3 = 100 ; arid its formula is CllH606,that of Rrodie's graphitic acid being CllH,O,. The maroon-brownproduct obtained at 20-25" has the composition of graphitic acid.The carbon obtained in presence of aluminium yields similar pro-ducts.The filamentous carbon obtained by the decomposition of cynnopenis not identical with any of the established forms of graphite orcarbon, and may be taken as a new moditication.Gas carbon, when treated two or three times in the cold with amixture of potassinm chlornte and nitric acid, yields a blackishpowder which deflaptes on heating. At 45-50", i t yields productssimilar to those obtained from cyanogen carbon.It follows that, theproperty of yielding hydroxides which deflagrate when heated is n o tpeculiar to graphite, but is shared by some forms of amorphous carbon.The authors consider that t h e term carbon hydroxide is preferable tosuch terms as graphitic acid or graphitic oxide.Allotropic Silver. By A. J. A. PRANGE (Rec. Tmv. Chint., 9,121--133).-With the object of ascertaining the existence ofargentous compounds, the author has examined the solutio~s of silver,and the silver dissolved therein, as described by Carey Lea (Abstr.,2890, 210), and confirms this ~Eserver'~ results.The red solution is obtained by treating with water the blne-black precipitate formed by the interaction of dilnto solutions offerrous sulphate, sodium citrate, and of silver nitrate.This solu-tion deposits a black powder in a few days, but when more dilute,remains free from precipitate for many weeks. I n either case, whenfreshly prepared, the solutions are perfectly transparent to both inci-dent and reflected light, whilst an intense ray of light passedthrough the solution undergoes no polarisation, thus proving theahsence of suspended matter. Exposure to diffused light or to solarlight causes decolorisntion and precipitation of t~ black substance, andC. H. BINORGANIC CHEMISTRY. 267a similar effect is brought about by the addition to the 8olution ofacids, alkalis, and neutral salts. As finely-powdered quartz orgraphite also effects the precipitntion, the author supposed a colloidalsilver to be present, and on di:rlysis of the solution no silver passedthe mcmbrane, but a deposit was thrown down thereon.Alternate freezing and thawing of the liquid causes decolorisationand formation of a precipitate.The soliltion has very great ahsorp-tive pomer ; a layer 1 C.C. thick, containing 0.7 gram silver per litre,allows no light to pass through.A solution containing 4.75 qrams silver per litre was of ft syrupyconsistence, the colour of bromine, very nnstable, and contzined muchiron salt associated with the dissolved silver. The heat of clissolutionfor 1 gram Ag in 2.179 litres of water = + 250.8 cal., and for 1 gramAp in 0.2258 litre of water = +126*73 cal.From the solution, the silver was obtainrd by adding ammoniumnitrate, and, after the blue-black precipitate thus obtained had beenwell washed with water, containing suficient ammonium nitrnte toprevent rediasolution, until the tracos of iron salts were removed asfar as possihle, it was treated with alcohol, to remove adheringammonium nitrate, and dried over suiphuric wid for several days ; a11these operations must, be carried out in darkness, or Carey Lea's goldenmodification (Zoc.cit.) is obtained, instead of a heavy, deep, lilue-black substance, which, on compression, assumes a metallic Inat.reand is easily powdered. This is quite insoluble in water, but dilutemineral acids and acetic acid dissolve it readily. When spread in theinoisb condition on glass or paper and dried, a beautiful mirror isobtained.Careful analysis proved it to be free from combined oxygen, buttraces of iron are a constant ini3urity. The heat of transformationto ordinary silver was calculatcd as i 6 0 cal.per gram.T. G. N.Ternary Alloys. By C. R. A. WRIGHT and C. THOMPSON (Proc.Roy. Xoc., 48, 25--45).--The authors iu this paper give an accountof their experiments with mixtures of lead, zinc, and tin at hightemperatures, and with mixtures of lead, zinc, and silver. Theirgeneral conclusions are as follows :-A mixture of tbree metals, A, B, and C, of which A and B are eachmiscible in all proportions with C, but not with each other, will ingeneral, when allowed to remain molten for rt sufticient length oftime a t constaut temperature, divide into two ternary alloys ofunequal density, if the proportion of C present falls below a certainamount; but if the quafitity of C present is above this limit, noseparation takes place, and a homogeneous alloy results.Under ordinary circumstances, the different alloys thus formed arerespectively a saturated solution of A in a mixture of B and C, andone of B in a mixture of A and C, the solubilities being such that thegreater the proportion of C present, the more of A (or B) is dissolved.Certain metals, however, appear to be capable of forming compoundsin atomic proportions (for example, AgZn5 and Ag4Zn5), in which casethe quantity of A (or B) dissolved does not alwayg vary directly with theamount of C present.The effect of temperature on diflerent mixturest 2 (it) ABSTRACTS OF CHEMICAL PAPERS.is very variable, but usually a rise of temperature increages thesolubility of A in BC, arid of B in AC, in sorrie cahes to a very con-siderable extent.The manner in mhhich C divides itfielf between thetwo alloys depends on the nature and proportions of the metalspresent.The numerical results me presented in numerous tables and curves.So-called Ammoniacal Mercury Compounds. By L. PESCI(Gazzetta, 20, 485-504; compare Abstr., 1889, 347 ; 1890, 1211).-Rammelsberg and Kane have shown that a number of the complexcompounds of mercury and ammonia may be regarded as containingthe radicle ( Hg2N)’, mwcwrummt~n‘I:7mn. Tbe author has nlso found(Abstr., 1890, 121 1) trhat compounds containing t h i s group aredecomposed by the halo‘id iirnmonium salts, and has described a methodof quantitatively determining the “ mercurammoniacd ” nitrogen incompounds containing the radicle.I t consists in placing under abell-jar a mixture of the compound with a saturated aqueous solutionof ammonium bromide coloured by litmus, and a vessel containing aknown quantity of normal oxalic acid. The whole is left until thebromide solution acquires a clear purple colour. One fourth of thenitrogen in the ammonia absorbed by the acid is derived from themercurammoninm group in the componnd, the reaction proceedingaccording to one of the following equations :-J. W.I. HgZNX + 3NH4X = 2HgX2 + 4NH3.TI. Hg2NR’ + 4NH4X = 2HgX2 + NH,R’ f 4NH3.111. (HgJ!J)&‘‘ + 8NHJ = 4H,EX2 + (NH4)ZR’ + 8NH3 (X =C1, Br, I ; R’ = N03, BrO?, &c. ; R” = SOp, C03, &c.).This method has been applied by the author to the elucidation ofthe constitution of the compound nitrates, sulphates, arid iodides ofmercury and ammonia, with the following results.(1).Nitrates.-Six coinpounds are described by Gmelin, namely :-CC. NH2( Hg302)N03 ; b. NH,(Hg20)N03 ;C. NH,(Ha.lO)NO,,NH*HgNO, ;e. 2NH3,2Hg(N0,)2;d. 2[ NHg(H~302)NO3],Hg(NO,X ;f. XHZ( H~g20)N 03,2NH,N O,,H,O.a WRS prepared by Pagenstecher by supersaturating a solntion ofmercuric nitrate with ammonia, filtering, and allowing to evaporate ;i he author confirms Meyer’s observation, that under these conditioristhe compound e only is formed. b was prepared by Ksne andSoubeiron by precipitating a dilute solution of mercuric nitrate withR slight excess of amtmnia, and washing the precipitate with boilingwater.The author’s annlyses show that this compound is nothingbut, mercurammoninm ni tinate, (Hg2N)N03. c, prepared by precipi-tating a neutral solution of mercuric nitrate with the necessaryquantity of dilute ammonia, has the compositionIt evolves ammonia when heated with caustic potash (contxary toKane’s stntement). and it is converted into mercurtlmmonium nitrateb~ the action of boiling water. d was prepared by Hirzel, by digesting(3Hg2Y)NO3,NH,NO3 + 2HzOINORGANIC CHEMISTRY. 2G9yelIow oxide of mercury with a moderately concentrated solutiouof animonium nitrate. By following Himel's directions, tbe authorwas only able to obtain mercurammonium nitrate.e, obtained asdescribed under u, has the constitution ( HgzN)N0,,NH4N0,,H,0.On treatment with boiling water, i t loses ammonium nitrate and isconverted into mercurammonium nitrate. j, prepared by Kane bydissolving c in a boiling 20 per cent. solution of ammonium nitrateand filtering, has the consti tutioii (Hg2N)N03,2NH4N03,2H,0. Itloses 1 mol. H,O at 110-115". It is decomposed by boiling waterinto mercurammonium nitrafe and ammonium nitrate.g. (HgzN)NO~SNH4NO3.-This is a new conipound which i sformed when a boiling 50 per cent. solution of ammouiuin nitrate isused in the preparatiun of the preceding compound. It may also beprepared by treating a concentrated solution of the basic nitrate,Hg20(N03)?, with a 50 per cent.solution of ammonium nitrate. Itcrystallises in colourless, transparent needles which become almostopaque after exposure to the air tbr some time. Cold water abstractsammonium nitrate from it, leaving the compoiind c ; boiling waterconverts it into mercturammoaium nitrate. It dissolves in ammonia,and on slowly evaporating the solutim the compound e crjstalliaesout in octahedra.SuZphutes.-Gtuelin describes the compounds-h. 2NH3,3Hg0,S03; i. 2NH3,2H,aO,SO3 ;j . 2NH,,HgO,SO, ;h, i, and j were prepared by Millon by saturating 100,70, and 40 C.C.respectively of concentrated ammonia witoh mercuric sulphate, allowingthe solution to evaporate over quicklime i n an atmosphere of gaseousammonia, and collecting the first crop of crystals in the first twocaws, bnt evaporating to dryness to obtain the compound j.Theauthor finds that whether 100 or 70 C.C. of ammonia are used, thefirst crop of crystals consist of octahedra baving the composition( Hg,N)2S04,'LH,0 ; the crystals subsequently deposited have no con-stant composition. The product j is obtained in the manner described,but it is doubtful whether it is not a mixture of several substsnces.I;, prepared by Schmieder by saturating a cold 20 per cent. solution ofammonium sulphate with yellow oxide of mercury and evaporating,has the composition (Hg,N),S04,3( NH4)2SOa,4H,0. It is convertedby cold water into the compound I, and by boiling water ultimatelyinto mercurammonium sulphate. I iA obtained by treating the pre-ceding compound with cold water.It has the composition7( Hg,N),S04,(NH4),S0,,12Hz0. It loses the whole of its water at113". m was obtained by Schrnieder by dissolving k in dilute siilph-uric acid and precipitatirig the solution with potash, b u t under theseconditions the author could only obtain mercurammoniurn sulphate.n. 5(Hg2N),S0,,14(NH~),S0,,16H,0.-This compound is formedwhen a mixture of a saturated solution of mercuric sulphate inammonia (sp. gr. = 0.906) with an equal volume of a solution ofammonia satiirated a t 0" is allowed to remain for 24 hours. Itcrystallises in rectangular prisms which become opaque on drying ink. 2NH3,Hg0,S03H20 ;1. 3[(NH:,,HgzO)zSO4],NHzHgSO4 ; m. NH,(H~~02),NH,Hg,O,S012'70 AlISTRACTS OF CHEMICAL PAPERS.the air. It isreadily soluble i n ammonia, and the soluhn, when exposcd to the airin presence of sulphuric acid, deposits crystals of mercurammouiumsul phate.Iodides.-Besides the compound NH2( Hg2O)T, shown by Rmnmels-berg to be the hydrate of mercurammonium iodide, namely, Hg2NI,H20,Gmelin describes the compounds 0, NH3Hg12, and p , 2iUH3HgI,.The former is considered by Rammelsberg to have the composicic;nHg(NH31), + HgI,, but the author's results lead to the formnla3Hg2NI,4HgT2,8NH,I ; p is regarded by Rammelsberg as Hg(NH,I), ;the author f i r d s , however, that it is formed when ammonia is addedtto a solution of mercuric iodide in ammonium iodide, and this rendersit probnble that its composition may be represented by the formulaHg2NT,3NH41, since ammonia precipitates " fusible white precipitate,"Hg2NC1,3N H4C1, from solutions of mercuric chloride in ammoniumchloride, and the compound Hg2NBr,3NH1Br from solutions ofmercuric bromide in ammonium bromide (Abstr., 1890, 1211).Manganese Oxides.By A. GORGEU (Bull. SOC. Chim. [3], 4,16-30; compare Abstr., 1889, 829; 1890, 260).-The author hasprepared and examined specimens of hydrated manganese dioxide bya11 the known methods, and gives aualytical data respecting thesever91 products. ' h e best yield is obtained by the action of dilutesolutions of manganese nitrate acd potassium permangsnate on eachother in presence of some free nitric: acid.As crystals of manganese nitrate when heated melt in their waterof cryst~nllisation, and then decompose a t 125-143" to form manga-nese manganites, and at 150-165" to form manganese dioxide, thefollowing method may be used for the production of anhydrousmanganese dioxide :-600 to 800 grams of manganese nitratle crystalsare warmed in a flask until red fumes appear, when the flask is to beremoved from the flame, and the clear liquid decanted from themanganese manqanites, and maintained at 150-160" for 40-60hours, when a black, crystalline precipitate containing 99 --lo0 percent.of manganese dioxide is obtained, which is identical withpolianite.The several hydrated manganese dioxides differ in the amount ofwater of hydration they contain, according to the reactions by whichthey are formed, and to the experimental conditions, and it appearsimpossible t o prepare a hydrated oxide by the wet method which&hall correspond with an oxide of the formula &ln02, on account of thete~deiicy existing i n this substance to combine with manganous oxideat the moment of liberation.The hydtated oxides prepared below 105" redden litmus, neu-tralise definite quantities of solutions of the alkaline hydroxides,and give a brown solutiori in water which is transparent to directlight, wbereas those prepared above 120", together with the anhydrousdioxides and the miiiei als pyrolusite and polianite, do not ; but eventlie last mentioned combine with hydrated manganons oxides toform manganese manganites, when left, in contact under water forsoine days, and the reaction is accelerated by heat.It is converted by cold water into the compound 1.S.B. A. AINORGANIC CHEMISTRY. 271The hydrated oxides combine more readily with manganons oxide.the rate of action varying directly with their amount of water ofhydration.Both bydmted and anhydrous manganese dioxides evolve ox-j-genat 400”.When hydrated manganese dioxide, prepared as above described, isleft for some time in contact with very dilute solutions of metallicsalts, corresponding manganites are formed, the cobalt and copperrnanganites corresponding with lanpadite aiid asbolite respectively.Potassium permangarial e is rapidly reduced to manganate by boilinga solution of the salt containing 20 per cent. of potassium hydroxidewitb an equivalent quantity of potassium manganite, produced by theaction of carbonic anhydride on an alkaline solution of potassiumperman gnna te.Violet Chromium Fluoride.By G. FARRIS (Gazzetta, 20,S82-5849.-W hen violet chromium snlphate is heated with an excemof normal ammonium fluoride, the green, crystalline precipitateformed has the composition CrF9,3NH4F. When the reaction isallowed to proceed in the cold, the hydrated fluoride, CrF3 + 9H20,is obtained. This compound is best prepared by adding the ammo-nium fluoride gradiially to a cold solution of the chromiutn sulphate.It IS insoluble in alcohol and in ammonium fluoride, and only verysparingly soluble in water ; it dissolves in hydrochloric acid and i npotasli, forming violet and green solutions respectively. When heatedin the air it loses its water, turns greeu, and is ultimately convertedinto chromium sesquioxide. 8. B. A. A.Artificial Production of a Chromium Blue. Bg J. GARNTER(Gompt. rend., 111, 7Yl).-Potassium chromate, 48.62 parts, calciumfluoride, 65 parts, and silica, 157 parts, are fused in a brasqued crucible.A blue glass is obtained, surrounded by a pelliole of metallicch rom i um. C. H. B.T. G. N.Action of Ammonia on Solutions of Normal AmmoniumTitanofluoride. By A. PICCINI (Chem. Centr., 1890, ii, 544 ; Rend.Acad. Lincei, 6, i, 568--5;1).-1f ail excess of ammonia is added t o asolution of ammonium titanofluoride, TiF4.2KH4tc’, the whole of thetitanic acid is precipitated. I f , however, ammonia is added drcp bydrop to the warm solution of the fluoride, the white precipitate whichfirst forms redissolves later, until at a certain point the liquid hasmerely an opalescent appearance : if now allowed t o remain, a white,crystalline precipitate setqles out. It is completely soluble in asolution of ammonium titanofluoride, but is decomposed by water,titanic acid being precipitated. The author ascribes to it the formula3 ( TiF4,2 N H, F) ,2’l’i 0,,3NH4 B . J. W. L.Atomic Weight Of Bismuth. By R. SCHWEIDER (J. pr. Chern.[2 3, 42, 553-565) -In this paper, the author criticises Classen’smemoir on this subject (Abstr., 1890, 706). He complains that theconsideration of Marignac’s work is dismissed too summarily b2 72 ABSTRAOTS OF OHEMIOAL PAPERS.Clamen, and that the criticisms thereon are not valid. The amma-tion against the bismuth which the author and hlarignac used, ofcontaining lead, is t'rivial ; for even if it contained as much as 0.25per cent. of lead, which is practically impossible, the atomic weightwould otily be raised 0.17, an amount which i s well within the limitsof variation in the determinations. The author criticises Classen'sapparatus and concludes that his atomic weight, 208.9 (0 = 16), isless likely to be correct than 208.07.Action of Hydrogen Sulphide on certain Metallamines.By E. F. SMITH and H. F. KELLER (Ba-., 23, 33?3-3375).-0npassing pure hydrogen sul phide over yalladio-ammonium chloi-ide a t70--8V0, the salt becomes black, and st higher temperatures am-monium chloride volatilises ; tlhe residue is insoluble in any one aciti,but dissolves sparingly in aqua regia, and probably has the formulaPd S. Pu rpureocobalt chloride, roseocobalt sulp hate, and luteocobaltchloride react in a similar manner with hydrogen sulphide a t ordi-nary temperatures, whilst purpureochromium chloride requires to beheated almost to the dissociation temperature of hydrogen sulphidebefore any uhauge occurs.A. G. B.J. B. T

ISSN:0368-1769    

DOI:10.1039/CA8916000260

出版商:RSC    

年代:1891

数据来源: RSC

摘要:

2 72 ABSTRAOTS OF OHEMIOAL PAPERS. M i n e r a l o g i c a l Chemistry. Celestine containing Free Sulphur. By H. J. JoHNsToN-LAvIs (rwin,. Mng., 8, 28-29).-The author describes sonie crystals of celestine from Girgenti, Sicily, containing as much as 13.59 per cent. of siilphur. The sp. gr. of the crystals was 3.739, the inclnded stilphur lowering the pp. gr. of its host. I t would appear that part of the sulphur crystals and celestine formed simultaneously, and the latter was compelled to include the sulphur grains as its crystals grew in size. B. H. B. Elaterite from Ross-shire. By W. MORRISON ( M k Mag., 8, 133-1 34) .-This mineral tar is an intensely black, lustrous, sticky substance foiiiid in fissures i n the conglomerate above the old red sandstone at the Craig Well, near Dingwall.On dry distillation, i t yields an inflammable oil, gas, and water. It melts at 140°, leaving on ignition a slight, ash cout.aining ferric oxide and lime. B. H. B. Analyses of various Minerals. By I. MACADAM (Min. Mag., 8, 135--137).-Tbe author gives the results of aualyses of diatomite from Mull, of bornite and malachite from the limestone of Kisborn, Rose-shire, of galena and zinc-blende from Tyndrum, Perthshii-e, of fich telite from Handforth, Chesliire, and from Shielding, in Ross-MINERALOGICAL CHEMISTRY. 2 i 3 shire, and lrtstly of elaterite from Dingwall. the preceding abstract, gave the following results :- The last, described in C. H. 0, &c. N, S. Total. 81.19 13.37 4.45 0.13 0.86 100.00 B. H. B. Identity of Bruiachite and Fluorspar. By M.F. HEDDLF: (Min. Mag., 8, 274-277).-The mineral ti-om Loch Bhruithaich, in Inverness-shire, described in 1887, under the name of Bruiachite (Min. Mug., 7, 42), is found by the author to be fluorspar, the analysis giving the follow-ing results :- Ca. F. BaSO,. Total. 51.12 48.56 0.23 99.91 B. H. R. Pyrargyrite and Proustite. By H. A. MIERS (Min. Mag., 8, 37--102).-This is an exhaustive monograph on the red silver ores. The literature is collated, and the crystalline forms previously oh- served are tabnlnted. Excludiug a number of doubtful forms, the author has determined 25 new fov*ms on pyrargyrite crystals, and four new forms on proustite crystals. The results itre given of 25 analyses of specimens in the British Museum. The variations in the rhombohedron angle among the whole series of pyrargyrite Ens- lysed fall within the irregular variations in individual specimens, imd cannot be ascribed t9 the presence of varying quantities of arsenic.The same is true of proustite containing antimony. (Com pare Abstr., 1888, 637.) B. H. R. Crystals of Copper Pyrites. By S. 11. PENFIELD (AWK J. Sci., 40, 2~7-211).-Tbe author gives a crystallographical description of some very unusual and interesting crystals of copper pjrites from the French Creek irou mines, Chester Co., Pennsylvania, the locality from which some curiously developed crystals of iron pyrites have been obtained. It is very remarkable that a t this one locality crystals of iron pyrites are found imitating tetragonal and orthorhornbic symmetry, and crystals of copper pyrites imitating isometric and hexagonal rhombohedra1 symmetry.B. H. B. Metacinnabarite from California. By W. .IT. MELVILLE (Amer. J Sci., 40, 291--295).-An excellent specimen of metacinnabarite found in the quicksilver mine of New Almaden, Califoruia, gave on hnalysis t.he following results :- S. Hg. Fe. Zn. Mn. CaCOB. Quartz. Org. matter. 13.68 78-01 0.61 0.90 0.15 0.71 4.57 0.63 The sp. gr. is 7.118. The mineral occnrs in finely developed and brilliant crystals be- longing to the rhombohedra1 system. The crystals exhibit a high metallic lustre and black colour. They are brittle with a hardntss o€ 2. (Compare Penfield on metacinna- barite crj stals from California, Abstr., 1886, 314.) B. H. B.2 74 ABSTRAOTS OF OHEMICAL PAPERS, Mangano-magnesian Magnetite.By A. H. CHESTER (5f;n. M(ig., 8, 125-126).--6 mineral from New Zealand was analysed with the following results :- Fe20s. FeO. Mn30,. MgO. CaO. 8i02. Total. 66-71 19.62 4.63 7.15 trace 2.38 100.49 From these figures, it, is seen to be a mapetite, in which part of the ferric oxide is replaced by manganic oxide, and part of the ferrous oxide by manganous oxide arid magnesium oxide. It may, t ha-eforc, be celled a mangano-magnesian mapetite, a variety not noticed hitherto. B. H. B. Dufrenite from Cornwall. By E. KINCH (Mitb. Mug., 8, 112- llj).-The mean of a number of analyses of botrjoidal dufrenite from W beal Phoenix gave the followirig r e d ts : - H20. SiOP P206. FeO. Fe203. Alto3. CuO. MgO. Total. 11.47 0.4;3 31.10 6-80 47.05 0.87 1.68 0.17 99-55 From these results, there seems no reason to doubt that pure specti- mens of dufrenite contain a higher ratio of acid to base than that indicated by the formula usually ascribed to the species, 2Fe2Oy,P,O5,3H20, The formula suggested by the author is 3Fe20,,Fe0,2P20,,6H20. B.H. B. Ferric Sulphates from Chili. By F. A. GENTH and S. L. PENFIELD (Amar. J. Sci., 40, 199--207).-l’he authors describe soitre excellent specimens of the ferric sulphates from the Mina de la Compania, near Sierra Gorda, in the Province of Tocapilla. 1. Amuradite (Abstr., 1888, 923).-The crystrtllisatiou is triclinic ; colour brownish-red ; hardness 2.5 ; ep. gr. 2.286. Analysis (No. I) gave the formula Fe2SzO9 + 7H20. [Compare analyses by Freilzel, Abstr., 1888, 923; Mackintosh, Abstr., 1890, 454; and Darapsky, Abstr., 1890, 456.1 2.Xidel.onntrite.-Opticnl properties indicate orthorhombic sym- metry. Analysis (No. 11) gives the formula 2Na2S04,Fe2S,0, + 7H20. 3. Ferronutrife (Abstr., 1890, 455). - No distinct crystals were observed, but the cleavage and the optical properties show thut tlle crystallisation must be hexagonal. Hardness ‘2.5 ; sp. gr. 2.547. Analysis (No. 111) gave results agreeing with the formula 3Na2SO4,Fe2S3O,, + GH,O. Hardness 1.3; sp. gr. 2.355. H20. SO,. Fe203. CaO. Na20. KzO. I. 28.29 35.46 3i.46 trace 0.59 0.11 111. 11.89 51.30 1 7 . 3 0.22 19-95 0.16 11. 17.07 44-23 21.i7 - 16.39 - 4. White.-Minute, brownish white scales from the Mimbres mine,JlINERACOOlCA L CH KMISTRY. 275 Georgetown, New Mexico, gave, ou analysis, results corresponding with the formula Fe2SOs. 5.The authors have also examined some perfect crystals of otacamite. brouirht with the ferric suhhates from the Sierra Gorda. The analysis gGe results agreeing witk the formula, CuC12,SCn( OH),. B. H. B. Contributions to Mineralogy. By F. A. GRNTR (Amer. J. S’ci., 40, 20~207).--YicrophurmucoZite, from Joplin, Missouri, occurring in incrustations of dolomite, appears to he a mixture of several varieties of the sa.me mineral. Analysis gave the following results :- H,O. CaO. MgO. MnO,. A S ~ ~ , . I. 23-11 22.42 6.64 0.26 47.60 11. 24-58 19-64 8.41 0. 9 47-74 111. 20.35 17.09 11-54 0.31 50.56 I, Botryoidal crusts, made u p of radiating fibres, sp. gr. 2.583. Formula (H,CaMg),As,O, + 6H20. 11. Crusts mixed with globular aggregations.111. Radiating silky groups, after the powder had been placed over sulphuric acid for a month. Fitticite, from the Clarissa mine, Tintic District, Utah, occurring in cryptocrystaliine masses, gave results corresponding with the formula ~(F~,AS,O~),F~,(OH)~ + 20H20. The so-called gibbsite from Chester Co., Pennsylvania, is found by the author to be a hydrous aluminium phosphate of unknown consti- t u t ion. B. H. B. Dudgeonite, Hydroplumbite, and Plumbonacrite. By M. F. HEDDLE (Min. Mug., 8, 6OO-203).--G~dgeonite is the name given by the author, after its discoverer, to a mineral found in t h e Pibble mine, Kirkcudbrightshire. It occurs in cavities in copper-nickel. It is n greyish-white solid, having a hardness of 3 to 3.3, aud giving, on analysis, the following results :- NiO.COO. CaO. A S ? ~ , . H,O. Total. 25.01 0.76 9.32 39-33 25.01 99.43 Its formula is ($Xi0 + +CaO),As,O, + 8H,O, hhat of annabergite with one-third of the nickel oxide replaced by lime. A mineral partially described by the author is thonght to have come from Leadhills, and to have the formula SPbO,H,O. The crjstals are white, and probably hexagonal. The name proposed is hydro- 2’ I umbite. A mineral from Leadhills, which appeared to be hydroplumbite, gave, on analysis, results corrcrsponding with the formula PbC03,3Pb0,B20. Not being a hydrated cerrusite, it may be called ylumbonawite. B. H. B. Silicate containing Copper and Silver. By E. JACQCEMJN (Bd1. SOC. Chim. [33, 4, 255).-A mined, called “pierre verte,” ob- t;iined from a lode near Bussang, contained silver, corresponding with 210-2.25 grams per tonne, and copper equal to 35-45 kilos.per tonne,276 ABSTRACTS OF OEEMlOAL PAPERS. and appears to be a copper hydrosilicate accompanied by a cupro- argontic silicate and cupric ferric silicate in a siliceous matrix. T. G. N. Minerals from the Lizard. By J. .J. H. TEALL (Mi)&. Mng., 8, 116--120).-The auttior gives the following aualytical results :- SiO% A1,03. Fe203. Cr203. FeO. MnO. CaO. MgO. Na&. KzO. Ignition. I. 49.9 6.2 1.7 0.6 3.9 0.4 20.4 16.1 - - 0.9 TI. 49.4 29.8 1.2 - - - 12.6 1.7 3.3 0.4 1.7 111. 48.8 10.6 1.7 trace 4.7 - 12.2 18.6 - - 1.8 JV. 52.8 2.8 1.8 - - - 25.2 16.1. - - 0.5 V. 50.8 3 6 3.7 trace 6.8 - 1.2 26.1 0.2 - 3-8 I. Chrome-diopside, found as a constituent of gabbro at Coverak, Cornwall.11. Labradorite, asso- ciated with the chrome-diopside and olivine in the gabbro mentioned above. 111. HornhZsnde, a very pale-coloured variety, occurring in a gabhro schist at Pen Voose. 1V. MuZacoZite, occurring with labra- dorite, sphene. anti an unknown mineral as constituents of an extremely hard and finely crystalline rock at Rnrakclews. Much of the so-called saussurite of the Lizard is similar to this rock in com- position. V. Anthophyllite, occurring in a zone surrounding the altered olivine in some varieties of the Lizard gabbros. I t is eri- dently a secondary mineral resulting from the altemtion of olivine. B. H. B. The mineral hans a ~ p . gr. of 3.2. Mordenite. By L. V. PIRSSON (Arne?. J. Sci., 40, 232-237).- Under the name of‘ mordenite, How published (Trans., 1864, 1QO) a, description of a new zeolite occurring a t Morden Point, Nova Scotia.To this species he assigned the formula R0,R203(Si0,),,6H20. The accuracy of t h i s formula has been questioned, but the author announces the re-discovery of this interestiiig mineral from the Hoodoo Mountain, i n Western Wyoming, and proves the accuracy of How’s work. The analytical results obtained were as follows :- Sin,. Alto,. Fe20R. CaO. MgO. G O . Na.,O. H,O. Total. 66-40 11.17 0.57 1.94 0.17 3.58 2.27 13-31 99 41 These results are closely in accord with HOW’IJ formula. Under the name of ptilolite, Cross and Eakins (Abstr., 1886, 990) described a new zeolite with B formula strikingly similar to that of rnordenite. In the crystal form and optical properties, however, the two zeolites are entirely unlike.B. H, R. Large Porphyritic Crystals of Felspar. By T. H. HOLLAND (Min. ,Mug., 8. 134--157).-Tn consequeni.,e of the striking analogies wbich have been shown to exist between the basalts of Iceland and those oE Mull, tbe author has undertaken an examination of the porphyritic felspars occurring in the lavas of Mull. The crystah exanlined are an inch or more across, yellowish-green in colour, and have a sp. gr. of 2.72. On analysis, they yielded-MINERALOGICAL OHEMISTRY. 277 Si02. A120, + Fe&. CsO. Nst0. Ignition. Total. 50.80 31.54 12.83 3.96 0.52 59.65 These results are in close agreement with those obtained by other observers with the Icelandic felspars. €3. a. B. Conversion of a Felspar into a Scapolite.By J. W. JUDD (Min. Mug., 8, 186-198).-A.t Bade, i n Norway, observations prove that a pyroxene-felspar rock has been converted into a horn- blende-sctlpolite rock. A microscopic study of this rock, described in great detail by the author, proves that the scapolite has been produced by a plagioclnse felspar, and tohat in most cases the change is incom- plete. After the felspar crystals had become charged along their solution planes with cavities containing sodium chloride, the effect of internal stresses in the rock-mass mas to bring about those chemical reactions by which the felspar molecules were broken up, and their material became united with the sodium chloride to form scapolits. B. H. B. Occurrence of Silver in Volcanic Dust.By J. W. MALLET (PTOC. Roy. Soc., 47, ‘L77-%31).--The author had already detecied silver in the volcanic ash from Cotopaxi (Abstr., 1877, 454). He has now found a trace of the same metal in the dust obtained during the eruption of Tunguragua (Ecuadur) on the 11th January, 1886. The mountain had been quiescent. for over a century. Besides the chief constituents, si lica and alumina., the ash contains considerable qnan- tities of the oxides of iron, calcium, and sodium, together with smaller quantities of the carbonates of calcium and mwgnesium. The silver amounts to one part in 107,200, and is probably present RS chloride ; for, though easily dissolved by Folution of potassium cyanide or thio- sulphate, i t is not extracted by nitric acid. The Cotopaxi aNh con- tltined one part of silver in 83,600.J. W. Two New Iron Meteorites. By E. E. HOWELL (Amer. J. $&., 40, 82:3--226) .-1. Meteorite from Hamitton Co., Tezus.-This was dis- covered in 1887. It weighed 179 lbs., the two greater dimensions being 17i and 13 inches. The Widmanstatten figures are brought out with remarkable rapidity on the application of very dilute acid. The amourit of troilite found in cutting the iron is not. great, and seems to be distributed in thin, narrow plates, no nodules having been met with. On analysis, the iron yielded the followiug results :- Fe. Xi. Co. Cu. P. S. C. Total. 86.54 12.77 0.63 0.02 0.16 0.03 0.11 1 0 ~ 2 6 Its sp. gr. is i.95. 8. Metetwite from Pi~quws, Chili.-This is said to hare been found in 1884. I t weighed 14 lbs. 79 om., the two largest diameters being 10 and 5$ inches.The snrface of the iron is unusually smooth, only a few shallow pittings being visible. The etched sections show that the mass has been subjected to fracture and dislocation, result-2i8 ABSTKAOTS Otr OHKMIOAL PAPERS. ing in an undoubted faulting of the Widmanstatten figures and of the troilite. In all probability these are the 6rst faults observed in an iron meteorite. They are clearly not produced by the impact of the fall umn the earth, h u t are a part of the meteorite’s earlier history. Be. Ni. Co. Cu. P. S. C. Total. 81.67 9-83 0.71 0.04 0.17 0.09 0.04 99-53 On analysis, the iron yielded the following results :- Its sp. gr. is 7-93. B. H. B. Five New American Meteorites. By G. F. Kmz (Am.er. J. Sci., 40, 312-323).-1.Metcorites .from Rrenham Township, Kiwa Go., Hansas.-20 meteorites, weighing altogether 2000 lbs., were found i n this district in 1886. The following is an analysis of these meteorites :- Fe. Ni. Co. Cu. P. S. C. Si. 88.49 10.35 0.57 0.03 0.14 0.08 trace trace The olivine (T) and the dark outer zone of olivine (11) gave the Si02. Al2OP Fe203. FeO. XiO. COO. MnO. MgO. S. following results :- I. 40.70 trace 0.18 10.79 0.02 - 0.L4 48.02 - 11. 34.14 - - 23.20 trace 0.03 0.09 40-L!j 5.42 The sp. gr. of the iron freed from olivine was 7.93, whilst that of the olivine was 3.376. The iron is brilliant white, enclosing the troilite, and surrounding the olivine crystals. The outer zone of dark-brown olivine is in reality con,posed of an intimate mixture of troilite and olivine.This group of meteorites is of special interest, because of the probable connection with the meteoric iron found in 1883 in the Turner mounds in Ohio. 2. Meteorite from Winnebago Go., Ima.-ThiB meteorite was observed to fall on May 2nd, 1890. I t is 8 typical chondrite, with a sp. gr. of 3.638, and is composed approximately of 19.40 per cent. of nickeliferous iron, 6.19 per cent. of troilite, 36.04 per cent. of silicatt,s soluble i n hydrochloric acid, and 38.37 per cent,. of dicates insoluble in hydrochloric acid. The nickeliferous iron on analysis gave the following results :- Fe. Ni. c o . P. Total. 92-65 6.11 0.65 trace 99.41 3. Meteoric Stone from Ferguson, Haywood Co., North Carolina.- This fell on July 18, 1889. Its weight was about 8 ozs., and it very closely resembled the meteoric stone from MOCB, Transylvania.4. Meteoric Iron from Bridgewater, Burke Co., North Carolina..- This weighs 30 lbs., and measures 224 by 1.5 by 10 cm. It belongs to the caillite group, and resembles the Cabin Creek and Glorietta Mountain meteorites in structure. Snalysis gave the following results :-MIXERALOGICAL CHEMISTRT. 279 Fe. Ni. c o . P. c1. Total. 88.90 9.94 0.i6 0.35 0-02 99.97 Its sp. gr. was 6.617. 5. Meteoric Iron from Sunzmit, Blount Co., Alabama. --hi3 meteorite weighs 2.2 lbs., and measures 5 by 2 by 3 inches. It con- tains a large quantity of free iron chloride, and showed only a slight, trace of the original crust, being alniost completely oxidised. On etching with nitric acid, no Widmanstatten figures were der eloped, but merely a fine marking similar to that of the Linnville meteorite.Analysis gave the following results : - Fe . Ni. co. P. Total. 93.39 5.62 0.58 0.31 99.90 The sp. gr. was found to be 6.949. B. H. B. Australian Meteorites. By A. LIVERSIDGE (ClLena. News, 62, 267).-The Thuizda meteorite, found near Windordi, i n the Diaman- tina District, Queunsland, weighed 137 lbs., had a sp. gr. 7.78, and tt well-marked crystalline structure ; it was also remarkable for nuuerous nodules of iron sulphide, which in crystallising seem to have given rise to the numerous fissures that proceed from them. I t con- sists essentially of nickeliferous iron containing a trace of cobalt and a small quantity of sulphur, phosphorus, and carbon. Various earthy meteoiites have been found in New South Wales.Of the three Barrutta meteorites, the first, which has already been described, has a sp. gr. 3.429; the second weighs 31 lbs., sp. gr. 3.706 ; the third weighs 48 lbs., sp. gr. 3.429 : the Gilgoilz metcorife weighs 67+ lbs., sp. gr. 3.857 ; the EZi Elwah, 33h lbs., with a sp. gr. of 3.537. These consist essentially of magnesium silicates (as ensta- tite), with more or less nickeliferous iron and some other substances in small quantities ; they resemble one anoi her i n character, showing some variation in being more or less cracked cr granular. D. A. L. Mineral Water of Penon de 10s Banos, Mexico. By L. L'H~TE (J. Plarin. [ 5 ] , 22, 427-430).--The spring occurs on the side of a hill of gravel about 4 kilorn. north-east of Mexico.The water is perfectly limpid and inodorous. Its taste is fir& slightly acid, then alkaline ; its temperature 4.5'. L. Hio de la Loza found the atmosphere at the spring to contain:-Air (?), 6.2; carhonic anhydride, 63.3 ; nitrogen, 28.8: water, 1.7 per cent. by volume. Sp. gr. of the water at 15" when received by the author, 1*00174. Total solid residue, 2.216 grams per litre. Arsenic, iodine, and bromine could not be detected. The solid residue contained :-280 ABSTRAOTS OF OHEMIOAL PAPERS. Sodium carbonate .......... Potassium carbonate ........ Calcium carbonat,e .......... Magnesium carbonate. ....... Sodium sulphate.. .......... .. phosphate.. ........ ,, borate ............. .. chloride.. .......... Lithium chloride. ...........Silica ..................... Alumina .................. Iron oxide.. ............... Organic matter ............. 0.1834 grams per litre. 02945 ,. 9 , 0-4039 ,, 7, 0.4'286 ,, 9 , 0.0074 ,, 9 9 0*001:3 ,, 9 , traces ,, 0.7366 ,, 9 9 0.0060 ,, 9 9 0.1522 ,( ? * 0.0012 ,, 99 0.0009 ,, 99 99 traces ,, 9 , 2'2160 The water is closely analogous to those of Royat and M.mt.-Doro (Auvergne) . J. T. Hot Spring Waters. Bg A. TJIVERSIDOE ( C l t m . NPWS, 62, 264-%6).-Four srr.mples of water from hot springs on Ferguson Island were examined. The surface rocks of this island are princi- prrllg slatey, but t,he immediate neighbourhood of tohe hot springs has all the usual charat-ters of such localities-incrustations, s u l phiir hillocks emitting sulphurous fumes and steam, seething mud pools, &c.Each of the four samples of water had a sediment consisting mostly of sulphur ; in one sample ( I ) it was blue, and contained a few diatom friistules and small crystals of Helenite, in another (4) it was brown, whilst in the others (2 and 3) it was yellow. Sample 1 reacted acid, bad a strong odour of sulphurous anhydride, deposited snlphur on exposure to the air, and, on evaporation, left a pale-brownish, hygro- scopic residue, which, on ignition, intumesced and gave off sulphuric fumes, leaving a mass, yellow when hot and brown when cold, con- sisting of soluble and insoluble silica, iron (originally ferrous), mag- nesia, lime, and sodium chloride in abundance. The other samples were very similar : sample 2 contained a good deal of free snlphiiric acid anti lithium, whilst, samples 3 and 4 contained both sulphurous acid and bydrogen sulphide, and also lithium.These samples gave, in parts per 1000, the numbms under 1, 2, 3, 4 in the following table :- 1. 2. 3. 4. 5. Total solids. ........ 14.10 4.90 3.10 7.58 0.i6 Loss on ignition ..... 9.63 1.27 0.63 2.1 1 0.34 Chlorine ........... - 1.24 0.73 1.39 - Sample 5 is a water from a hot spring on Srtvo Island; i t bad a black deposit consisting of particles of iron sulphide, of quartz, arid other transparent minerals with a few diatom frustules. The water was clear, slightly acid, highly charged with hydrogen sulphide, and on exposure deposited sulphur. The residue from its evaporation was whitish, sulphurous, aud silky-looking, and on ignition gave offORGANIC CHEXISTRY, 281 much stearn, and blackened; the carbonaceous matter burnt away slowly. Hydrochloric and sulphuric acids, hydrogen sulphide, silica, iron, aluminium, calcium, magnesium, and sodium were detected.A sample of water from a fresh water lake on the raised atoll known as Santa Anna was of the density of fresh water, tasted flat and fresh, rapidly decolorised permanganate, and contained, besides plenty of chlorides, some lime arid ammonia. The lake is cut ot€ froin the sea by a swampy tract one-third of a mile across. Some samples from the trachytic island of Simbo were examined. This island at the southern portions has indications of dying volcmic activity. At nn elevation of 300 feet, there ftre fnmeroles emitting steam, temperature 208-210" F., hydrogen sulphide, and sulphurous acid, and depositing sulphur, alum, sodium chloride, milky opal, iron stains, $c.; the water from them shows sulphurous acid and hydrogen sulphide, but 110 hydrochloric or carbonic acid. A fumerole at pLn elevation of 1100 feet above the sea discharged prin- cipally aqueous vapour at a temperatui-e of 175-180" F., very slightly acid, but containing neither hydrogen aulphide nor hydrochloric acid, nor sulphurous or carbonic anhydride, and forming no deppsit round the oritice. D. A. L.2 72 ABSTRAOTS OF OHEMIOAL PAPERS.M i n e r a l o g i c a l Chemistry.Celestine containing Free Sulphur. By H. J. JoHNsToN-LAvIs(rwin,. Mng., 8, 28-29).-The author describes sonie crystals ofcelestine from Girgenti, Sicily, containing as much as 13.59 per cent.of siilphur.The sp. gr. of the crystals was 3.739, the inclndedstilphur lowering the pp. gr. of its host. I t would appear that part ofthe sulphur crystals and celestine formed simultaneously, and thelatter was compelled to include the sulphur grains as its crystalsgrew in size. B. H. B.Elaterite from Ross-shire. By W. MORRISON ( M k Mag., 8,133-1 34) .-This mineral tar is an intensely black, lustrous, stickysubstance foiiiid in fissures i n the conglomerate above the old redsandstone at the Craig Well, near Dingwall. On dry distillation, i tyields an inflammable oil, gas, and water. It melts at 140°, leavingon ignition a slight, ash cout.aining ferric oxide and lime.B. H. B.Analyses of various Minerals.By I. MACADAM (Min. Mag., 8,135--137).-Tbe author gives the results of aualyses of diatomitefrom Mull, of bornite and malachite from the limestone of Kisborn,Rose-shire, of galena and zinc-blende from Tyndrum, Perthshii-e, offich telite from Handforth, Chesliire, and from Shielding, in RossMINERALOGICAL CHEMISTRY. 2 i 3shire, and lrtstly of elaterite from Dingwall.the preceding abstract, gave the following results :-The last, described inC. H. 0, &c. N, S. Total.81.19 13.37 4.45 0.13 0.86 100.00B. H. B.Identity of Bruiachite and Fluorspar. By M. F. HEDDLF:(Min. Mag., 8, 274-277).-The mineral ti-om Loch Bhruithaich, inInverness-shire, described in 1887, under the name of Bruiachite(Min. Mug., 7, 42), is found by the author to be fluorspar, theanalysis giving the follow-ing results :-Ca.F. BaSO,. Total.51.12 48.56 0.23 99.91B. H. R.Pyrargyrite and Proustite. By H. A. MIERS (Min. Mag., 8,37--102).-This is an exhaustive monograph on the red silver ores.The literature is collated, and the crystalline forms previously oh-served are tabnlnted. Excludiug a number of doubtful forms, theauthor has determined 25 new fov*ms on pyrargyrite crystals,and four new forms on proustite crystals. The results itre given of25 analyses of specimens in the British Museum. The variations inthe rhombohedron angle among the whole series of pyrargyrite Ens-lysed fall within the irregular variations in individual specimens,imd cannot be ascribed t9 the presence of varying quantities ofarsenic.The same is true of proustite containing antimony. (Compare Abstr., 1888, 637.) B. H. R.Crystals of Copper Pyrites. By S. 11. PENFIELD (AWK J. Sci.,40, 2~7-211).-Tbe author gives a crystallographical descriptionof some very unusual and interesting crystals of copper pjrites fromthe French Creek irou mines, Chester Co., Pennsylvania, the localityfrom which some curiously developed crystals of iron pyrites havebeen obtained. It is very remarkable that a t this one locality crystalsof iron pyrites are found imitating tetragonal and orthorhornbicsymmetry, and crystals of copper pyrites imitating isometric andhexagonal rhombohedra1 symmetry. B. H. B.Metacinnabarite from California. By W. .IT. MELVILLE (Amer.J Sci., 40, 291--295).-An excellent specimen of metacinnabaritefound in the quicksilver mine of New Almaden, Califoruia, gave onhnalysis t.he following results :-S. Hg.Fe. Zn. Mn. CaCOB. Quartz. Org. matter.13.68 78-01 0.61 0.90 0.15 0.71 4.57 0.63The sp. gr. is 7.118.The mineral occnrs in finely developed and brilliant crystals be-longing to the rhombohedra1 system. Thecrystals exhibit a high metallic lustre and black colour. They arebrittle with a hardntss o€ 2. (Compare Penfield on metacinna-barite crj stals from California, Abstr., 1886, 314.) B. H. B2 74 ABSTRAOTS OF OHEMICAL PAPERS,Mangano-magnesian Magnetite. By A. H. CHESTER (5f;n.M(ig., 8, 125-126).--6 mineral from New Zealand was analysedwith the following results :-Fe20s. FeO. Mn30,. MgO. CaO. 8i02.Total.66-71 19.62 4.63 7.15 trace 2.38 100.49From these figures, it, is seen to be a mapetite, in which partof the ferric oxide is replaced by manganic oxide, and part of theferrous oxide by manganous oxide arid magnesium oxide. It may,t ha-eforc, be celled a mangano-magnesian mapetite, a variety notnoticed hitherto. B. H. B.Dufrenite from Cornwall. By E. KINCH (Mitb. Mug., 8, 112-llj).-The mean of a number of analyses of botrjoidal dufrenitefrom W beal Phoenix gave the followirig r e d ts : -H20. SiOP P206. FeO. Fe203. Alto3. CuO. MgO. Total.11.47 0.4;3 31.10 6-80 47.05 0.87 1.68 0.17 99-55From these results, there seems no reason to doubt that pure specti-mens of dufrenite contain a higher ratio of acid to base than thatindicated by the formula usually ascribed to the species,2Fe2Oy,P,O5,3H20,The formula suggested by the author is 3Fe20,,Fe0,2P20,,6H20.B.H. B.Ferric Sulphates from Chili. By F. A. GENTH and S. L.PENFIELD (Amar. J. Sci., 40, 199--207).-l’he authors describe soitreexcellent specimens of the ferric sulphates from the Mina de laCompania, near Sierra Gorda, in the Province of Tocapilla.1. Amuradite (Abstr., 1888, 923).-The crystrtllisatiou is triclinic ;colour brownish-red ; hardness 2.5 ; ep. gr. 2.286. Analysis (No. I)gave the formula Fe2SzO9 + 7H20. [Compare analyses by Freilzel,Abstr., 1888, 923; Mackintosh, Abstr., 1890, 454; and Darapsky,Abstr., 1890, 456.12. Xidel.onntrite.-Opticnl properties indicate orthorhombic sym-metry. Analysis (No. 11) gives theformula 2Na2S04,Fe2S,0, + 7H20.3.Ferronutrife (Abstr., 1890, 455). - No distinct crystals wereobserved, but the cleavage and the optical properties show thut tllecrystallisation must be hexagonal. Hardness ‘2.5 ; sp. gr. 2.547.Analysis (No. 111) gave results agreeing with the formula3Na2SO4,Fe2S3O,, + GH,O.Hardness 1.3; sp. gr. 2.355.H20. SO,. Fe203. CaO. Na20. KzO.I. 28.29 35.46 3i.46 trace 0.59 0.11111. 11.89 51.30 1 7 . 3 0.22 19-95 0.1611. 17.07 44-23 21.i7 - 16.39 -4. White.-Minute, brownish white scales from the Mimbres mineJlINERACOOlCA L CH KMISTRY. 275Georgetown, New Mexico, gave, ou analysis, results corresponding withthe formula Fe2SOs.5. The authors have also examined some perfect crystals ofotacamite. brouirht with the ferric suhhates from the Sierra Gorda.The analysis gGe results agreeing witk the formula, CuC12,SCn( OH),.B.H. B.Contributions to Mineralogy. By F. A. GRNTR (Amer. J. S’ci.,40, 20~207).--YicrophurmucoZite, from Joplin, Missouri, occurring inincrustations of dolomite, appears to he a mixture of several varietiesof the sa.me mineral. Analysis gave the following results :-H,O. CaO. MgO. MnO,. A S ~ ~ , .I. 23-11 22.42 6.64 0.26 47.6011. 24-58 19-64 8.41 0. 9 47-74111. 20.35 17.09 11-54 0.31 50.56I, Botryoidal crusts, made u p of radiating fibres, sp. gr. 2.583.Formula (H,CaMg),As,O, + 6H20. 11. Crusts mixed with globularaggregations. 111. Radiating silky groups, after the powder hadbeen placed over sulphuric acid for a month.Fitticite, from the Clarissa mine, Tintic District, Utah, occurring incryptocrystaliine masses, gave results corresponding with the formula~(F~,AS,O~),F~,(OH)~ + 20H20.The so-called gibbsite from Chester Co., Pennsylvania, is found bythe author to be a hydrous aluminium phosphate of unknown consti-t u t ion.B. H. B.Dudgeonite, Hydroplumbite, and Plumbonacrite. By M. F.HEDDLE (Min. Mug., 8, 6OO-203).--G~dgeonite is the name given bythe author, after its discoverer, to a mineral found in t h e Pibblemine, Kirkcudbrightshire. It occurs in cavities in copper-nickel. Itis n greyish-white solid, having a hardness of 3 to 3.3, aud giving,on analysis, the following results :-NiO. COO. CaO. A S ? ~ , . H,O. Total.25.01 0.76 9.32 39-33 25.01 99.43Its formula is ($Xi0 + +CaO),As,O, + 8H,O, hhat of annabergitewith one-third of the nickel oxide replaced by lime.A mineral partially described by the author is thonght to have comefrom Leadhills, and to have the formula SPbO,H,O.The crjstals arewhite, and probably hexagonal. The name proposed is hydro-2’ I umbite.A mineral from Leadhills, which appeared to be hydroplumbite, gave,on analysis, results corrcrsponding with the formula PbC03,3Pb0,B20.Not being a hydrated cerrusite, it may be called ylumbonawite.B. H. B.Silicate containing Copper and Silver. By E. JACQCEMJN(Bd1. SOC. Chim. [33, 4, 255).-A mined, called “pierre verte,” ob-t;iined from a lode near Bussang, contained silver, corresponding with210-2.25 grams per tonne, and copper equal to 35-45 kilos.per tonne276 ABSTRACTS OF OEEMlOAL PAPERS.and appears to be a copper hydrosilicate accompanied by a cupro-argontic silicate and cupric ferric silicate in a siliceous matrix.T. G. N.Minerals from the Lizard. By J. .J. H. TEALL (Mi)&. Mng., 8,116--120).-The auttior gives the following aualytical results :-SiO% A1,03. Fe203. Cr203. FeO. MnO. CaO. MgO. Na&. KzO. Ignition.I. 49.9 6.2 1.7 0.6 3.9 0.4 20.4 16.1 - - 0.9TI. 49.4 29.8 1.2 - - - 12.6 1.7 3.3 0.4 1.7111. 48.8 10.6 1.7 trace 4.7 - 12.2 18.6 - - 1.8JV. 52.8 2.8 1.8 - - - 25.2 16.1. - - 0.5V. 50.8 3 6 3.7 trace 6.8 - 1.2 26.1 0.2 - 3-8I. Chrome-diopside, found as a constituent of gabbro at Coverak,Cornwall. 11. Labradorite, asso-ciated with the chrome-diopside and olivine in the gabbro mentionedabove.111. HornhZsnde, a very pale-coloured variety, occurring in agabhro schist at Pen Voose. 1V. MuZacoZite, occurring with labra-dorite, sphene. anti an unknown mineral as constituents of anextremely hard and finely crystalline rock at Rnrakclews. Much ofthe so-called saussurite of the Lizard is similar to this rock in com-position. V. Anthophyllite, occurring in a zone surrounding thealtered olivine in some varieties of the Lizard gabbros. I t is eri-dently a secondary mineral resulting from the altemtion of olivine.B. H. B.The mineral hans a ~ p . gr. of 3.2.Mordenite. By L. V. PIRSSON (Arne?. J. Sci., 40, 232-237).-Under the name of‘ mordenite, How published (Trans., 1864, 1QO) a,description of a new zeolite occurring a t Morden Point, Nova Scotia.To this species he assigned the formula R0,R203(Si0,),,6H20. Theaccuracy of t h i s formula has been questioned, but the authorannounces the re-discovery of this interestiiig mineral from theHoodoo Mountain, i n Western Wyoming, and proves the accuracy ofHow’s work.The analytical results obtained were as follows :-Sin,. Alto,. Fe20R. CaO. MgO. G O . Na.,O. H,O. Total.66-40 11.17 0.57 1.94 0.17 3.58 2.27 13-31 99 41These results are closely in accord with HOW’IJ formula. Under thename of ptilolite, Cross and Eakins (Abstr., 1886, 990) described anew zeolite with B formula strikingly similar to that of rnordenite.In the crystal form and optical properties, however, the two zeolitesare entirely unlike.B. H, R.Large Porphyritic Crystals of Felspar. By T. H. HOLLAND(Min. ,Mug., 8. 134--157).-Tn consequeni.,e of the striking analogieswbich have been shown to exist between the basalts of Iceland andthose oE Mull, tbe author has undertaken an examination of theporphyritic felspars occurring in the lavas of Mull. The crystahexanlined are an inch or more across, yellowish-green in colour, andhave a sp. gr. of 2.72. On analysis, they yieldedMINERALOGICAL OHEMISTRY. 277Si02. A120, + Fe&. CsO. Nst0. Ignition. Total.50.80 31.54 12.83 3.96 0.52 59.65These results are in close agreement with those obtained by otherobservers with the Icelandic felspars. €3. a. B.Conversion of a Felspar into a Scapolite. By J. W.JUDD(Min. Mug., 8, 186-198).-A.t Bade, i n Norway, observationsprove that a pyroxene-felspar rock has been converted into a horn-blende-sctlpolite rock. A microscopic study of this rock, described ingreat detail by the author, proves that the scapolite has been producedby a plagioclnse felspar, and tohat in most cases the change is incom-plete. After the felspar crystals had become charged along theirsolution planes with cavities containing sodium chloride, the effect ofinternal stresses in the rock-mass mas to bring about those chemicalreactions by which the felspar molecules were broken up, and theirmaterial became united with the sodium chloride to form scapolits.B. H. B.Occurrence of Silver in Volcanic Dust. By J. W. MALLET(PTOC. Roy.Soc., 47, ‘L77-%31).--The author had already deteciedsilver in the volcanic ash from Cotopaxi (Abstr., 1877, 454). He hasnow found a trace of the same metal in the dust obtained during theeruption of Tunguragua (Ecuadur) on the 11th January, 1886. Themountain had been quiescent. for over a century. Besides the chiefconstituents, si lica and alumina., the ash contains considerable qnan-tities of the oxides of iron, calcium, and sodium, together with smallerquantities of the carbonates of calcium and mwgnesium. The silveramounts to one part in 107,200, and is probably present RS chloride ;for, though easily dissolved by Folution of potassium cyanide or thio-sulphate, i t is not extracted by nitric acid. The Cotopaxi aNh con-tltined one part of silver in 83,600.J. W.Two New Iron Meteorites. By E. E. HOWELL (Amer. J. $&., 40,82:3--226) .-1. Meteorite from Hamitton Co., Tezus.-This was dis-covered in 1887. It weighed 179 lbs., the two greater dimensionsbeing 17i and 13 inches. The Widmanstatten figures are broughtout with remarkable rapidity on the application of very dilute acid.The amourit of troilite found in cutting the iron is not. great, andseems to be distributed in thin, narrow plates, no nodules havingbeen met with. On analysis, the iron yielded the followiugresults :-Fe. Xi. Co. Cu. P. S. C. Total.86.54 12.77 0.63 0.02 0.16 0.03 0.11 1 0 ~ 2 6Its sp. gr. is i.95.8. Metetwite from Pi~quws, Chili.-This is said to hare beenfound in 1884. I t weighed 14 lbs. 79 om., the two largest diametersbeing 10 and 5$ inches.The snrface of the iron is unusually smooth,only a few shallow pittings being visible. The etched sections showthat the mass has been subjected to fracture and dislocation, result2i8 ABSTKAOTS Otr OHKMIOAL PAPERS.ing in an undoubted faulting of the Widmanstatten figures and ofthe troilite. In all probability these are the 6rst faults observed inan iron meteorite. They are clearly not produced by the impact ofthe fall umn the earth, h u t are a part of the meteorite’s earlierhistory.Be. Ni. Co. Cu. P. S. C. Total.81.67 9-83 0.71 0.04 0.17 0.09 0.04 99-53On analysis, the iron yielded the following results :-Its sp. gr. is 7-93. B. H. B.Five New American Meteorites. By G. F. Kmz (Am.er.J.Sci., 40, 312-323).-1. Metcorites .from Rrenham Township, KiwaGo., Hansas.-20 meteorites, weighing altogether 2000 lbs., werefound i n this district in 1886. The following is an analysis of thesemeteorites :-Fe. Ni. Co. Cu. P. S. C. Si.88.49 10.35 0.57 0.03 0.14 0.08 trace traceThe olivine (T) and the dark outer zone of olivine (11) gave theSi02. Al2OP Fe203. FeO. XiO. COO. MnO. MgO. S.following results :-I. 40.70 trace 0.18 10.79 0.02 - 0.L4 48.02 -11. 34.14 - - 23.20 trace 0.03 0.09 40-L!j 5.42The sp. gr. of the iron freed from olivine was 7.93, whilst that ofthe olivine was 3.376. The iron is brilliant white, enclosing thetroilite, and surrounding the olivine crystals. The outer zone ofdark-brown olivine is in reality con,posed of an intimate mixture oftroilite and olivine.This group of meteorites is of special interest,because of the probable connection with the meteoric iron found in1883 in the Turner mounds in Ohio.2. Meteorite from Winnebago Go., Ima.-ThiB meteorite wasobserved to fall on May 2nd, 1890. I t is 8 typical chondrite, with asp. gr. of 3.638, and is composed approximately of 19.40 per cent. ofnickeliferous iron, 6.19 per cent. of troilite, 36.04 per cent. of silicatt,ssoluble i n hydrochloric acid, and 38.37 per cent,. of dicates insolublein hydrochloric acid. The nickeliferous iron on analysis gave thefollowing results :-Fe. Ni. c o . P. Total.92-65 6.11 0.65 trace 99.413. Meteoric Stone from Ferguson, Haywood Co., North Carolina.-This fell on July 18, 1889.Its weight was about 8 ozs., and it veryclosely resembled the meteoric stone from MOCB, Transylvania.4. Meteoric Iron from Bridgewater, Burke Co., North Carolina..-This weighs 30 lbs., and measures 224 by 1.5 by 10 cm. It belongsto the caillite group, and resembles the Cabin Creek and GloriettaMountain meteorites in structure. Snalysis gave the followingresults :MIXERALOGICAL CHEMISTRT. 279Fe. Ni. c o . P. c1. Total.88.90 9.94 0.i6 0.35 0-02 99.97Its sp. gr. was 6.617.5. Meteoric Iron from Sunzmit, Blount Co., Alabama. --hi3meteorite weighs 2.2 lbs., and measures 5 by 2 by 3 inches. It con-tains a large quantity of free iron chloride, and showed only a slight,trace of the original crust, being alniost completely oxidised.Onetching with nitric acid, no Widmanstatten figures were der eloped,but merely a fine marking similar to that of the Linnville meteorite.Analysis gave the following results : -Fe . Ni. co. P. Total.93.39 5.62 0.58 0.31 99.90The sp. gr. was found to be 6.949. B. H. B.Australian Meteorites. By A. LIVERSIDGE (ClLena. News, 62,267).-The Thuizda meteorite, found near Windordi, i n the Diaman-tina District, Queunsland, weighed 137 lbs., had a sp. gr. 7.78, and ttwell-marked crystalline structure ; it was also remarkable fornuuerous nodules of iron sulphide, which in crystallising seem to havegiven rise to the numerous fissures that proceed from them. I t con-sists essentially of nickeliferous iron containing a trace of cobalt anda small quantity of sulphur, phosphorus, and carbon.Various earthy meteoiites have been found in New South Wales.Of the three Barrutta meteorites, the first, which has already beendescribed, has a sp. gr.3.429; the second weighs 31 lbs., sp. gr.3.706 ; the third weighs 48 lbs., sp. gr. 3.429 : the Gilgoilz metcorifeweighs 67+ lbs., sp. gr. 3.857 ; the EZi Elwah, 33h lbs., with a sp. gr.of 3.537. These consist essentially of magnesium silicates (as ensta-tite), with more or less nickeliferous iron and some other substancesin small quantities ; they resemble one anoi her i n character, showingsome variation in being more or less cracked cr granular.D. A. L.Mineral Water of Penon de 10s Banos, Mexico. By L.L'H~TE (J. Plarin. [ 5 ] , 22, 427-430).--The spring occurs on theside of a hill of gravel about 4 kilorn.north-east of Mexico. Thewater is perfectly limpid and inodorous. Its taste is fir& slightlyacid, then alkaline ; its temperature 4.5'. L. Hio de la Loza foundthe atmosphere at the spring to contain:-Air (?), 6.2; carhonicanhydride, 63.3 ; nitrogen, 28.8: water, 1.7 per cent. by volume.Sp. gr. of the water at 15" when received by the author, 1*00174.Total solid residue, 2.216 grams per litre. Arsenic, iodine, andbromine could not be detected. The solid residue contained :280 ABSTRAOTS OF OHEMIOAL PAPERS.Sodium carbonate ..........Potassium carbonate ........Calcium carbonat,e ..........Magnesium carbonate. .......Sodium sulphate.. .......... .. phosphate.. ........,, borate ............... chloride.. ..........Lithium chloride. ...........Silica .....................Alumina ..................Iron oxide.. ...............Organic matter .............0.1834 grams per litre.02945 ,. 9 ,0-4039 ,, 7,0.4'286 ,, 9 ,0.0074 ,, 9 90*001:3 ,, 9 ,traces ,,0.7366 ,, 9 90.0060 ,, 9 90.1522 ,( ? *0.0012 ,, 990.0009 ,, 9999traces ,, 9 ,2'2160The water is closely analogous to those of Royat and M.mt.-Doro(Auvergne) . J. T.Hot Spring Waters. Bg A. TJIVERSIDOE ( C l t m . NPWS, 62,264-%6).-Four srr.mples of water from hot springs on FergusonIsland were examined. The surface rocks of this island are princi-prrllg slatey, but t,he immediate neighbourhood of tohe hot springs hasall the usual charat-ters of such localities-incrustations, s u l phiirhillocks emitting sulphurous fumes and steam, seething mud pools, &c.Each of the four samples of water had a sediment consisting mostly ofsulphur ; in one sample ( I ) it was blue, and contained a few diatomfriistules and small crystals of Helenite, in another (4) it was brown,whilst in the others (2 and 3) it was yellow.Sample 1 reacted acid,bad a strong odour of sulphurous anhydride, deposited snlphur onexposure to the air, and, on evaporation, left a pale-brownish, hygro-scopic residue, which, on ignition, intumesced and gave off sulphuricfumes, leaving a mass, yellow when hot and brown when cold, con-sisting of soluble and insoluble silica, iron (originally ferrous), mag-nesia, lime, and sodium chloride in abundance. The other sampleswere very similar : sample 2 contained a good deal of free snlphiiricacid anti lithium, whilst, samples 3 and 4 contained both sulphurousacid and bydrogen sulphide, and also lithium. These samples gave,in parts per 1000, the numbms under 1, 2, 3, 4 in the followingtable :-1. 2. 3. 4. 5.Total solids. ........ 14.10 4.90 3.10 7.58 0.i6Loss on ignition ..... 9.63 1.27 0.63 2.1 1 0.34Chlorine ........... - 1.24 0.73 1.39 -Sample 5 is a water from a hot spring on Srtvo Island; i t bad ablack deposit consisting of particles of iron sulphide, of quartz, aridother transparent minerals with a few diatom frustules. The waterwas clear, slightly acid, highly charged with hydrogen sulphide, andon exposure deposited sulphur. The residue from its evaporationwas whitish, sulphurous, aud silky-looking, and on ignition gave ofORGANIC CHEXISTRY, 281much stearn, and blackened; the carbonaceous matter burnt awayslowly. Hydrochloric and sulphuric acids, hydrogen sulphide,silica, iron, aluminium, calcium, magnesium, and sodium weredetected.A sample of water from a fresh water lake on the raised atollknown as Santa Anna was of the density of fresh water, tasted flatand fresh, rapidly decolorised permanganate, and contained, besidesplenty of chlorides, some lime arid ammonia. The lake is cut ot€froin the sea by a swampy tract one-third of a mile across.Some samples from the trachytic island of Simbo were examined.This island at the southern portions has indications of dying volcmicactivity. At nn elevation of 300 feet, there ftre fnmeroles emittingsteam, temperature 208-210" F., hydrogen sulphide, and sulphurousacid, and depositing sulphur, alum, sodium chloride, milky opal,iron stains, $c. ; the water from them shows sulphurous acid andhydrogen sulphide, but 110 hydrochloric or carbonic acid. Afumerole at pLn elevation of 1100 feet above the sea discharged prin-cipally aqueous vapour at a temperatui-e of 175-180" F., very slightlyacid, but containing neither hydrogen aulphide nor hydrochloric acid,nor sulphurous or carbonic anhydride, and forming no deppsit roundthe oritice. D. A. L

ISSN:0368-1769    

DOI:10.1039/CA8916000272

出版商:RSC    

年代:1891

数据来源: RSC

摘要:

ORGANIC CHEXISTRY. 281 Organic Chemistry. Active Amy1 Derivatives. Rg P. A. GUYE (Compt. rend. 111 74.5-74i).-If the views previously explained (Abstr. lS90 722) are correct any substitution in the group CH,Cl in active amyl chloride that keeps the mass of this group higher than that of the nr,altered H Me and Et gronps will yield derivatives with a rota- tory power of the same sign as that of the amyl chloride. Examina- tion of forty amyl derivatives which may be regarded as derived from the active chloride in the way indicated proved that this deduc- tion is correct. C. H. B. Hydrolysis of Halogen Carbon Compounds. By C. CHARRIR (Corapt. rend. 111 747-748).-Ethylene fluoride is obtained as a colourless gas by heating ethylene bromide ak 200" with silver fluoride. It is absorbed by lime water with formation of glycol and calcium fluoride.The author is endeavouring to obtain ergthrol in a similar manner. He has also investigated the action of haIogen derivatives on boric anhydride at a high temperature. Ethylene bromide and glycerol tribromhydrin yield a considerable quantity of boron bromide at 250". Carbon tetrachloride yields boron chloride i n large quantity ; tetrachloretbjlene reacts with less energy arid hexa- chlorobenzena yields no boron chloride. Carbon tetrachloride silver fluoride and amorphous boron yield gases containing fluorine VOL. LX. U282 ABSTRAOTS OF OHEMIOAL PAYERS. chlorine carbon and boron with some deposition of carbon mil boron and a small quantity of silver. p-Dipropylene. By F. COUTUR~ER (BUZZ.Soc Chim. [3] 4 30-31).-1f pinacone after treatment with sulphiiric acid i R suh- milt& to distillation i t yields in addition to pinacoline a liquid boil- ing at 60-70° which on fract,ionation affords an impure substance boiling a t 65" ; this when heated with calcium chloride in senled tubes and subsequently fractionated over sodium yields /3-dipropylene C6H10 which boils at 69.5". It neither forms a compound with cuprous chloride nor with silver nitrate in ammoniacal solution but yields a tetrabromide CsHloBr4 which is Poluble in alcohol and in ether; i t must therefore dij3er in constitution from the isomeric hydrocarbon boiling at S9" prepared by Favorsky (Abstr. 18M 798) by the action of alcoholic potaqb on pinacolirie dichloride and probably has the con- stitution CH,:CMe*CMe:CH2.By the action of acetic anLydride on pinacone at 80-90" for several days a crystalline dittcetyl derivative of pinacone and a small quantity of P-dipropylene are obtained ; the ;ield of the diacetyl derivative is further enhanced if the action is maintained in the cold during several weeks when it may be extracted by dissolving the exrefis of pinscone in water and re- crystallising the residual crystals from ether. Constitution of Fulminic Acid. By R. SCHOLL (Bey. 23 3505 -3519).-Although the author's researches on this subject are not yet complete he has thought it necessary in view of the recent paper of Holleman (this vol. p. 64) t o publish the results obtained up to the present time. From results obtained in hi8 re- searches on the alkylated glyoxime peroxides it appeared not impossible Hy :N*?.HC:N*O that fulminic acid might be glyoxime peroxide itself Against this supposition however is the fact that phenylglyoxime peroxide does not yield salts (see tbis vol.. p. 316) and that ethereal salts cannot bs prepared from mercuric fulminate. The author also finds that it cannot be convertcd into acid derivatives of phenylgly- oxime peroxide but that by the action of acetic chloride the chief product obtained is acetylisocyanic acid CONAc. To carry out the last-named reaction mercuric fulrninat,e is mixed with light petroleum and an excess of acetic chloride added. Hydrocyauic acid and a small quantity of isocyanic acid are evolved and acetvlisocyanic acid passes into solution. The latter has not yet8 been isolated but that it has raally the constitution assigned to it is shown by the facts t h a t it unites with alcohol forming ethyl acetylcarbclmate NHAc*COOE t with ammonia to form monacetylcarbamide H,N*CO*NHSc and with acctrtmide to form symmetrical diacetylcarbamide CO(NHAc)?.Further it is resolved by water into carbonic anhydride and acet- amide. The residue which remains after separating the light petr- oleum solution consists chiefly of mercuric chloride but contains also small quanti ties of acetylcarbalnide and symmetrical diacetylcsrb- omide. The formation of the latter can be readily explained as part of the acetylisocyanic acid i b 6ecomposed by traces of moiature with C. H. B. T. G. N.ORGANIC CHE3lISTRY. 283 formation of acetstniide which then combines with unaltered acetyliso- cpnic acid forming symmetrical dincetylcarbamide.The properties of this siihstance agree fally with the deseriptiorr of Schmidt (Ahstr. 2872 718) who does notl however give its melting point which the author finds to be 152-153". Attempts were made t o isolate acetylisocyrtnic acic1 by using nitrobenzene as diluent in the above reaction and carefully fmctiona- ting the product under diminished pressure.. A liquid was obtained boiling at 78-80' whicli is not however pwe acetylisocyanic acid but appears to contain about 14 per cent. of acetouitrile. Some- what similar results were obtained by Schiitmnberger (C'ompt. rend. 54 154) in attempting to prepare this compound from acetic chloride and silver isocyanate. The yield of acetylisocyanic acid actually obtained amounted to more than 50 per cent.of the theoretical and it would therefore appear that this is the only primary reaction and tohat the other products are all formed by secondary reactions. The formula which most readily explains this is Steiner's (Abstr. 1883 1074) namely HO*N:C:C:N*OH but it is difficult to understand how a compound of this constitution containiug two carbon atoms united by double linkage should be formed by the oxidation of alcohol. H. G. C. Action of certain Inorganic Salts on the Specific Rotatory Power of Cane-sugar. By K. FARKSTEINER (Ber. 23,3570-3378). -In this paper an account is given of the action of the chlorides of the metals of the alkalis and o€ the alkaline earths on the specific rotatory power of cane-sngar.The author finds that with a constant relation of sugar to water the chlorides of strontium barium and magnesium cause ft decrease in the rotation which coiitinues to diminish as the quantity of salt added is increased. The first action of chloride of calcium is to cause a decrease in the rotation which however on the addition of a certain quantity of the salt. reaches a maximum further addition causing an increase in the rotation which eventnally exceeds that of the pure sugar solution. If the relation of sugar to tbe salt be kept constant and the quantity of water varied it is found that the addition of water caiises in all cases an increase in the specific rotatory power that is tbe action of the salts is lessened. The speeitie rotator7 power is almost unai€ected by varying the quantity of sugar with a constant relation between salt and water.The chlorides of lithium sodium and potassium behave in a similar manner. An examination of the action of the same quantities of different salts shows that in the case of strontium calcium and magnesium the depression varies inversely with the molecular weight and that the product of tbe two quantities is approximately a coilstant. Brlrinm chloride does not tact in the same manner but the chlorides of the alkalis show a similar relation. The relation however only holds within each group of chlorides and not for two salts belonging to different groups. H. G. C . u 2284 ARSTRACTS OF CHlr,MICAL PAPERS. Starch. By C. SCHEIBLER and H. M~TTELML~PR (Bey.23. 34T3). -A reply to the recent communication of Zulkowsky (this vol. p. 165) on the same subject. Gummy Exudation from the Sugar Beet. By E. 0. v. LIFP- MANN ( Ber. 23 3564-3566) .-A number of large unripe beet-roots which had teen nllowed to remain for some weeks in paper were found at. the end of that time to show D verg remarkable appearance. Without any particular brnisinq being visible a number of resinous drops had separated out in the furrows which commonly occnr in the root and had flowed together forming a hard brittle tasteless and odourless mess which could be rtsadily and completely separated froin the roots. In appearance it resembled the ordinary plant gums; i t was insoluble in cold water and alcohol and on burning evolved the c-haracteristic odour of the carbohydrates leaving only & trace of ash.Tt slowly dissolved in boiling alkalis and was precipitated from the neutralised solation by alcohol. When freshly precipitated it dis- solved in water forming a neutral dextrorotatory eolution. On boil- ing with dilute sulphuric acid furfuraldehyde distilled over and arabinoso and galactose were found in tlie residue; when oxidised with nitric acid it yielded mucic acid. From these result& i t would appertr possible that the compound in an anhydride of arabinose and galactose C5H,,05 + C6H& - H20 = C1lHmO,,. The aualysis of the crude compound agrees fairly closely with this formula as also does the quantity o€ furfummide and of mricia acid obtained in the fore- going reaction The lack of material has however put an end to further investigation tu no other case of the formation of the gum- like compound has been obeerved even when the m t s have been specially bruised.H. G. C. Diisobutylamine Ethyl Oxalate. By H. MALBO'I' (BUZZ. &c. Chim. [3] 4 253).-When an alcoholic solution of oxalic acid is added to diisobutylamine a white precipitate is formed which consists of diisobutylamine hydrogen oxalate tirid of diisobntylatnine ethgl oxalate resulting from tlie action of the former Rubstatice on the alcohol ; the mixture ia crystallised from boiling alcobol when the diisobutylamine hydrogen oxslate first separates &s brilliant scales and the ihother liquor on evaporation yields acicular crystals of the ethyl salt COOEt.C00*NH2(CaH,)2 ; these are dried over sulphuric acid and are recrystallised from boiling ether.When tlie Rubstance is heated with water in a reflux apparatus for several days diisobutylamine hydrogen oxalate is produced. The author is con- tiuuing the study of tlie compound. Action of Propaldehyde on Alcohols. By S. B.NEH*BIJRY and M. W. BARXUIK (Amer. Chenz. J. 12 319-520; compare Genther Annalen 126 63).-P~olyZidene diethyl ether CH2Me*C H (OEt) is obtained by heating for 12 hours in a closed flask at 100" a mixtnre of propaldehyde (1 vol.) ethyl alcohol (2 vols.) and glacial acetic acid (8 vol.). The product is Abaken .witoh a strong solution of calcium chloride to remove unchanged alcohol dried and submitted T. G. N.ORGANIC CHEMISTRY. 283 to frrlctional distillatien. pressure of 74A rum. and has a specific gravity of 0.8825 at 0".8G-88" aud has a specific gravity of 0.8657 at 0". The puye ether boils at 122.8" nuder R Pvopycllideue dimethyl ether obtained in a similar way boils at Action of Alcohol on Acraldehyde. Rg S. B. NEWRURT and R. M. CHAMOT (Arner. Chem. J. 12 521-525).-The yield of isotri- ethylin prepared according to the instructions given by Alsberq (Jahrsber. 1864 495) is very unsstisfatctory and uncertain. The (*ompound is best prepnrcd hy heating a mixture of ncraldehjde ( 1 vol.) and ahsolute alcohol ( 3 vols.) at a temperature of 50" for five days. On shaking the product with a strong solution of calcium chloride ne:irly the whole of i t separates as a n oily layer which is dried and distillea in a vacuum. The purified product is a colourlesv liquid having a fruity odour boiling a t 85" under a pressure o f 11 mm. and with deccniposition a t 180-18t" under ordinary pressure and having a specific gravity of C.8959 at 0".That it is isotriethylin or triet hoxgpropane is shown by its behaviour towards bromine and by analy-is but its properties are diiferent from those ascribed to that coinpound by Alsberg. The position of the third ethoxy-group is not cstablished althongh the facts that i t readily decomposes on boiling and thak the dieerence between the boiling point of this substance and that of propplidene diethyl ether (compare preceding abstract) is nearly the same as that between the boiling points of auetal and ethosyacetal point to the third group as occupy- ing the a-position and to the constitution of the compound being OEt*CHMe*CH( OEt),.G . T. 31. G. 1'. M. Action of Crotonaldehyde on Alcohol. By S . B. NEWBURY and W. S. CALKIN (Ainer. Chem. .J. 12 5%3-525).-Wben mixtiires of (.rutonaldehyde m d alcohol are heated for a considerable time at temperatures up to loo" the substances remain unchanged ; combination however readily takes place when 60 grams of the former arid 120 grams of the latter are heated i n a closed bottle for six days at SO" with 30 grams of dry zinc chloride. The product trietltoaybutane probably having the constitution CH2Me*CH( i)Et)-C H(OEt) is a colourless liquid of pleasant friiit,y odour boiling at 88-90" under a reduced pressure of 150 mrn. and with slight decomposition at 190" undor ordinary pressures.The specific gravity of the liquid at 0" is 0.88%. G. T. 31. The Indian Grass Oils. By F. D. DODGE (Amer. Clbern. J. 12 ,553-564 ; compare Abstr. 1890 231).-Citrone2tic aldehyde has a density of 0.8560 a t 20" and a rotatory power expressed by [a] = +Po 50'. Its malecular refraction R a = 47-60 does not correspond with that cttlcdated for an aldehyde having a hexntotnic nucleus like the menthol series but agrees with that calculated for the open chain formula C,Hg*CH:CHCJHs*COH or a similar one ; Lence citronellic aldehyde must be regarded as a homologue of286 ABSTRACTS OF OEIEMlOAL PAPERS. acraldehyde. On distilling the bromine additive product 0btrtinr.d from 100 grams of the aldebyde 13 gmms of cymene were obtained. Thia compound however was not formed when the aldehyde wtis treated with iodine and the product distilled but a hydrocarbon boil- i u g near 160" was obtained.CitroiieZlaZ-p?iqhoric acid is prepared as follows :-Phosphoric anhydride ( 5 grams) is covered with dry benzene (20 c.c.) and treated with water (@55 gram) dissolved in ether (30 c.c.). A cake of meta- phosphoric acid forms and the greater part of the liquid is theii poured off. To the rmidue citroncllic anhydride (10 grams) 01- citronella oil (20 grams) is added and the conttrining vessel kept at ~t temperature of 70" for .Revera1 hours. A concentrated solution of sodium carbonate is added until the solution becomes alkaline tbe exoess of oil separated and the aqueous solution extracted with ethei.. Should the aqueous liquid remain colonred a few drops of hydro- chloric acid are added and the treatment with ether contiiiued; this part of the process is repeated until the solution becomes coloui*- less.Excess of concentrated hydrochloric acid is now. added tbe solution cooled and filtered and the precipitated acid crystallised from warm dilute alcohol. It is sparingly soluble in water from which it crystallises in prisms or long flat needles hut dissolveu readily in alcohol from which on slow evapomtdion of the solvent it crystallises in square plates melting at 203". It is a monobasic acid ; the potassium salt crystalhes in long needles and is very soluble i u water ; the sodium salt crystallisea in forms resembling those of the free acid ; the aniline mlt and the quinoline salt both crystallise in white needles the former melting at 1639 The acid is dextro- rotatory and most probably has the constitution although the author has not succeeded in forming similarly consti- tuted compounds from other aldtbhydes.L e w G'rirss Oil.-This substance is of uncertain botanical origin. It resembles citzonella oil insomuch as its cbief constituent is an aldebjde which may be isolated by treating the oil with sodiurri hydrogen sulphite. When 1000 grams of the dry sulphite are dis- solved in 5 litres of hot water 1 litre of the oil added whilst the solution is still warm and the mixture vigorously stirred a pasty mass of tho hydrogen sulphite compound separates. On remaining for tmo or three hours this precipitate dissolves leaving a heavy aqueous solution containing the aldehyde and a layer of residual oil (300 c.c.) above. In 24 hours the solution is perfectly clear and may be siphoned off filtered and made strongly alkaline with sodiuni hydroxide.The supernatant layer of aldebgde ie separated filtered and dried when i t forms a yellow oil (yield 63-68 per cent. of the grass oil taken) of pleatiant citrene odmr and iR slightly volatile i t 1 a current of steam. It boils with gradual decompcrerition at 225" has h y gr. = 0.8'368 at 15.5" is probably inactive behaves with silver riitra te plenylhydiazine aniline and paratohidine like citronellic aldehyde ; gives palamethylpropylhetrzene on distillation with yhon- phoric anhydride a d cjinene on distilling with steam the red oil c~H,,-cH< :> YO~OH,0 RGANIC CHEMISTI’r Y.287 ohiained by the action of concentrated hydrochloric acid ; on treat- ment with zinc-dust and acetic acid it gives a product which is prob- ably the corresponding alcohol. Analysis of the aldehyde shows that it is isomeric with camphor CloH,,O. The above-mentioned aqueous liquid containing the aldehyde appears to be not merely a solution of the hydrogen sulphite compound in excess of sulphite for a crystalline substance having approximately the formula C ,,H180,2NaH S O1,4Na2S O3,50H,O can be separated from it and further additions of the aldehyde to the solution do not cause the whole to precipitate as the sodium hydrogen sulphite compound. That portion oE the lemon grass oil which doe& not combine with sodium hydrogen sulphite appears to contain a terpene as well as cymene.Indian Geranium Oil.-Samples of this oil differed greatly in be- haviour when distilled (compare Semmler Abstr. 2890 Y51). G. T. M. Action of Dilute Nitric Acid on Acetone. By S. B. NEWBURY and W. R. ORNDORFF (Amer. C’hem. J. 12,517-519 ; compare Uebus Aiznnlen 100 1 and Lubavin J. Russ. Cheirt. BOG. 1881 329 aud 49S).-Acetone (I kilo.) was added to nitric acid of sp. gr. 1-42 (1 kilo.) the mixture placed in tall glass cylinders and a few drops of fuming nitric acid introduced t i t the bottom of each by means of a long pipette. I n a few hours bubbles of carbonic anhydride corn- rrienced to iorm and the evolution of gas continued stetkdily for several weeks. At the end of two months the liquid which had a marked odour of hydrocyanic and acetic acids was poured into a large dish and allowed to evaporate spontaneously. After several months crystals of ammonium tetroxalate and free oxalic acid were found iu the syrupy residue which on further concentration and cooling with ice yielded a large quantity of crystals the chief prodnct of the reaction. These crystals agreed in every respect with hydroxyiso- butyric acid OH-CMe2*COOH and the original syrup furnished zinc hydroxyisobutyrate when boiled with zinc oxide.The mother liquor contained the zinc salt of another acid but in quantity too small to admit of its identification. Neither pyruvic acid nor any other pro- ducts of simple oxidation without a breaking up of the acetone mole- cule were formed in perceptible amounts. The production of hydro- cjanic acid by the oxidation of organic substances has been explained by Hantzsch (Annalen 222 65) and the formation of hydroxyiso- hutyric acid from acetone hydrocyanic and hydrochloric acids by Btaedeler (ibia.111 3%). G. T. M. Action of Hydroxylamine on Isonitrosoketones. By R. SCHOLL (Ber. 23 3 5 ~ 4 5 8 1 ) . - W hen concentrated boiling aqueous solutions of Iiydroxylamine hydrochloride and isonitrosoacetone ‘alp mixed the heat developed in the reaction causes the boiling to COW tinue for some time. On neutralising with aqueous soda a yellowish powder crystallises out from which ether extracts met h ylg ly oxime The residue is practically insoluble in the common solvents but dis- 8olve8 in small quantity in boiling alcohol or water separating from288 ABSTRACTS OF CHEJlICAL PAPERS.the latter in white matted needles. It becomes brown R t 180-200" and explodes at 238-247' ; it dissolves readily in mineral acids and solutions of sodium hydroxide and carbonate and is reprecipitated on neutralisation. Its composition as found from analysis and the deter- mination of the molecul&r weight by Raoult's method is CaHgN,03. Ita hydrochloride C6H9Ns03,HC1 is fornied by psssinq hydrogen chloride into the dry substmce suspended in et.her aud forms a hard crystalline cake which dissolves fairly readily in absolute alcobol melts at 112-113" and explodes at a higher temperature. lsonitrosoacetophenone reacts with hydroxylamine i n a similar manner forming phenylglyosime and tt substance insoluble in ether and in all common organic solvents. It dissolves i n soda with a yellow colour and is reprecipitated by acids in white flakes having tho composition Cl6H,a$O$.It also dissolves in hot hydrochloric acid but separates out unaltered on cooling and is probabiy identical with the compound obtained by Miiller and Pechlnann by the action of hydroxylamine on phenylglyoxal (Abstr. 1890 51). Formation of Zinc Propionate by the Action of Carbonio Anhydride on Zinc Ethide. BV I-t. SCHMITT ( J . pr. Chem. [Z] 42 568-569) .-Wanklyn (AmhaZen 107 125) obtained sodium propion- ate by acting on zinc sodium ethide with carbonic anhydride. The author has succeeded i n synthesising zinc propionate by acting on zinc ethide with liquid carbonic anhydride in cm autoclave a t 150-160". At the same time there is a secondary reaction by which ~ o m e of the zinc propionate is decomposed iuto diethyl ketone and einc carbonatc A.G. B. H. G. C. Preparation of Cerotic Acid. By T. MARIE (J. Phnl*m. [ 5 ] 22 343-344).-125 grams of bees'-wax is heated with 3 litres of 9;+" filcohol for two hours. After cooling the alcoholic jelly is ponied off and the treatment w i t h Hlcohol is repeated two or three times and each time for a longer period until the whole of tho cerotic acid is removed. The alcoholic portions are united filtered and distilled with a little potash to retain the volatile acids which have been re- moved from the wax and the distillate serves to dissolve the impure mid upon the filter. This solution being heated to boiling the rnyricin contained forms minute droplets which are deposited on cooling quietly and adhere closely to tho flask.The supernatant jelly is poured on to a tilter and washed with a small quantity of alcohol. After three such treatments and two crystallisations from alcobol the acid is colourless and melts a t 76-77" ; i t is then almost pure. If con- verted into the lead salt according to Brodie's method ether extracts but rtn insignificant amount of matter and the regeuerated acid melts at 7s". J. T. Formation of Ethereal SaIts by Means of Ethyl Chloro- caxbonate. By R. OTTO and W. OTTO (Areh. Phumn. 228 500-516). -When ethyl chlorocarbonate is gradually added to sodium formate covered with about twice its volume of alcohol carbonic anhydride i R at once evolved ; after remaining some time at the ordinary tempera-ORGANIC CHEMISTRY. 289 ture the liquid contains besides sodium chloride aad ethyl carh- onate ethyl formate and free formic acid.with perhaps some free hydrochloric acid. To separate the ethyl formiate the solutioti is supersaturated with sodium carbonate water added iE necessary and sodium chloride to reduce the solubility of the formate which is then siphoned off placed over ignited potash and purified by frac- tional distillation. An intermediate carboxy-compound is supposed to be formed during the reaction thus:-H.COCbNa + ClCOOEt = NaCl + HCO*O.COOEt ; this ethylic carboformate is partly decom- posed directly thns :-HCOOCOOEt = CO + HCOOEt (I) and the remaining part under the action of water from the alcohol gives HCO*O*COOEt + H,O = CO + EtHO + HCOOH (11).If alcohol and water be excluded equation (1) still holds good but the remaining part of the carbuformate is decomposed as follows :- ‘LHCO*O*COOEt = Et,CO + CO + (HCO),O (111) the latter immediately decomposing into formic acid and carbon monoxide. Sodium acetate treated with alcohol and ethyl chlorocarbonate similarly yields acetic anhydride and also ethyl carbonate showing that a reaction analogous to (111) holds good here thus:- 23leCO*O*CC;OEt = (MeCO),O + Et,CO + CO,. Calcium pro- pionste sodium isovalerate and sodium stearate yielded analogous ethyl compounds. Three monobasic acids of the aroniatic series were next examined. Sodium benzoate when acted on by ethyl chloro- carbonate in presence of alcohol formed essentially et,hj1 benzoate and benzoic anhydride whilst when water is excluded ethyl carbonate is also formed.Here also an intermediate carboxg-compound C,H,CO-O.COOEt is supposed to enter into the reaction analogous to the compound formed with formates. Potassium metstolnate jielded ethyl metatoluate and a larger amount of metatoluic an- hydride. Next the sodium salt of an isomeride of the last acid phenylacetic acid was treated. This yielded &hyl phcnylacetate but no anhydride and in t h i s respect resembles the fatty series. Of bibasic acids the potassium salt of oxalic acid yielded scarcely any ethyl oxalate in presence of alcohol owing to the precipitation of the salt from its aqueous solution by this alcohol. I n the absence of alcohol a small quantity of ethyl oxalate was formed after some days.With potassium succinate the reaction was very energetic. E thy1 potassium succinate was produced and a little ethyl carbonate. In the bibasic aromatic series potassium phthalate was employed. Ethyl phthalate was formed but much phthalic mid was re-formed. h’inally sodium salicylate yielded a little e t h j l salicylnte and car- bonate and agaiu much of the salicylic acid w a s regenerated. Pimelic Acids.. By C. A. BISCHOFF and K JAUNSNICRER (Bey. 23 3399-3409).-Symmetrical dimethylglutaric acid (m. p. loso) from methyl iodide and ethyl isobutenyltricarboxvlate is identical with i he “ trimethylsuccinic acid ” from ethyl methglmaloiiate and ethyl bromisobutyrate and also with the acid from ethyl methylmalonats find methyl iodide as well as with Zelinsky’s acid (compare Abstr.1890 132). On heating with hydrochloric acid in a sealed tube for 24 hours nt 2;?0-250° the para-acid is formed (Eoc. cit.). J. T.?!I0 ABSTRACTS OF OHEnlICAL PAPERS. After the separation of dimethylglutaric acid from tho prodnct o l the action of met'hyl iodide on ethyl isohutenyltricurboxylate the lower fraction boiling at 209-245" yield8 a compound which has the formala CsH,,04 ; two preparations showed the melting points 88-92' and 103-1 13O whilst the electrolytic conductivities [ u ) ~ = 353 are K = 0.0114 and 0.0112 respectively. This acid appears to occupy a position in tbe series intermediate between nieth,ylsuccinic acid and antidimethylsuccinic acid ; the formnla points to its being an isomeric dimethylsuccinic or ethylsuccinic acid.The paper concludes with a systematic comparison of the acids obtained (I) by the oxidation of castor oil; (11) from rtmjlene bromide (tri- methylsuccinic acid) ; (111) from rnethylene iodide and ethyl methyl- mitlonate (dimet,hylglutaric acid) ; (IV) ftom methyl iodide amd et by1 isobutenyltricarboxylate. Ethyldimethylsuccinic Acid. By C. A. BISCHOFF and N. MINY z (Ber. 23 34lO-;J41~).-Et~yZd~~~e~h~Zsu~in~c acid J. B. T. C 0 0 H* C H E t.CMe2*C 0 0 H is prepared by heating ethyl orthobromisobutyrate with ethyl sodium etjhglmalonate i n xylene solution at 180-190" for 21 hours under a presstire of 3 atmospheres the product appears to consist of :I mixture of two ethereal salts; it is hydrolysed with potash and after purification the pure acid crptnllises from benzene or water in locg concentric prisms melts at 139" (uncorr.) and is insoluble in light pehroleum carbon bisulphide and xglene but readily dissolves in ether acetone chloroform or glacial acetic acid. The electrolytic conduc- tivity is K = 0.0582 [joa = 3511.The barium and silver salts have been prepared ; the latter is crystalline and insoluble in water. J. B. T. Tetramethylsuccinic Acid. By K. AUWERS and J. A. GARUKER (Rer. 23 3622-3625).-!f'etrameth ylsuccinimide CsH,2<CO>NH co is prepared by dissolving tetramethylsuccinic acid in aqueous ammonia ; the solution is evaporated and the residue heated at 230" for several hours in a sealed tube; the compound crystallises from R mixture of benzene and light petroleum in flat needles melts at 187" arid may be distilled without decomposition ; i t may also be prepared by heating the auhpdride with aqueous ammonia at 100".The phen?yZimide C,H,,<CO>NPh is obtained by the action of aniline on the acid or anhydride and crystallises from dilute alcohol or a mixture of benzene a,nd light pctroleum in needles melts a t 88" and is insoluble in cold water. By treatitig tlhe acid with phenplhydrazine only one compound is obtained which crystallises in flat lustrous needles melting at 124"; it may be volatilised without decomposition and has the formula I > or I >N*NHPb. The anhydride i u the sole product formed by the action of phosphorus pmtachloride co C bIe2*CO*lfH- CMe,+CO CMe2*CO*NPh CMe,*COORGANIC OHEMISTHY. 29 1 on tetramethylsuccinic acid or its salts.With resorcino1 the acid jields a fluorescein derivative which dissolves in acids with a red coloration and a green fluorescence. J. B. T. Homologues of Male'ic Acid. By C. A. BISCHOFF (Ber. 23 3414-343;3).-A reply to Anschutz's paper (this vol. p. 176). The affinitj of sodium for oxygen is greater than that of hydrogen conseyuently in bydrogen sodium carbonate the oxygen of the group ONa is at a greater distance from the carbon atom than that of the group OH; in carbonic acid however the oxygen atoms of both hydroxyl grmps are equally distant from the carbon atom ; hence c.ollisions readily occur and the compound decomposes into water and carbonic anhydride. The same principle is illustrated by reference to acetaldehyde arid ohloi*al hydrate A comparison is then institated by means of models between succinic and maleic acids on the one hand and symmetrical dimethylsuccinic and pyro- cinchonic acids on the other ; i t is shown that the hydroxyl groups approach as closely as in the case of carbonic acid.As regards the intiuence of the other atoms or groups in the molecule the elimirrs- tion o€ two hydrogen atoms from succinic acid or their displacement hy two methyl groups facilitates the formation of mbydrides. It is proposed to determine what influence the ethyl and methyl groups have on the elimination of water from maleic acid. By the actiou of bromine on propenyltricarboxylic acid carbonic anbydride and bydrogen bromide are evolved and the resulting succinic acid derivative C0OH.C HMe*CHBr.COOB yields citraconic acid on distillation whilst by the action of bydrocldoric *acid a t 160° mesaconic acid is formed.Ethy Imale'ic and ethylfumaric acids itre prepared in a similar manner from butenyltricarboxylic acid. Uisubstituted maleic acids may be obtained from the corresponding succinic anhydrides (compare Bischoff and Voit Abstr. 1890 743). Eth!~lmethyEmaleac anhydride is a colourless oil which boils at 237" is soluble i n potash and is reprecipitared unchanged by hydrochloric acid. Xeronic anhydride is formed in the same way from diethyl- succinic anhydride. .J. B. T. Combination of Malic Acid with Potassium Sodium Molyb- date and with Acid Sodium Molybdate. By D. GERNEZ (Compt. rend. 111 T92-794).-Thc salts were added gradually to a solution of a defi~iite quantity of malic acid the totcrl volume of liquid being kcpt constant and the rotatory power was determined in the manner previously described.With potassium sodium molybdate K,0,2N~0,3M00~,14E,O the Isevorotatory power at first increases in proportion to the quantity of salt added and attains a maximum when three equikalents of acid are present for each equivalent of salt. Subsequent variations in rotstory power indicate the formation of compounds containing respectively 3 equivalents of acid and 2 of the salt 3 equivalents of the acid and 3.5 of the salt aud 3 of the acid and 6.5 of the salt. With malic acid and ths acid sodium molybdate 3Na20,7N00* the292 ABSTRAOTS OC OEEMIOAL PAPEnS. variations in rotation indicate the formation of a compound of 3 equivalents of acid and 1 of the salt and a cornpound of equal equivalents of the acid and the salt the phenomena being analogous to those observed with ammonium molgbdate although the rotatory powers are somewhat larger.C. B. 13. Ethyl Isobutenyltricarborrylate. By C. A. BISCHOFF (Ber. 23 8395-3399) .-Auwers and Jackson have shown ( Abstr. 1890 1098) that the compound obtained by the action of ethyl methylmalolrate on ethyl bromisobatyrate has the formula C Me (COOE t),*CH,*CHMe*C OOEt and when h ydrolysed yields dimethglglutsric acid with elimination of carbonic anhydride. The author had howecer previously prepared in I) similar manner an identical conipound from ethyl isobutenyl- t.ricrlrboxylata and methyl iodide which he considered to bo trimethyl- mccinic acid.Further investigation has shown that " ethyl iso- butenyltricrtrboxjlate " consiRts of two compounds of the formulru CO OEt.CMe,*C B ( COOE t)a COOE t*CHMe*C H;C H (COOE t)? respectively and that on hydrolysis and elimintltion of carbonic anhydride it yields a mixture of a-methylglutaric acid and dimethyl- mccinic acid which may be separated by fixctional dietillation. No trimethylsuccinic acid could be isolated from the methyl iodide and ethyl isobnt~nyltricar~oxylate product which therefore consist8 only of dimethglgliitaric acid. Trimethylsnccinic acid has however previously been prepared and is known hy the name isopimelic acid (compme this vol. p. 289). and J. B. T. Action of Nitrous Acid on Amido-derivatives. By E. A. KLOIIBIE (Rec.Trav. Chim. 9 134-154).--The action of nitrous acid on the following compounds has been investigated by the author i n order to determine the influence on the action of the accumulation of uegakive groups in the amido-derivative. Nitrous acid acts on methyl amidoformate to farm methyl alcohol with evolution of nitrogen and carbonic anhydride. With the same reagent ethyl methyhmidoformate yields a nitroso-derivative NO*NMe*COOEt which i R a red liquid of sp. gr. 1.133 at 15" boiling at 70" under a pressure of 27 mm. Methyl methylamidoformate also forms a nitrom-compound NO*NMe-COOMe having similar proper- ties to the last-named compound. hlethyl ethylamidoformate in aqneous solutioa is acted on by a current of nitrogen trioxide and forms a nitroso-derivative NO*NEt*COOMe which is a dark-orauge liquid of sp.gr. 1.143 at 15'. Methyl acetylamidrtforrnate which is obtained by the achion oE ethyl methylcarbamrcte on acetic chloride at a moderate heat is a crystd- line substance which melts at 93" and is very soluble in water alcohol ether chloroform and cryatttllisee easily from benzene. 0 1 1 treating an aqueous solution of thiR substance with nitrogen trioxide decomposition occnrs according to the equation CH&O*NH*COOMo + HNO = CH,*COOH + N2 + CO -t MeOH.ORQANJC OHEM ISTRY. 293 Methyl imidodiformate NH( COOMe) is prepared by mixing methyl cirloroformate (1 rnol.) and methjl amidoformate (1 mol.) with 4 part,s of tolnene arid acting on the mixture with sodiiim (1 mol.). After filtration of the product the unattacked sodium i s removed from t11e residue and the mass is treated with dilute sulphuric acid wliich yields up to toluene a crystalline substance melting at 134" ; this is very soluble in water.alcohol acetone and chloroform slightly soluble in ether and almost insoluble in light petroleum. Nitrous ;wid has no action whatever on this substance neither has i t any action on ethyl dimethylamidoformate or on the corresponding methyl derivative. Eth!jl methylacetylamiiJoformute cannot be made by acthg on ethyl nitrosomethylamidoformate with acetic arihydride or on et.hyl niechjlcarbamate with the same reagent; but in presence of ziuc chloride the reaction occurs in the latter case. Ethyl metliylcarb- amate (60 grams) acetic anhydride (30 grams) and zinc chloride (4. grams) are heated for some minutes a t tlie boiling point ot'the mixture until a yellow coloration is produced; the liquid is ex- tracted with ether and yields on distillation a liquid which boils at 189' (corr.) and hrls i t sp.gr. 1.083 at 15" its melting point being 8-9". Ethyl uiti~osomethylamidoformate NO*NMe*COOEt. This red liquid is dissolved i n all proportions by alcohol ether and benzene and is but slightly soluble i n water although distillable with steam. The analogy in the compmition of this substance to that of ethyl nitromethyl- carbamate led the author to treat it with ammonia which does not react except in the presence of water when it forms ethyl carbaniate and methyl alcohol with evolution of nitrogen pointing to the xorma- tion of a compound NHMe*NO which immediately decomposes.Aqueous solutions of mono- and of di-methylamine react similarly to form the componnds NHMeeCOOEt and NMe2*COOEt boiling a t 165" and 14'7" (corr.) respectively. Ebhyl ethylcarbarnate reacts on the substance with formation of nitrogen carbonic anhydride aiid ethyl methylamidoformate. I n contradistinction to the nitro-derivative NO,*NMe-COOE t which yields with ammonia an acid nitr~rnii~e N HMe-NO the nitroso-derivative f urtiishes only decomposition products of a corresponding nitrosamine NHMe*NO ; the author endeavoiired to isolate its potassium and barium salts bnt was an- successful. Mineral acids decompose ethyl nitrosomethylamido- formate with substitution of hydrogen for the group NO ; oxidation is eifected by an acid solution of potassium perwanganate but the nitroso-compound is not converted into the nitro-compound. By reductiou of ethyl nitroso~nethylamidoforriiate with zinc-dust and acetic acid a colourless solution is formed having strong reducing properties and probably containing the hydrazine NH,*NMe*COOEt ; but this the author was unable to isolate o r to obtain a condensation product of with aldehydes.At the same time a small quantity of a white powder which melts at 127-128" and sublimes at 180" is obtained ; this appears to be ethyl dimethyltetrazoriedicarboxjlat,e N,(NMe.COOEt),. This substance is also formed when the liquid resulting from the reduction of a solution of the zlltroso-compouud Nitrous acid does not act on this substance.294 ABSTRACTS OF OHEMIOAL PAPERS.is oxidised by potassium permanganate ferric chloride or bromine water the last reagent affording the better yield. It is soluble i n alcohol benzene acekone or acetic acid but is insoluble i n water ether light petroleum or solutions of the aqueous hydroxides or the mineral acids. By similar reactions methyl nitrosoamidoformate yields tbe tetr- azone N2(NMe*COOMe)2 which melts at 184" ; and methyl nitxoso- methylamidoformrtte the correspondinq derivative N2( NEt*COOMe)? me1 ting at 88-89'. The author concludes with theoretical specula- tions as to the rationale of the reactions. T. G. 3. Reduction of Glycuronic Acid by Sodium Amalgam. By H. THIKRFELDER (Zait. physiol. Chew. 15 71-i6 ; compare Abstr. 1%7 717 ; 18P9 337).-Pure sodium glyciironate was dissolved in five times its weight of water in a loosely-stoppered flask and a littla 2.5 per cent.sodium amalgam added when hydrogen was evolved ; the liquid was then neutralised by sulphui*ic acid and more amalgam added; after some weeks all the glycuronic acid had disappeared. The liquid w w filtered acidified with sulphuric acid and excess of alcohol added ; the sodium sulphate thus prccipitated was filtered off and the filtrate evaporated to dryness on the water-bath with the nddition of barium carbonate. The residue was taken up wiih water filte-red concentrated acidified with salphuric acid and extracted with a mixture of alcohol and ether. The extract was evaporated to a syrup when after a Fthort time small colourless crystals were deposited ; on recrystallisation from water rhombic crystals 1 cm.long were obtained. Details are given relating to the measurement of the ci-ptals. The substance has a slightly swept taste is readily soluble in water hut only sparingly in alcohol. It melts at 178-180" and has the composition CsHl2O7. Its barium calcium and potassiuni salts were examined. Examination of the solubilities and circular polarisation (the free acid is optically inactive) excluded gluconic and gdactonic acids. It does not reduce Fehling's solution so it cannot be nisnnitic acid. Similar considerations lead to the conclusion that i t is not either of the three niannonic acids so it is not the same as any known acid with the formula C,H,,O,; the nature of the new acid must therefore be the subject of renewed investigation.W. D. H. Action of Methyl Iodide on Furihrylamine. By M. ZENON1 (Guzzetta 20 513-557).-Furfurylamine may be readily prepared in considerable quantities by reducing furfuraldoxirne with alcohol and sodium. The yield is 20 per cent. When a solution of furfuryl- amine (1 part) in twice its volume of methyl alcohol is heated with methyl iodide ( 5 parts) the product after purification is a white crystalline powder which melts at 118-12Uo and has the composition C,A,,ONI. This substance has the general properties of the iodides of the organic bases. It is soluble in water a.nd alcohol and is reprecipitated from the aqueous solotion on addition of potash The correspond- Its constitution is probably CH< CH:Q*CH2*NMe,I CH.0ORGANIC CHENTSTHY. 2 95 ing hydmx;de is formed by the action of moist d v e r oxide on the iodide and mag be obtained as a deliquescent crystalline mass which abRorbs carbonic anhydride from the air.The ch2oride is obtained by treating the iodide with fresh moist silver chloride. It is ~1 deli- quescent crystalline compound. The aurochloridp C8H140NCl AuCI platinochloride and picrate are yellow crvstnlline compounds ; the latter melts with decomposition at about 180". On distilling the hydroxide an alkaline liquid having a11 odour resembling that of trirnethylamine and an oily product which is resinified by hydrochloric acid pass over. Action of Acid Chlorides on Bases in presence of Alkalis. B y C. ScaoTrEN (Ber. 23 3430-3431).-Polemical remarks on Marckwald's paper (this vol. p. 181). S.B. A. A. Pyromncic and Dehydromucic Acids. By M. ZENONI (Gazzetfn 20 517-580).-The author further confirms the results obtained by Oliveri and Peratoner (Abstr. 1890 1242) ; both the solid product of the distillation of mucic acid and the mother liqoor after mfficieilt purification yielding ordinary pyromucic acid melting at 132-13.3". I n the course of the experiments a considerable quantity of a reddish- yellow residue consisting of debydrornucic acid. was obtained. This compound would appear to be more particularly formed when mucic acid is distilled at a low temperature. 'l'he methyl salt of this acid C,H20,Mez crystallises from water in large white needles and melts at 112". The hydrazone CIOH1*CO*N2H2Pb obtained by heating the theore- tical quantities of pyromucic acid and phenylhydrazine crystallises in white needles and melts at 142-143" ; its solution i n concentrated sulphiiric acid is coloured deep violet on the addition of ferric chloride.S. B. A. A. I t i s not affected by treatment with bromine or nitric acid. Bromobenzonitriles. By M. SCHOPFF (Ber. 23 3435 -3440).- The best method of preparing these nitriles is to distil the correspond- ing brorriobenzoic acids wikh lead thiocyanste. The yield of nitrib appears to be better the lower the melting point of the acid 01.thobro.mo2,pn,.onitriZe is formed by distilling orttiobromohenzoic acid ('20 grams) with lead th'ocyanate (36 grams) and purifying the product by steam-distillation. It crystnllises in white needles melts at 51" arid boils at 251-253" (uncor.) under 754 mm.pressure. It is easily soluble in hot water and alcohol and has a characberistic odour resembling that of benzaldehgde and benzonitrile. The yield amounts to 4.5 per cent. of the theoretical. Orthobromobenzonitrile can also be obtained by distilling orthobromobenzamide with phos- p boric anhydride. Ortlrobromobenzoic chloride prepared by the action of equal weights of phosphorus pentachloride and orthobromobenzoic acid is a colouy- less liquid which b d s at 241-243" (uncorr.) under 757 mm. pressure and gradually solidifies after tt time. It has a n odonr resembling that of benzoic chloride but less pungent. It is slowly decomposed hg cold water more quickly by hot water and reacts very energetically296 ABSTRACTS OF OHEMlOAL PAPERS. with ammonia. Orthob?.onzl,be?azamids prepared by treating the chloride with finely powdered ammonium carbonate a t the tempera- ture of the water-bath cry~trtllises from hot water or alcohol i u long hard needles melts at 156" when heated rapidly and sublimes above 100".Metnhromobenzonitrile is obtained by distilling metwbromohenzoic acid with lead thiocyanate and is extracted from the distillate witli ether after the uiirtltered acid has been neutralised with dilute am- monia. Parnbromobenronit ri!e is best prepared from parabromo benxamid e by distillation with phosphoric anhydride and purif~cation of the pro- duct by steam-distillation. Owing to the high melting point of para- bromobenzoic acid only 3.3 per cent. of the theoretical Field is obtained on disbilling it with lead thiocyanate.It crystdlises from hot water o r alcohol in slender white needles melts a t Il3" is some- what less volatile with steam than the ortho-compound sublimes 111 white needles and boils a t 235-237" (uncorr.). When orthobromobenzonitrile is nitrated and the product hydro- lysed it is converted into orthobromometanitrobenzoic acid melting at 179 -18UO. Parabromobenzonitrile when treated in the same way yields parabromometanitrobenzoic acid melting at 193". The nitra- tion is best effected by means of a mixture of potassium nitrate and sulphnric acid. By employing f uniing nitric acid the nitrile remains unaltered. Orthobromo.171~taniirr,benzonitrile crystallises from water in needles melts at 117" and is volatile with steam. ParctbromometaiLitrob~!l~zoiLitrite crystallises in white needles melts at 120" i R not so volatile with steam as the ortho-compound dissolves easily in hot water aloohol and acetone less easily in chloroform and benzene and is insoluble in light petroleum.The amide is alone formed i f the parabromometanitrobenzonitrile is allowed to remain in the nitric acid mixture for tl Abort time. The amide forms colour- less needles melts at 156" and is not volatile with steam. It crystallises in needles melts at 38O and boils at 22.5". E. C. R. Action of Methylchloroform on Phenol in presence of Potas- sium and Sodium Hydroxides. By P. BIGIKELLI (Chem. Cent?.. 1890 ii 620 from Ann. C%m. Farm. 12 65-68).-With the object of genrralising the reaction between chloroform and phenol ill pressnce of potash by which hydroxyaldehydes are produced the author substituted methy1chloroforni for chloroform when if the re- action were similar hydroxybenzyl methyl ketone should be produced.Instead of this a substance of the formula C14HE,,0? is formed which the author regards as diphenyletbylidene ether CH,:C(OPh),. I t is very soluble in ether and melts at 95-96'. It does not dissolve in potash neither does it react with phenylhydrazirie. With bromine water a compound of the formula CI4H,,Br2O2 is foiwied without any hydrogen bi-omide being produced. It crjstallises in plcttes which melt at 125". A secoiid substance is formed in the above reaction a liquid which diBtila vvit,h steam ; after drying over siilphuric acid the analysis p v e the formula C,H,O which agrees with that of orthobydroxy-ORGANIC ChEMISTRY.297 acetophenone. It does not however appear to combine with phenyl- hydrazine or with hydroxylamine. By treating it in methyl alcohol solution with sodium amalgam a crystalline substance smelling strongly of oil of roses was obtained. Tetrachlorophenol. By L. HUGOUNENQ (BUZZ. SOC. Chim. [3] 4 8-9 ; compare Abstr. 1890 2il).-Tetrachlornnisoil is heated with hydriodic acid of sp. gr. 1.5 (4 paris) in sealed tubes at 145-148" for 20 hours and from the solution of the prodiict in aqueous soda tetrachlorophenol is precipitated on the addition of hydrochloric acid and after washing and drying is crystallised from light petroleum. Thus prepared it forms white needles melts a t 152" is sublimable and boils a t 278" with decomposition.Tebrachlorophenol is insoluble in water but dissolves in organic solvents; the alcoholic solution decomposes carbonates and seems not to be poisonous. A mixture of nitric and sulphoric acids decomposes the substance with formation of chloronitroquinones. The aut hoi* has prepared the acetyl deriva- tive C6HC14Ac and the ammonium silver lead and copper salts. J. W. L. T. G. N. Constitution of Thymoquinone and /?-Hydroxythymoqui- none Derivatives. (By G. MAZZAHA Qnzzettn 20 481-485) .- In a previons paper (see Abstr. 1890 Y65) the preparation o f 13-hydroxythymoquinone from carvacrol [Me 0 Pr OH = 1 3 6 4 51 was described. To charncterise this compound more fully the anilide and toluidide [NHPh or NH*C6H4Me = 21 were Iwepared by boiling the alcoholic solution of the quinone with aniline 01' toluidine respectively.The anilide crystdlises from alcohol in minute deep-hlue scales dissolves in alkaliue hydroxides forming a violet solution and melts a t 185-187" whilst the isomeride derived from a-hydroxjthymoquiiione melts at 135". The toluidide t h o crjstallises i n blue scales which melt however at 196-197" ; whereas the corresponding isomeride melts at 165'. I t is noticeable that in compounds derived from thymol the melt- ing point is lowered in passing from the nitro- to tlte dinitro- dei.ivatives and from the hydroxyt hymoquinone to either the anilide or toluidide whilst the reverse occurs in the corresponding com- pounds from cnrvacrol. The author regards it as finally estqtliahed that the B-bromo- and p-bromohydro-thymoquinone tire really a-derivatives [ Br = 21.Thymoquinone Dioxime. By F. KEHBMANN and J. MESSINQER (Ber. 23 3557-356t).-As already shortly mentioned (Abstr. 1890 140;3) thymoquinono dioxime C6T32Pr3.Me(NOH)2 may be obtained by the action of hydroxylamine on thymoquinone monoxime (nitrosothymol). In order to prepare it a hot saturated alcoholic solution of the latter is hiled with double the theoretical quantity of liydroxylamine bydrochloride the acid set free being nearly neutral- ised from time to time. The rebulting crystalline powder is dis- solved in warm soda precipitated by acetic acid and recrystn.llised from boiling alcohol. It forms yellowish-white granules n. hich are S. B. A. A. VOL. LX. &298 ABSTRAOTS OF OHEMIOAL PAPERS.insoluble in water and ammonia sparingly soluble in cold alcohol and acetic acid and readily in solutions of the caufitic alkalis forming Ralts which are decomposed by carbonic anhydride. It becomes brown at 200" and decomposes with evolution of pas a t 255". Its solution in soda has the cQlonr of an alkaline solution of potassium ferricyanide andon the addition of very concentrated alkali the sodium salt separahes out in golden-yellow prismatic crystals which are very soluble i n water. The dioxime is not identical with the yolgthymo- quinone dioxime described by Liebermann and Ilinski (Abetr. 1886 239). When an alkaline solution of potassium ferricyanide is added to a Rimilar solution of thymoquinone dioxime a green flocculent precipi- tate of dinitroscscumene separates.It has an odour resembling that of iodine and of thymoquinone and is volatile with steam. undergoing consideraldle decomposition at the same time. It is soluble in alcohol ether and acetic acid with an intense green colour the solutions also mpidly undergoing decomposition. In the dry state it is fairly stable and melts a t 72" to a greenish-yellow liqiiid which tbeu solidities and again melts a t 130° with decomposition. The authors regard i t as most probable that the compound has the formula When boiled with nitric acid of sp. gr. 1-35 it is converted iiito paradinitrocumene C6H2MeP~( NO,) which crystallises from hot dilute alcohol in large colourless thick prisms melts a t 77-78" and is readily soluble in alcohol ether acetic acid and benzene.When reduced with tin and hydrochloric acid it8 yields paradio;midocumene which may be more readily obtained from thymoquinone dioxime by suspending it in alcohol warming with an excess of stannous chloride and hydrochloric acid evaporating the alcohol diluting with water and adding aqueous Rod%. The base is extracted with ether and the solution agitated wit.h concentrated hydrochloric acid as long as separation of the hydrochloride takes place. The latter is dis- solved in the least possible quantity of hot water and concentrated hydrochloric acid added i t then separates in well-developed colour- less four-sided plates which are quite stable in the air whereas the free base readily undergoes oxidation. The diamidocnmene hydro- chloride obtained by Liebermann and Ilinski (Zoc.cit.) is identical with the foregoing but the latter investigators do not appear to have obtained it quite pure. On boiling paradiamidocumene hydrochloride wit,h acetic anhydr- ide and anhydrous sodium acetate i t yields the diacehjl compound C,,H,,,N,O crystdlising in slender white silky needles and melting ill 260". H. G. C. Cholesterol. By K. OBERM~~LLER (Zeit. physiol. Chem. 15 37- 48 TWO forrnulse C,6H,0 and C2,HM0 (Reinitzer Abstr. 1888,1076) have been asmibed to cholesterol (cholesterin). The chief object of the przsent research was by the analysis of certain cholesterol compounds to determine which is the correct one. The general result of theOR(3ANIC CHEXISTRP. 299 analyses is that Reinitzer's formula is correct. The Collowing c3m- pounds were prepared :- Potassium cholest.roxide CnHUOK was prepared by placing potas- sium in an ethereal solution of cholesterol.I t agrees i n all its pro- perties with Reinitzer's sodium cbolesteroxide. Cholesteryl propionate C1,H15*C3HS02 was prepared by heating a mix t8ure of cholesterol with propionic anhydride on the water-bath for half-an-hour ; on cooling it sets to a fatty mass ; tbis is extracted with ether and the propionate precipitated from the extract by tillcoho1 in the form of rhombic plates ; melting point 98". It is easily soluble in ether benzene arid carbon bisulphide sparingly soluhlc in alcohol. After fusion. there is on cooling a play of colours observed blue green orange and red in the order named by reflected light; the complementary colours are seen by transmitted light.I n order to use this reaction as a test for cholesterol the latter must first be obtained in a pure condition ; it may be most readily freed from the fats with which i t is usuallv mixed by the method of saponification before described (Abstr. 1890 1474). Cholesteryl benzoate C,7H4b*C,H502.-This is best prepared by the action of benzoic chloride on cholesterol ; and this preparation may be used for the quantitative estimation of cholesterol. The crystals are plates which show two melting points namelg 145'and 178". A compound with similar propertieR was prepared from isocholesterol. Cholesleryl phthalate CsH,(COO*Cz,H,5)2 was prepared by herttinq phthalic anhydride and cholesterol at 180" and crystals obtained by the addition of alcohol to a hot ethereal solution.It is sparingly solnble in cold ether ; melting point 282.5". Chotesteryl benzy Z ether. CziH45*O*C7H7 prepared by heating sodium cholesteroxide and benzyl chloride at loo" mas crystallised from an alcoholic-ethereal solutim in thin plates me1 ting at 78". Cholesferyl propionate dibromide. C27H&r2*C3R50z.-This additive product is similar to that prepared previously by Wislicenus and Moldenbaaer c27Bd6Brz0 (AnmaZen 146 178) by the action of bromine dissolved in carbon bisulphide on pure cholesterol and to that prepared by Reinitxer (Wiener Momtsh. 1888 Heft 5 ) by the action of bromine on cholesteryl acetate. This substance is impor- tJant as the relation between carbon and bromine gives a key to the formulft of cholesterol.Cholesteryl bromobenzoate C7HQBrO2~CZ,H4~ was also prepared and analped. W. D. H. Derivatives of Diphenylamine. By 0. ERNST (Ber. 23 3423- 3430) .-Amidochlorodiphenylamin~ NHPh*CsH,Cl*NH [NHPh NHZ C1 = 1 2 51 is prepared by t.he reduction of the nitro-compound with stannons chloride tin and hydrochloric acid in alcoholic solut,ion ; it crystal- lises from alcohol iu long colourless needles melts at 99" and is readily soluble in ether benzene and cbloroform. The picrate crpstallises in yellowish-brown plates. N HPh*C,H,Cl*NHAc The acetyl derivative x . 2300 ABSTRACTS OF CHEMICAL PAPERS. is formed bg the action of the calculrtted quant,it,v of acetic anhydride at ~uV mil crystallises from alcohol in silky lustrous needles which melt at 150". Eth~nylo~thamidochlo~od~pph~nyl~~m~ne CMeGN -> CsBJCI is ob- tained on boiling the amido-compound with excess of acetic anhydride ; it crystnllises with difficulty in small coloiirlcss needles.The plafino- chloyicle crystallises from alcohol in long brown needles. Phen~lux~midoahlo~obe~~~ene N < E y > CaB3C1 is prepared by the action of nitrous acid on orthamidochlorodiphenylamine ; it crystal- lises from alcohol in colourless lustrous needles and melts a t 1%". By the cxidation of an acid solution of amidochlorodipheriylamin~ m-itrh ferric chloride a violet-red (lye is produced the hydrochloride of which crystallises in yellowish-green metallic lustxous needles ; the picrate is deposited in dark-green needles ; the sulphafe resembles the Ilydr+ochloride.The free base is obtained by the action of ammonia 011 the salts as a brownish-red crjstallitie precipitate. On heating orthamidochlorodiphenylamine mit,h an equal mole- cular proportion of aniline hydrochloride at ZOO" a deep-blue colouring matter is formed ; dilute solutions exhibit. a coprer-red fluorescence. The addition of ammonia changes the colour to reddish-violet witli yellow-red fluorescence. A similar substance is formed by heating orthamidoc.hloro~iptienylarnine bydrochloride alone. This compound probably bclongs t o the fiuorincliue group but its constitution like that of the previonq dye is unknown. NPh DzIiitropl(enylusnidotoluyZallline C6H,(N0,),.N~-1csH~~e.NH [NH (NO,) = 1 2 4; NH NH = 1 21 i s prepared by the action of dinitrochlorobenzene on orthotolaylene- diamine ; it crystallises from alcohol in brownish-yellow needles melts at 147" m d is iiisoluble in water but readily dissolves in benzene or (Moroform.The compound is soluble in acids with a pale-yellow colour. J)initroy,lienylazimiclotoluene N<$H3Me>N*C6H3(N0,)z - is ppe- pared by the action of nitrous acid 011 t,he previous compound; it c.rystallises from ~lcohol in small pale brownish-yellow needle< melts at. 186" and is insoluble in ether but readily dissolves in benzene chloroform or glacial acetic acid. Dinitroplim yZ-,9-naphthylumine C,oH7*NH*C6H3(N02)2 [NH (NO?) = 1 2 41 is prepared from dinitrochlorobenzene and /3-naphttiyl- amine ; i t is somewhat sparingly soluble in alcohol from which it is deposited in brick-red crystals and ~nelts at 179".Dinitr~hen.yl-p-naphdhoi C,,H,*O*CsH,(NO& [ 0 (NO,X = 1 2 41 is obtained from P-naphthol as a pale-yellow viscid liquid which solidifies after some time and crystallises from alcohol in stellate groupa of pale-yellow needles melting at 95". The corresponding diatnido-derivatives are prepared by the redoc- tion of these t h e e n i t ro-compounds ; d.ia~iidopkenylaii~idotoluyEamirieORGANIC CHEMISTRY. 30 1 and diamidophPnyt-P-n(~p~l~ylani~ne yield azo-derivatives on oxidatior but diamidophenyl-P-naphthol does not yield any colouring matter. Action of Phosphorus Pentachloride on Hydroxyazobemene. Ry K. HEUMANN and R. PAGANINI (Ber. 23 3550-3354).-The action of phosphorus pentachloride on hjdroxyazobenzene was first examined in 1870 bg Kekulh and Hidegh (BPY.3 235). who obtained a compound which they believed to be hydroxgazohenzene J. B. T. N*Ph 0<hc6H4*0H The reaction was also examined by Wallach aud Belli and Wallach and Kiepenheuer (Abshr. 1880 5.56 ; 1889 393) who also found the formula CI2H1,,N2O2 and showed that the substance is reconverted by sodium in alcoholic solution into hydroxyazobenzene but that I t does not yield an ncetyl compound and is insoluble in alkalis. The last two properties are not in filvour of the above constitutional formula and the authors have therefore reinvestigated the reaction. They find that when equal parts of hydroxyazobenzene and phosphorus pentachloride are warmed on the water-bath until evolution of hydrogen chloride ceases and the product no longer dissolves in alkali with a dcep-yellow coloixr a mixture o€ two compounds is obtained which may be separated by the difference in their solubilities in alcohol.The one agrees in all its properties with the so-called 11 y droxgaznxybenzene and crystallises from acetone i n golden-y ellow plates melting a t 148". It was however found to contain phosphorus the empirical formula being CjgH?,N6O4P which agrees equally well with the figures for carbon hydrogen and nitrogen gi-i-en by tbe inves- tigators named above. Jts ready conversion into hydroxyazobenzene is due not to a reducing action b u t t o the alkali present as zinc-dust and alcohol are without action on it. It is therefore beitzeneazophenyl 1. hosphute PO(O*C6H4*N:NPh)3 and may also be prepared by acting 0 1 the potassium salt of hydroxyazobenzene with phosphorus oxychloride. The second product of the reaction crystallises in broad orangs- yellow needles melts a t H8' and siiblinies in golden plates.It is idontical with the pnrnclilorazrobenzene prepared by Heumann and Mentha (Abstr. 1886 874) from paramidoazobenzene. Thiophenylhydrazine. By J. RUHL (Ber. 23 3482-3483).- Thiophetqlhydrazine S( CRH,*NH*N H?)? may be readily obtained from thioaniline by diazotising adding sodium hydrogen sulphite and reducing with zinc-dust. On the addition of concentrated hydro- chloric acid the lrydrochloride separlctes out as a sparingly soluble salt which IS collected pressed dissolved in water and treated with alkali which precipitates the free base in small plates. The latter* after washing with cold water is recrystnllised from the hot liquid and separates in yellowish lustrous plates which on drying form i h mass resembling paper.It melts at 115" decomposes at 130° is sparingly soluble in cold more readily in hot water easily in alcohol and reduces Fehling's solution in the cold. Its hydrochloride and sulphate foim white powders. H. G. C.302 ABSTRACTS OF CHEMICAL PAPERS. T biophenylh ydra zine readily corn bines with 2 m 01s. ben zaldeh y de forming the crystalline hydrazone S(CsH,*N2H:CHPh) ; i t a h corn- bines with phenylcarbamide. Diamylphenylhydrazone. By S. G RIMALDI (Chern. Centr. 1€!90 ii 553; trom L'Orosi 13,19+-193).-1n manner similar to tbat used for the preparation of nonylmethylphenylhydrazone (Abstr. 1890 1394) the author has now prepared its isomeride diamyZyhenyZh?ydr- azone from diamyl ketone which was obtained by the dry distillation of calcium capronate.The ketone combines readily with phenyl- hjdrazine the elimination of water commencing at ordinary tern ye- mtures and considerable development of heat occurring during the process. Dinmyl~henylhydrazorLe C( C,H,,),:N.NHPh is an oily slightly-red liquid having a strong agreeable odour bnt burning ta te. It is neutral insoluble in water soluble in ether alcohol chloroform &c. ; sp. gr. = 0.93896 at 0". It remains fluid at -9*5O. Isomeric Forms of Orthonitrophenylglyoxylic Hydrazone. By A. KRAUSE (Ber. 23 3617-3622 ; compare Pelidin Abstr. 1890 1117).-The hydrazone is converted into an isomeric form (m. p.188-189") by the action of aqueous potash in the cold ; soda is how- ever without action. Both compounds yield lead salts from which on treatment with sulphuric acid the original substances are regene- rated. Isatic hydrazone together with a little aniline is formed irom each compound on reduction with stannous chloride. By heating the hydrazone with sodium ethoxide and twice the molecular proportion of ethyl iodide in a sealed tube for three hour3 at 13U-l4O0 the ethyl salt is obtained crystallising from alcohol ill vellow prisins melting at 126-128". No diethyl derivative could be prepared. When treated with hydrochloric acid the hydrazone decomposes into ammonia aniline and resinous matters. Metanitrophenylglyoxglic hydrazone is dissolved in alcohol and treated with aqueous potash ; a sparingly soluble salt is formed which is allowed to remain for 24 hours ; on the additioo of hydrochloric acid evolution of gas takes place and a green insoluble compound is obtained which melts at BP-285".The aiithor considers t h a t from these results the formnlse previously advanced for the tKo orthonitro-derivatives are no longer probable atid be suggests that the isomerism of the compounds may be of a stereometric nature similar to that of many oximes and explicable by the same hypotheses. Phenacyl Sulphide. By J. TAFEL and A. MAURITZ (Bey. 23 3474-34753 .-In a paper recently published by Delisle (Anualen 260 250) the latter bas described acetotryl phenyl sulphide and has announced his intention of preparing other ketonic sulphides.The authors have idready obtained plzenacyE suZphide S(CH,*COPh) and in view of the above paper of Delisle now publish the results of thvi r i n res tigati on. Pheiiacyl sulphide is readily prepared by dissolviiig 100 parts of H. G. C. J. W. L. J. B. T.OR0 ANIC OHEXISTRI'. 303 bromacetophenoue in 400 parts of alcohol and adding a solution of 12 parts of sodilim in 400 parts of rrlcohol saturated with hydrogen sulpbide cooling well during the addition and subsequently heating for a short time on the water-bath. I t crystallises frotn alcohol in compact colourless prisms melts at 77" is very slightly soluble in hot water readily in alcohol acetic acid cbloroform and benzene and also dissolves in cold concentrated sulphuric acid with a pliow colour. I t is coloured yellollr by boiling alkalis and reduces Fehling's solution without deposition of cilpric sulphide.On treatment with an alkaline solution of hydroxylainine it yields the dioxini e S ( C H2.C P h NOH) which is recrystallised from acetic acid. It melts at 151" and is sparingly soluble in water light petroleum and benzene readily in alcohol ether and acetic acid. S(CB2*CPh:N2HPh) obtained by heating the sulphide with phenylhydrazine a t 100" crystallises from alcoh(J in slender colourless needles which become yellow in the air; it melts at 146-147'. It is readily soluble in beuzene and chloroform almost insoluble in water and dilute acids but dissolves in cold concentrated sulphnric acid with a yellowish- green colour. When bromncetophenone is boiled with alcoholic soda it yields a crystalline corn pound of as yet unascertained cocstitution which seems to have the formula C16Hrd02Br.The dihydrazone H. G . c'. Metaparadiamidobenzoic Acid. By A. ZEHRA (Ber. 23 3625-3635).-[N H C = 1 'L 41 Difurar~,ylquiiLoxalinemetncal.b- oxylic acid (? 'C'H30):N>c~H3*coOH is prepared by the action of furile on metaparadiamidobenzoic acid in glacial acetic acid sohltion ; it crystallises from alcohol in pale-yellow needles softens at 235" and melts at 245". The compound is insoluble in benzene but dissolves i u dilute ammonia or alkaline cltrboriat,es ; with bydrochloric acid it yields a yellowish-red colour whilst the sulphuric acid solution is cherry-red and the original substance is precipitated unchanged on the addition of water.The barium saZt (CJ3~N204)2Ba crytjtallises iu Dale-vellow needles. C(CdH3O):N K J Diphenylquiitoxalinemetacarboxylic acid ~pb:N>C6H,*coOH prc- CPh:N pared from diamidobenzoic acid and benzile crystallises from glacial acetic acid or alcohol in yellowish plates or needles softens at 280" and melts a t 288". It is very sparingly soluble in organic media but dissolves in alkaline carbonates aud hjdIochloric acid. The bariiisri salt (C2,H13N202),Ba + 3H,O crystallises from dilute alcohol in small white needles. The ethyl salt is deposited from alcohol in white needles melts at 151" aud is insoluble in ammonia. Dirnet h y 1 q uiii ma 1 inemetacar boz y lic acid > C~H,*COOH is CMe:N804 ABSTRAOTS OF CHEMICAL PAPERS. prepared from diamidobenzoic acid and diacetyl ; it crystnllises from alcohol in small white needles softens at 250" and melts at 257-260' with decomposition.It is readily soluble i n alkaline carbonates and hydrochloric acid but more sparingly in benzene or ether. The silver solt CI1H9N2O2Ag is obtained in small white insoluble needles. > CsH,.C OOH FMe=N C(0H):N Methyl h y drox y q uinoxd inerar box y lic acid prepared from diamidohcnzoic acid and pyruvis acid resembles the previous compound and crystallises in white needles which blacken at 330" without melting. The barium s d t (CloH;N203)213a + 3H20 is deposited in pale-yellow needlee. Met h'yl pl~enylenedicarboxynaetayrzradicn?.bamat~ C6H3( NH*COOMe),*COOH is obtained from diamidobenzoic acid and methyl chloroformate ; i t crystallises in lustrous needles softens at 300" and melts a t 35.0" with gas cvolution; it is insoluble in water but dissolves in alkaline carbonates. Cadamidornetapheny lcarboxy lic acid CO < NH > C6H,*C0 0 H pre- pared from diamidobenzoic acid nod carbonyl chloride is deposited in snlall needles or plates which are scarcely altered at 360" ; it is very sparingly soluble except i n alkaline carbonates.Diacet y lmetapnradiamido benroic a.c*id !&H,( NH Ac) ?* C 0 OH cry s t a1 - lises from alcohol in small white needles melts at 218" with evolu- tion of gas and is sparingly soluble in dilute hydrochloric acid. Fo~myZparamidobe.nzoic acid COOH*C,H,*NH*COH [N C = 1 41 is prepared by dissolving paramidobenzoic acid in concentrated formic acid ; i t crystallises from alcohol in short white needles and melts a t 268' with decomposition. Metaniti.oformylparcimidobenzoic acid is formed by the action of fuming nitric acid on the previous compound ; it8 crystallises from alcohol in pale yellow needles and melts at 221" with evolution of gas.The silver salt is gelatinous. NH ~~ethenylamidin~henylenemetacarboxylic acid is prepared by the reduction of the nitro-compound and crystallises from dilute formic acid in white needles which decompose a t 325" without melting. The hydrochloride sulphate and nitrate are crystal- line. 5. B. T. Substitution of the Anilido-group for Halogen Atoms in the Benzene Nucleus. By M. SCHOPFF (Ber. 23 3440-3445).-Th~ behaviour of aniiine towards parabromometanitrobenzoic acid has rtlreadg been described (compare Ahstr.1890 374). The author finds that a similar reaction takes place between auiline and ortho- bromomefanitrobenzoic acid and the corresponding ortho- and para- nitriles and amides and the sodium salts of the acids. ~efalzitro-orthanilidobenztn'c acid N H PhCsH3 (NOz) GOOH pre- pared by the action of aniline on orthobromometanitrobeuzoic acid ISORGAN10 UHEMISTRT. 305 obtained in small straw-coloured needles by precipitating its alco- holic solution with water ; i t melts at 247 -248". 'l'he anliydrous sodium salt in obtained as a brick-red compound by adding the theoretical quantity of sodiuni to a solution of the acid in absolute rilcohol; i t absorbs moisture from the air and theu crystallises in yellow needles containing '2 mols. HzO which are lost over sulphuric acid.The barium calcium lead copper silver and mercury salts were also prepared. The rthyl salt of the above acid crystallises from alcohol in yellow plates and welts at 121". Mctariitrr~nraniliclobeiazonitrzle NHPh*C6H3(N0,)*CN is obtained hy carefully heating the bromonitrile with aniline for a short time ; it crystallises from alcohol in short brick-red needles or plates and from hot water in needles melts a t 126' and is easily soluble in alcohol acetone cbloroforrn and benzene less soluble in light petroleum. Nitrariilidobenzanilide and nitrmilidobenzamide are formed in this reaction if the heating is prolonged as the hydrogen bromide liberated in the formation of the anilidonitrilc hydroljses i t to amide. These two compounds are easily separated as the former is only slightly the latter easily soluble in hot alcohol. Metanitro- paranilidobeiizamide crystallises in yellow needles melts a t 187" and by the further action of aniline is converted into metanitroparanilido- benzanilide.MetarLiti.o-o?.thaniZidobenzon,itri~e NH Ph*C6H3(NO2)*CN is sparingly soluble in hot water but easily soluble it1 alcohol ; by precipithon with water i t is obtained in lemon-yellow needles which melt a t 370". Unlike the para-compound it is not hydrolysed by prolonged heating with the hydrogen bromide formed in the reaction. E. C. R. Derivatives of Parabromometanitrobenzoic Acid. By A. GROHMANX (Uer. 23 3445-3450) .-Pal.abro)nometanitrob~nzoic chlwide NOL*C6H,Br*COCI obtained by the action of phosphorus pen tachloride on pnrabromometmitrobeiizoic acid forms yellowish- white needles melts a t 51-53" and is soluble in benzene acetone and chloroform slightly soluble in light petroleum. When this compound is gently warmed with aniline parabrotnometanitrobenz- anilide is formed ; at a higher temperature and in presence of excess of aniline metanit roparanilidobenzanilide is formed.Purabromometa- witrobenzniiilide crystallises from a,lcohol in beautiful orange-yellow crystals belonging to the monosymmetric system and melts at 156". It is soluble in alcohol ether benzene carbon bisulphide chloroform and acetone sparingly soluble in light petroleum arid insoluble i n water Metariitroparanilidobenzanilide forins leafy crystals melts n t 216" and is soluble in alcohol benzene chloroform acetone and acetic acid but insoluble in light petroleum.Parabromometctnl'trobenzamide is best prepared by warming the chloride with ammonium carbonate. It crystallises from alcohol in colourless needles melts at 156" (compare preceding abstractl) and is soluble in alcohol ether and awetone insoluble in water light petroleum chloroform benzene and carbon bisulphide. Metanitro- PclrarnitlobenzanLitie obtained by heating the bromnmide with alcoholic306 ABS'IRAOTS OF CHEMICAL PAPXKS. ammonia at 180° crystallises in lemon-yellow needles melts at 227" and is soluble in acetone acetic acid sparingly in alcohol and insoluble in water benzene light petroleum and chloroform. By the action of ammonia or aniline on ethyl parahromometanitro- benzoate the halogen i s displaced by the amido- or anilido-group ; the ethoxy-group remains urinltered.Ethyl metariitroparamidobenzoate melts a t 3 45' and is soluble in alcohol benzene chloroform acetone ether acet io acid and a.uiIine irisolnble in light petroleurn. Ethyl rnetanitroparanilidobenzoate melts at 125" (compare Abstr. 1890 374). Toluidonitrobenzoic Acid and Naphthylamidonitrobenzoic Acid. By E. HEIDEXSLEBBN (Ber. 23 3451-3458) .-Metarritypara- (ortho)toZiiidobenzoic acid C,H4Me*NH*C6Hl,(N O,)*COOH is prepared hy heating equal weights of orthotoluidine bromonitrobenzoic acid and glycerol in a reflux apparatus until the liquid 011 cooling solidi- fies to a brown mass. I t crystalliscs from dilute alcohol in bright- brown needles melts at 219-211° and ip easily soluble in alcohol chloroform benzene acetic acid and ether.The sodium Fdlt! pre- pared by adding sodium to tlie alcoholic solution of the acid crystal- lises in beautiful dark-red needlcs. The ethyl salt forms bright- yellow plates melts at lW" and is easily soluble in alcohol ether chloroEorm and benzene. E. C. R. Metamidopwra (orttio) to luido benzoic acid is prepared hy heating the nitro-acid with alcoholic ammonium sulphide at 120". It crystallises from dilute alcohol in white needles melts a t 167" rapidly colours in the air and dissolves in alcohol acetone and benzene. The ethyl salt is prepared by reducing the corresponding nitro-compound with alcoholic ainnionium sulphide ; i t melts at 115" and is easily soluble in alcohol ether abd chloroform slightly soluble in benzene.Met anitropcLra( para) toluidobenzoic acid has already been described by M. Schopff. The sodium salt forms beautit'ul da1.k-red needles. The ethyl salt crystallises in beautiful dark-yellow shining plates melts at 115- and is easily solable in alcohol ether and benzene. Jletumidopara(para)toluidobenzoic acid c6 H ,IMe*N H*C,H,( N H2)*C OOH crystallises from dilute alcohol i n bright yellow needles melts a t l85*5" and is easily soluble in alcohol and acetoile insoluble in water. Tho ethyl salt crystallises in colourless needles which turn blue OIA exposure to air melts at 145" and dissolves easily in alcohol ether aud chloroform sparingly in benzene. Azimidopara( para) to1 uidobenzoic a?cid is obtaiaed by acting on metamidoparn (para) toluidobenzoic acid (3 grams) dissolved in abso- lute alcohol (20 c.c.) with amjl nitrite (4 c.c.) and a few drops ofORGANIC CHEMISTRY. 307 concentraked hydrochloric acid.It crystallines from alcohol in beautilul rose-i*ed needles and melts at 271". The nitrazimido- compound is obtained by dissolving the azimido-componnd in fuming nitric acid and precipitating with water. It forms a yellowish-white non-crystalline powder and melts at 253". 0 rthamidop7ienylpara (para)tohyl amine C6H4Me*N H*C6H4*NH2 is obtained by distilling the amido-acid under diminished pressure and mag be purified by precipitation from its aqueous solution with ammonia. It crystallises from water in colourless plates wbich reddeti on exposure to air melts at 74" arid is easily soluble in alcohol ether.chloroform and benzene. When dissolved in hydrochloric acid oxidation takes place and the solution becomes red. Melanitropara-p-nnphthylamidobenzoic acid C,H,*NH*C,H,( NO2>*COO H is best prepared by heatiog a mixture of parabromometanitrobenzoic acid (1 part) /3-naphthylamine (2 parts) and glycerol (3 parts) to boiling in a reflux apparahs. The compound when pure is brick-red arid is soluble in alcohol acetone and acetic acid lesg soluble in benzene and chloroform and insoluble in water. The sodium salt is a red amorphous powder soluble in water. The ethyl s I l t crystallises from ether in beautiful bright-yellow needles melts at 127-5 and is soluble in alcohol acetone acetic acid and chloro- form. Metanitropara-a-nnphth.ylamidohenzoic acid is prepared in the same way as the ,%acid.I t forms a red-brown amorphous powder and is easily soluble in dilute alcohol kc. and somewbat soluble in hot water. The scdium salt forms a dark-red amorphous powder. The ethyl salt crystallises in beautiful red-brown plates melts at log" and is e d y soluble in alcohol benzene acetic wid and chloroform. M~tamidopara-a-nuphthylwmic~obenzoic acid C,,H,.NH*C,H,(NH2)*COOH prepared by reducing the nit.ro-acid with alcoholic ammonium sulphide crystallises in white needles which become red on exposure to air decomposes at go" and is easily soluble in alcohol bcanzene ether and chloroform insoluble in water. E. C. R. Nitration of Hydroxybenzoic Acids by Nitrous Acid. By A. DENINGER (J. pr. C'hem. [ d ] 42 550-553).-When salicylic acid is nitrated with nitric acid the nitro-acid of m.p. 228" is the chief product that of m. p. 144" being obtrtined in small quantity only. By the following methods each cau be obtained practically free from t.he other. Asymmetrical metanitro~alicylic acid [m. p. 228" ; COOH OH NO = 1 2 51 is obtained by mixing salicylic acid (100 grtms) and sodium nitrite (130 grams) with water (150 grams) and slowly adding 1.2 litres of sulphuric acid (sp. gr. 1.5%) so that the tempe- rature may not rise above IS0 vigorous stirring being kept up during the process. After some four hours the liquid is warmed to 50,308 ABSTRACTS OF CHEMICAL PAPERS. and after several hours more the solid is filtered and recrystallised from water. Consecutive metanitroiJalicylic acid (m. p. 144") is obtained by mixing salicylic acid (100 grams) and sodium nitrite (170 grams) with water (150 grams) and adding 1 litre of sulphuric acid (8p.gr. 1-52) at 60" all at once so that the temperature may rise quickly a s otherwise much of the acid oE m. p. 228" will be formed. The solution of the d i d mass in water must be heated with animal charcoal for some time to eliminate orthonitrophenol. Metanitroparahydroxybenzoic aciii (m. p. 185') is obtained by mix- ing parahydroxgbenzoic acid (100 grams) and sodium nitrite ('LOO gramsj with water (ZOO grams) addiug 1 litre of siilphuric acid (sp. gr. 1.52) at 40" and heating for a long time on the water- bath. When sodium nitrite and cold sulphuric acid are added to the parahydroxy-acid no nitro-acid is formed ; but if the nitrite and sulphuric acid are nrixed first and the hydroxybenzoic acid then added the jield of nitro-acid is abundant ; this shows that the formation of ni trosylvulphuric acid is necessary a conclusion proved by substitat- ing this acid for the mixed sodium nitrite and sulphuric acid vith good results.Ortho- and Meta-cresotic Acid. By R. NIETZKI and F. RUP- rEnT (Ber. 23 347tj-3480).-0rthocresotic acid unites with diazo- benzene chloride in the usual manner forming an azo-dye which is readily converted by reduction with stailnous chloride into amid- cwthocresatic acid. On the addition of concentrated hydrochloric acid the hydrochloyide separates a s a precipitate which is readily soluble i n water although but sparingly in hydrochloric acid and may be readily purified by dissolking in water and precipitating with acid.0 1 1 diwolving it in aqueous sodium carbonate and sat,uratinp with Rcetic acid the free amido-acid is obtained in smdl colourless plates which are very sparingly soluble in the common solvents and melt with decomposition above 300°. According to Jncobsen ortho- cresotic acid has tlie constitution [OH Me COOH = 1 2 61 and as the azo-group almost invariably replaces the hydrogen atom in the para-position to the hydroxyl gmup it is probable that the amiclo- group in the above acid occupies the position 4. When arnidoi thocresotic acid is treated with acetic anbydride and sodium acetate it yields a cliircetyl compound which is very soluble and difEcult to purify. On warming it with dilute alkali the acetyl group in combination with the hydroxyl is eliminated and on the addition of an acid the monacetyE derivative is precipitated in small colourless needles melting at 275".On treating the amido-acid with riitrous acid a very stable diazo-compound is formed which may bo recrysrnllisedfrom hotwater; on reduction,it yields a hydrazine deriva- tive. On distilling the acid with quicklime or sodium carbonate. it yields paramidorthocresol t h u s confirming the above assumption with regard to the position of the amido-group. When acetylamidocresotic acid is nitrated in acetic acid solution the carboxyl group is eliaiinatcd and its place taken by the nitro- group. The tccetylamidon itrucresol thus formed crystsllises from Phenol cannot be nitrated like this.A. G. B.OttQANlC CHERL 1 STRY. 309 alcohol in thick yellow needles which melt at 217"; on boilinq wit,h dilute sulphuric acid i t yialds the corresponding amidonitrocresol. This separates from alcoholic solution in long brownish-red needles melting at 118" and forms beautiful red crystalline salts with alkalis. On treatment with nitrous acid it yields a diazo-compound cry~tallis- ing in yellow needles which may be dried at 70-80" but explode at a higher temperature. It is almost unalterpd by boiling alcohol but the diazo-group may be removed if a moderate quantity of alkali be added t,o the boiling solution. 'the nitrocresol t h u s formed is identical with the one obtained by Hofmann and v. Miller which hRs the constitution [Me OH NO = 1 2 31 showing that the nitro-group has in reality 1 aken the position previously occupied by the crtrboxyl.Metacresotic acid was treated in exactly the same manner as the ortho-compound. The antidometacresotic cr.cid obtained from it forms small colo:irless plates which melt at 265". From analog? the most probable constitution is [OH:Me NH, COOH = 1:3:4:6],and this is proved by the fact that on distillation with sodium carbonate,it yields yararnidometacresol which is converted by oxidation into toluquinone. On treatment with nitrous acid amidometacresotic acid yields R d iazo-compound similar to that obtained from the ortho-compound ; this also yields a liydrazine on reduction. The diacetyl and moo. ncetyE compounds are also obtained i n a similar manner. The latter may also be nitrated with eliminatioti of the carboxgl group b u t in this case a dinitro-compound is obtained which forms thick yellow crystals melting a t 225" arid has acid properties forming a potassium salt which crystallises in beautiful red needles.On warming w i t b dilute sulphuric acid it yields anzidodinitrocresoE which crystallises from alcohol in ruby-red needles melting at 160" and has both acid and basic properties. On heating with acetic anhydride it yields a diacefyl derivative melting at 17;". Wheu amidodinitrocresol is treated with nitrous acid i t yields a very explosive diazo-compound crystallising in yellow plates. The diazo- 5roup may be removed by boiling with alcohol in weak alkaline soln- tion ; the dinitrocresol thus obtained crystallises in orange-red needles melting at 99".The constitution of the latter can only be represented by one of the following formult-e if i t be assumed that one nitro-group takes the place of the carboxpl in the amido-acid I. [OH NO Me NO = 1 2 3 61 Of these the former is the more probable as compounds in which the Iiitro-groups occupy the adjacent position are usually unstable ; moreover on reduction it yields a diamido-compound which does not form an azine or quinoxaline on treatment with orthodiketones. Saligeninoxyacetic Acid. By P. BIGIXELLI (Chem. C'enfr. 1890 ii 623-624 ; from An%. Clrim. Farm. 12 69-72).-Saligeninozy- crcetie acid OH*CH2*C6Hp*O*CH~*COOH is prepared by warming sali- genin with chlorncetic acid in presence of sodium hydroxide. The mixture is first warmed on the water-bath and finally over the flarna directly. The mass is then dissolved in a little water and the acid 11.[OH Me (N02)2 = 1 3 5 61. H. G. C.310 ABSTRACTS OF CHEMlCAL PAPERS. liberated by the addition of sulphuric acid. The acid may be recrys- tallised from water and is thus obtained in white lustrous plates melting at. 120". The solutions of the sodium and potassium salts are precipitated by lead acet.ate calcium chloride and silver nitrate but not by barium chloride. The lead and ca-lcium salts are powdery ; the silver salt has the formula C9H,0,Ag + 2H,O. It loses 1 mol. H20 readily but retains the second molecule somewbat persistently. By treating the silver salt with methyl iodide an ethereal salt of the formula C,,H,O is obtained which probably has the constitutional formula OB~CH2*C~H,*O*CH2*COO*CH~L*C6H4*O*CH2*COOMe. I€ salipeninoxyacetic acid is heaied in a current of dry air a t 100-108 it loses 1 mol.H20 and becomes converted into a caramel- like substance of the formula CYH803 and melting at 140'. It is insoluble in all ordinary menstrua and dissolves only i n soda 01' potash. J. W. L. 8 Thionylamines a New Class of Compounds containing Sulphur. By A. MICHAELIS and R. HERZ (Ber. 23 348&3482).- It has already been shown by Michaelis (Abstr. 1890 617) th3t thionyl chloride readily acts on primary and secondary asymmetrical hpdrazines forming compound,s in which the hydrogen atoms of tlie NH group are displaced by the SO2 group. The authors find t h a t the same reaction takes place even more readily with the simple nruido-compounds.The action of this reagent on aniline has also been examined by Schiff (Anrden. 102 111) and Bottinger (Abstr. 1878 863). The mthors proceeded in a similar manner to the last- named dissolving 20 g r a m s of aniline in double its volume of dry benzeiie and adding 20 grams of thionyl chloride also diluted with benzene when separation of a solid substance and developinent of heat takes place. The viscid mass is then heated in a reflux apparatus when R further reaction takes place and tho contents of the flask become thin. After cooling the precipitated aniline bydrochloride is filtered off and the clear liquid distilled. As soon as the benzene has passed over the thermometer rises to 198-200" and a yellow liquid con- denses which after redistillation is quite pure and as shown by its analysis consists of thionylanihe S0:NPh.This boils at 200" has an aromatic and somewhat pungent odour and is slowly decomposed by water and dilute acids and quickly by alkalis with formation of aniline atid an alkaline sulphate. ThionyZparutoluidine C7H7*N:S0 is prepwed in a similar manner ; it is a yellow liquid which has an aromatic odour boils at 224" and solidifies in a freezing mixture to well-developed yellow crystals melting at 7". The reactilm arpears to be quite general the thionyl groap playing the same rale with primary amines as the nitroso-group does with secondai y amines. H. G. C. Metethoxyphenylsulphonic Acid. By A. DELfSLE and G. LAGAI ( Bw 23 3392-339 4) .-Potassium metethox~phenylgulphonate OEt*C,H,*SO,K + H20,ORGANIC OHEMISTRY.31 I is deposited from water in hard octahedrnl crystals and from dilute alcohol in long flat lustrous needles. The harium wZt CeHBSOIBa + 4E3,0 crystallises in needles ; the calciuni. salt (C8H9S04)&a + 3H20 is deposited in thin colourless plates. The free acid crptallihes with difficulty and is readily soluble in water or alcohol. The sulpho- chloride crystallises from ether in hard pale-yellow needles and melts at 38". The sulphonamide crystallises from water in long white needles and melts at 131". The hydrosulphiJe OEt.C,H,*SH is pre- pared by the reduction of the sulphochloride boils at 238-239" and on warming with suiphuric acid gives a yellow coloration which changes successively to red green and blue.Synthesis of Indigo and Allied Dyes. By K. HEUMANN (Ber. 28 ~3431-3435).-Phenylg\gcocineorthocarboxylic acid is prepared by heating anthranilic acid (63 parts) with chloracetic acid (47 parts) and water (500 parts) for t w o hours in a reflux apparatus. It crptallises from hot water as a yellowish granular maw and melts at about 200" with decomposition. It is only slightly soluble iu cold water. The alcoholic solution shows a blue fluorescence. The pre- paration of indigotin from this compound is best carried out as follows :-Phenylg1ycocineorthoca:boxylic acid (1 p:irt) is fused with potash (3 parts) and water (1 part) with consbant stirrirrg and the mixture heated at 180-200" as long as it deepens i n colour. The melt is treated with water oxidised with a current of air or with ferric chloride and hydrochloric acid and the precipitated indigo collected and washed.The temperature of the reaction is 60-80" lower than is the case when phcnylglycocine is employed (compare this vol. p. 75). By L. LEDERER (J. pr. Chem. [2] 42 565-567) -The author combats Heurnatin's claim for priority in this matter (this vol. pp. 75,206). With regard to Heumann's criticism that the indigo cannot actually exist in the melt the author points out that when indigotin is melted with sodium hydroxide in a test-tube the melt first becomes yellow and then orange-red subsequently again giving indigo-blue when treated with dilute sulphuric acid this behaviour is exactly similar to that of J. B. T. E. C. R. Synthesis of Indigo from Phenylglycocine.pbenylgly Locine and sodium hydroxide wheu meked together. A. (3. B. Action of Methyl Iodide on Hydro-a-methylindole. By C. ZATTI and A. FERRA'rINI (Chem. Centr. 1890 ii 554; from Bend Acad. Lincei 6 i 463-466) .-By boiling hydro-a-methglindole (1 pa.rt) with methyl iodide (3 parts) for 20 minutes in a reflux apparatus an oil is formed which is insoluble in the excess of iodide. After distilling off the methyl iodide the oily substance solidifies and may be re- crystallised from alcohol. It is of a slightly red colour smells of indole and melts at 200-202". It is the iodide of an ammonium base Cs&<g2Z>CHMe and dissolves in water and alcohol. By the action of moist silver oxide the free base may be obtained. The latter ie crystalline and absoisbs moisture and carbonic auhydride312 ABSTKACTS OF (YEEhlPCAL P IPEKS.from the air. chloride the chloride is formed which is also hygroscopic. the aurochloride and platinoch loride may be prcpared. By agitating the iodide with freshly precipitated silver From it J. W. L. Indazole Derivatives. By 0. N. W m E. N~~LTING and E. GRANDWOEGIN (Ber. 23 3635-3644) .-The conversion of nitro- toluidine [Me NH NO = 1 2 41 into the corresponding phenol by means of the diazo-reaction io only complete under cerkain special conditions for example by the addition of sodium nitrite to the base dissolved in hot hydrocbloric acid ; i n ordinary circumstance8 more or less nitroindazole is formed probably on account of the close proximity of the methyi and diazo-groups.flu Nitroindazole NO,*C,H,<i/">NH [CH NH NO = 1 2 41 N- is prepared by dissolving nitrotoluidine (30 grams) in 60 grams of con- centrated snlphuric acid dilut,ed with 1 litre of water; the solution is cooled mixed with 14 grams of sodium nitrite dissolved in 200 C.C. of waier mid slowly warmed on the water-bath ; it is finally boiled for a short tJnie and on cooling a mixture of nitroindazole and nitro- cresol is depouit.ed ; this may be separated by repeated crystallisation from water or xylene ; the pure product is obtained in white lustrous needles which melt at 181" and in small quantities may be volati- lised without decomposition. The sodium. salt crystallises in yellow needles. The silver salt is also yellow. The methyl ether CH N- NO,*C,H,< I >NMe is obtained by the action of methyl iodide ~ find alcoholic potash on nitroindazole or the mixture of this and the cresol; it crystallises from benzene in pale-yellow flat needles melts nt l59" is insoluble in light peti-oleurn and yields azoxy-derivatives 011 prolonged heating with alcoholic potash.The corresponding derivative of iiitro-orl hocresol cr-ystallises from light petroleum in colourless needles melting at 74". Acetylriitroii1,dazclZe crystallises irom alcohol iii lustrous needles melts at 139-140" and sublimes without decJm posi ti on. By the action of aqueoiis bromine on nitroindazole a nioncibromo- derivative is formed which is deposited from benzene in small yellow prisms and from alcohol in small needles which melt at 229". The sodium salt crystallises in red needles.No satisfactory results were obtained by the oxidation of nitro- i ndnzole. Nitroindazole niay be reduced by the action of stannous chloride in acid solution ; it is however preferable to employ ammonium sulphide. Amidoindnrole NH,*C6H3< I >NH crystallises from water in white plates or needles ; the former contain water of cryst,al!isation whilst the latter are anhydrous and melt at 210". The hydrochloride is deposited from alcoholic solution in white needles decomposes at 230" without me1 ting and is readily soluble. By the action of sodium nitrite on a salt of ttmidoindazole hydrozy- CH N-ORQANIC CHEMISTRY. 313 C H N- indazole OH*C,H,< I >NH is obtained; i t is deposited from water in colourless crystds melts iit 215-216" ( ? 265-266") and sublimes without decomposition. Irdazole is prodnced by elimina- tion of the amido-group from nniidoindnzole and is fonnd to be identical with a specimen prepwed according t o the method of E.Fischer and Knzel. No indazole could be obtained from ortho- toluidine by the method described above. J. B. T. Derivatives of Beneidinemetasulphonic Acid. By A. ZEHRA (Ber. 23 3459-3464).-Sodium dicrcetylbenzidinemetaszdphonate NHAc*C6H&H3(NHAc)*SO3Na is prepared by heating sodium benzidinesulphonate with somewhat more than an equal weight of acetic anhydride. Unlike most alkali salts of acetamidosulphonic acids i t is sparingly soluble in cold water but etzsily soluble in hot water from which it crystallises i n beautiful long colourless needles.iMetadinitrodiacetylbenzidinexetasulphonic acid NO,*CsH3(NH Ac)*CGH~(NHAC) (NO,)*SO,H obtained by treating a solution of the above compound in concen- trated sulphuric acid cooled to +So with a mixture of concentrated nitric and sulphuric acids has an orange-yellow colour and is estzemely soluble in water and alcohol. The potassiurtz salt crystal- lises from hot water in yellow needles. By heating with dilute sulphuric acid (1 Z ) the ncetyl groups are eliminated and meta- c~initroben=idine?,.e~~.~~~l?~h~~il~ acid NO,*C,jH (NH?) *CGH (N H2) (NO,) S 03H is obtained as a dark-red granular mass very slightly soluble in both hot and cold water but somewhat soluble in dilute mineral acids. The potassium salt crystallises in bright-red needles and is only slightdy soluble in hot and cold water; the ammonium and sodium salts show the same behariour.The tetrazo-compound yields with &naphthol a blue-black dye of coppery lustre which does not dye cotton aiid dyes wool in an acetic acid bath a garnet-red; with P-naphtholdisulphonic acid R. it gives a beautiful reddish-violet and with P-naphtholdisulphonic acid G. a violet-black dye. ~ ~ ~ e t a d i a m i d o ~ ~ ~ ~ z i d i r i e m ~ t a s u l p h o n ~ c acid C6H3 (NH,),.C,jH,!NH,),.SO,H is obtained by reduciiig the nitro-compound with tin and hpdro- chloric acid. The hydrochloride is extreiuely stable and is easily solable in hot water slightly so in cold water. Sodium nitrate when added to the acid solution causes the precipitation of fine yellow flocks consisting probably of the azimide but owing to the small quantity it could not be examined. Ferric chloride instantly darkens the solution and precipitates tl black compound.Platinic chloride does not form a double salt but acts as an oxidising agent. The picratc crystsllises in bright-yellow needles and is sparingly soluble in VOL. LX ?I314 ABSTRACTS OF CE€EMICAL PAPERS. alcohol and water. with the potassium salt of croconic acid the azine When a hot acid solution of the diamine is treated is formed ; this when dry has a black colouy and green metallic lustre and is very slightly soluble in water but more soluble in dilute alkali from which the potassizcm salt is precipitnhed in black micro- crystalline needles on the addition of concentrated potash. An aqueous solution of the azine is completely decolorised by barium cbloride and a heavy black compound separates.E. C. R. Fluorene Hydrides. By P. A. GUYE (BdZ. SOC. Chim. [ 3 ] 4. 266-268 ; compare Abstr. 1889 720).-Fluorene (3.6 grams) phos- phorus (3 grams) and hydriodic acid sp. gr. 1.7 (9 grams) were heated in sealed tubes at 250-260" for 6-7 hours and the liquid resulting from the extraction of the product with ether was frac- tionated over sodium. Two hydrides were obtained a decahydride C,,H, which boils at 254-256" under a pressure of 727 mm. and which is still liquid at -15" but crystallises above -73" and is oxidised on contact with air and an octohydride Cl3HI8 boiling at d72-275" having properties similar to the former. Both these hydrides are soluble in ether and benzene and have an odour like that of diphezlylmethane.In addition to these hydrides a sample of fluorene containing traces of phenanthrene yielded phenanthrene octohydride boiling below 300". T. G. N. Oximes of Halo'id Benzophenones. By R. DEMUTH and M. DITTRICH (Bey. 23,3609-361 7).-Parachlorobenzophenone prepared from chlorobenzoic chloride and benzene when acted on by hydroxyl- amine and excess of alkali in the cold yields two oximes which may be separated by fractional crystallisation from alcohol ; the one melts at 155-156" instead of 149" as previously stated by Beckmann and Wegerhoff (Abstr. 1889 1066) and is termed the a-oxime. The second or p- and more soluble modification is de- posited from dilute alcohol in square prisms melting at '35". No other oxime could be isolated.Both compounds dissolve completely although with some difficulty in aqueous alkalis. The p-oxime is converted into the a-modiiication by heating for about three hours on the water- bath but no change occurs on boiling with alcohol. Both compounds yield chlorobenzophenone when heated with hydrochloric acid for eight hours at 100". a-,4cetyl~artcchlorob enaophenone crystallises from alcohol in rhombo- hedra and melts at 147-148". The /3-acetyE derivative is readily soluble in alcohol from which it is deposited in long slender needles and melts at lOFi-106". The hydroximes are regenerated from both compounds by the action of alcoholic potash. a- Pal-achlorobenzophetmne benzyl ether is obtained by treating the hydroxime with benzyl chloride and sodicm ethoxide and crys talliseaORGANIC OEEMSTRY.315 from alcohol in short prisms melting at 74-75'. The corresponding /3-derivative is deposited from alcohol in long flst needles and melts at 98-99'. Both compounds yield benzyl iodide when heated with hydriodic acid. ~~tadi1,rornoberLzophelzolLe is best prepared by heating benzophenone with the calculated quantity of bromine t$ogether with a little iodine and water in a senled,tubs for €oar hours at 1.50" ; a f h r purification the product crystnllises from alcohol in broad lustrous needles and melts at 141"; the yield is 40 per cent. On gently he Ltiny with solu- tion of hydroxylamine hydrochloride an oxime is obtained which is sparingly soluble in alcohol and crystallisev i n slender needles ; the yield is quantitative.The ketone is regenerated by the action of hydrochloric acid. No other oxime could be separated and only the one compound is formed on treating the ketone with hydroxylamine and excess oE alkali in the cold. All attempts to transform the oxime into a second modification were fruitless. From these results it would appear that the power of forming two oximes is dependent on the symmetry or otherwise of tho molecule. Action of Nitrogen Tetroxide on Aromatic Hetoximes and on Glyoximes. By R. SCHOLL (Ber. 23,3490-3505).-The author has previously shown (Abstr. 1888,443) that aliphatic ketoximes when treated with nitrogen tetroxide i n ethereal solution are converted into pseudonitroles. The aromatic ketoximes behave in a somewhat similar manner but the compounds obtained appear to correspond not with the fatty pseudoni troles but with the dinitro-compounds obtained by the oxidation of the latter.When benzophenonoxime (6 grams) is dissolved in ether (120 grams) and nitrogen tetroxide (3.5 grams) added a brown solution is formed which after remaining for 10 minutes is shaken with soda solution to remove nitric and nitrous acids dried wiih calcium chloride and allowed to evaporate in a vacuum. The product of the reaction is thus obtained in large colourless seemingly monosymme tric plates which may be purified by the addition of water to the hot alco- holic solution. It has the composition CLBH10N204 melts at 78-78.5" decomposes with evolution of brown fumes at 98" and is soluble in the common organic solvents.The simplest slipposition is that it is diphenyldinitrornethane CHPhZ(N0&. That the nitro-groups have not entered the benzene riiig is shown by the fact that on reduction it yields benzophenonoxime and benzgl hydrylamine CHPhz*NHz ; the formation of the first-named compound is not howecer altogether in favour of the supposition that ths above substance is a dinitro- compound and it is not impossible that both this compound and also the corresponding fatty dinitro-compounds may have a constitution expressed by the general formula Xz:C:N<0,N02 which agrees with fht formula recently suggested by V. Meyer (Abstr. 1888 702) for the pseudonitroles namely XZ:C:N*O*NO2. For the sake of simplicity however these substances may for the present be regarded as dinitro- compounds .Acetophenonoxime is acted on by nitrogen tetmxide in the same J. B. T. 0 312316 ABSTRACTS OF CHEMICAL PAPERS. manner but the oil obtained contains acecophenone which conld not be sepmated. On heating to 60° the oil clecomposes with evolntion of nitrous fumes. Nitrogen t etroxide acts 011 sldoximes in quite a different manner ; SL sirnplc oxidation taking place with formation of peroxides thus benzaldoxime yields diphenyZg1yoxime peroxide Ph'F:hf'? already Ph.CN.0' described by Reckmann (Abstr. 1889 %30) under the name azodi- benzenjl peroxide. The reaction is also :jimilar to the formation of diphenyldinitrosacyl (dibenzoylglyoxin~e peroxide) by the oxidation of nitrosoacetophenone with nitric acid (Hollemann Abstr. 1889 49). As it apeeared not impossible from the autlior's esperiments t h a t I I fulminic acid has theconstitution H(?:"*(? (see this vol.p. %2) HCX-0 the oxidation of the glyoxinies has been more closely investigated. Methylethylglyoxime is readily oxidised both by alkaline potassium ferricyanide and by nitrogen tetroxide the latter giving the best yield ; the prodact of oxidation is a colourless refractive pleasant-smelling liquid which boils at 115-116" (uncorr.) under 16.5 nim. pressure and is miscible with the ordinary opganic solvents but is only sparingly soluble in water and insoluble in alkalis. Its nnalysis agrees with the formula C,H,N,O and on distillation at the ordinary pressures i t is partly decomposed into isocyanates a11d is therefore in all prob- ability methyZethylglyo:cii77 e peroxide The corresponding dimethylglyoaime pwoxide is readily obtained by oxidising dimethyl- glyoxime with nitrogen tetroxide in cthereal solution.It) closely resembles the foregoing but boils practically witliont decomposition at 222-223" under 726 mzn. pressure. The oxidation of monornethylglyoxime does not proceed as smoothly a s in tbe two previous cases an oil being obtained which is soluble in water but very readily decomposes. It yields a -yellow compound with soda which also quickly becomes resinous. When the action of nitrogen tetroxide is allowed to continue for some time a crystalline compound of the formula CJ&N306. is also obtained wbich has Me?:X*? EtC:N*O' Me? :Ni?-' NOz*C:N*O' probably tbe constitntion More stable products are obtained from monop henylgljosime.This is best prepared by the action of a boiling solution of hydroxyl- amine hydrochloride on the crude sodium salt of isonitrosoaceto- phenone obtained by Claisen and Manasse's method (Abstr. 11&7 944). The oxidation cannot be carried out in alkaline solution as the peroxide is at once decomposed by alkalis but nitrogen tetroside in etbereal solution readily effects the change. The resulting solution after washing with water is evaporated the residue extracted w i t h chloroform and purified by precipitating its chloroform solution 1% i th light petroleum or its acetic acid solution with water. Analysis and determination of the molecular weight by Raoult's method showcd its formula to be CsHGN202 which agrees with the expected consti tu-ORGANIC CHEMIS'L'RI'.317 It has a bitter taste melts with decom- Ph7:N.Y HC3J-O' t ional formula position at 89-95" is readily soluble in ether acetone chloroform and acetic acid more sparingly in alcohol sand insoluble in light petroleum. On recrystallising from alcohol it is partially converted into benzaldehyde and the odour of the latter and of phenylcarb- amine is also observed on boiling it with water. With concentrated hydrochloric acid it yields hydroxylamine. All attempts to displace the hydrogen atom by metals have been without success. H. G. C. Ethers of Benziloximes. By M. DITTRICH (Ber. 23 3589- 3608) .-Attempts to prepare the methyl ether of ybenziledioxime according to the method of Japp and Klingemann resulted iu the formation of products identical with those from P-benziledioxime showing that the y-oxime had become converted into the more stable ,%modification by the action of the alkali. The hydrochloride of fi-benzildioxime methyl ether softens atl 130° and melts at 14O-14dc instead of 130" as previously given.a-Benziloxime methyl ether is prepared by the same method and crystallises from alcohol in lustrous plates; it melts at 62-63" is readily soluble in ordinary media and does not combine with hydro- chloric acid. No isomeric compound could be detected. yBenziZoxime methyl ether is obtained as an oily liquid which boils at 219-220" under a pressure of 40 mm. ; the distillate solidifies on cooling and may be crystallised from alcohol from which it is de- posited in prisms melting a t 64-65" ; by distillation under ordinary pressure it is decomposed and it does not combine with hydrochloric dcid.The a-ether is unaltered by boiling with hydrochloric acid but on heating with this reagent in a sealed tube for several hours at loo" it is con-rerted into the y-modi- fication; by treating the latter compound in the same manner a t 120-130" it decomposes into benzile and ammonium chloride. Determinations by Raoult's method with benzene as solvent show that the methyl ethers of benxiledioxime have identical molecular ,weights. By the action of a-methylhydroxylamine on benzile a t ordinary temperatures a compound is obtained which crystallises from dilute alcohol melts at 64" and closely resembles ybenzilemonoxime methy i ether in appearance and behaviour.p - ~ e t h y Zhydrozylurnine NHMe-OH is prepared by heating P-benzile- dioxime methyl ether with hydrochloric acid ; the hydrochloride is deposited i n long prismatic crystals which melt at 85-90" and readily reduce alkaline copper solution. Neither the free base nor the hydrochloride reacts with benzile at ordinary temperatures whilst on warming and in preseace of excess of alkali the base is completely decomposed. On heating the dibenzyl ethers of a- and P-benziledi- oxime with hydriodic acid benzyl iodide is eliminated proving that the compound contains the group LNOH. By the action of a-benzyl- hydroxylamine on 7-benzilemonoxime benzyl ether at 130- 150° a dibenzyl ether of a-benziledioxime melting at 153-154" is formed. No isomeric ether could be isolated.318 ABSTRACTS OF OHEMICAL PAPERS.Tbe same compound is also prepared from a-benzyl bydroxylamiue and a-benzilmonoxime proving that the a-dibenzyl ether contains two ZNOC,H groups and it is assumed that the metbyl ethers have an analogous constitution. Similar experiments with p-benzylhydroxylamine gave negnti T-e results. Methyl iodide does not react with the non-basic methyl ether of a-benziledioxime whilst by beating the second modification (q) with methyl iodide at loo" it yields a-benziloxime metbyl ether. On treating this same dimethTl ether (a2) with hydriodic acid at 200' methyl iodide and ammonia me formed. Tbese results show that the two a-benziledioxime methyl ethers are not geometrical isomerides but are structurally different ; it.is sug- gested that wliilst the non-basic modification (a,) bas the formula RO.N:CPh.CPh:EOR the second (Q) contains the groups ZNOR and <XR ; the above experiment with hydriodic acid tells however. - somewhat against this view. Benzile is formed by the action of amyl nitrite a t ordinary temperatures on a- or ybenzileoxime ; a-benziledioxime is converted to a considerable extent into the p - e x i m e ; the latter by similar treatment yields crystals of an oxidation product which melt at 1 1 4 O and give phenyl cyanste on distillation. J. B. T. By R. DE NEUFVILLF and H. F. PECHMAXN (Ber. 23 33i5-3387) .-Tlibenzoylmethane is dissdved in chloro- form and treaitd with bromine in molecular proportion mixed with 3 parts of chloroform; during the addition of the bromine a.stream of dry air is drawn through the liquid in order to remove hydrogen bromide ; the residue obtained after evaporation of the chloroform consists of dibenzo?jEbromometha?se CBBrBz ; it crystal- lises from chlcrofom on the addition of light petroleum in lustrous needlts melts at 93" and gives no coloration with ferric chloride. Dilmroylcarbinyl acetate CHBz2*OAc is prepared by the action of rtnbydrous potassium acetate on the bromide ; it crptalliscs from dilute alcohol in needles melts at 94" is insoluble in water 01' light petrolenm and gives a brown coloration with ferric chlopide ; the yield is 80 per cent. Dibenzoylbromocal-binyi acetate CBz,Br*OAc is obtained by the action of bromine on the pet-ious compound ; it is readily soluble in the ordinary media and is deposited from chloro- form on the addition of light petroleum in white crystals which melt a t 101-102" ; by beating the compound either alone or in solution acetic bromide is eliminated and the triketone is formed.Dibenro?lldibromonzetliane CBr2Bz2 is prepared by the action of dibenzoylmethane on twice the molecular proportion of bromine ; it crystallises from alcohol and melts at 95". The compound is com- pletely decomposed by the action of alkalis whilst small quantities of triketone are formed on boiling an alcoholic solution with fiilrer oxide carbonate or nil rate ; an acetic acid solution of potassiuni acetate causes a similar reaction. Nitrosodibe~~zo2~lmethane CBz,:N*OH is formed by treating dibenzoylmethane with amyl nit<rite ; it crystal- Diphenyltriketone.ORGANIC CHEMISTRY.319 lises from a mixture of chloroform and light petroleum melts at 146' and is soluble in alkalis with a yellow colour. Diphenyltriketone or dibenzoy 1 ketone CO ( CO*CsH5) is prepared by heating dibenzoylcarbinyl acetate or by the action of nitrous acid on nitrosodibenzoylmethane ; it crystallises from anhydrous light petro- leum in golden-yellow needles melts at 69-70" and boils Lct 247-248" under a pressure of 60 mm. and a t 289" under a pressure of 175 mm. ; is very hygroscopic and readily dissolves in all solvents except water. '' Diphenyltriketone hydrate," dibewomethylene glycol CBZ,(OH)~ is formed as a white flocculent precipitate on dissolving the ketone in alcohol or glacial acetic acid and adding water ; it melts at go" and is also formed by boiling dibenzoylbromocarbinyl acetate with glacial acetic acid or by the action of potassium acetate on dibenzoyldibrumo- methane.Chemically the hydrate resembles the ketone ; both give a brilliant blue coloration on the addition of sulphuric acid to a benzene solution. The hydrate readily dissolves in alkalis with the formation of phenylbenzoylhydroxyacetic acid OH*CPhBz*COOH which has not yet been isolated. After the solution has remained for some time this compound is decomposed by the further action of the alkali; part yields benzoic acid and phenylhydroxyacetic acid wliilst carbonic anhydride and benzoin are produced from the remainder. On treating the triketone with phenylhydraziue in molecular' pro- portion at ordinary temperatures a compound is deposited which crystallises from a mixture of chloroform and light petroleum i n aggregates of almost colourless needles melts at 1:35" and acquires a red colour after remaining in contact with tbe air.The snb- stance bas the formula C,,HI6N,O2 but i t is uncertain whether it is really a phenylhjdrazone ; it dissolves in concentrated sulphuric acid with a yellow coloui* but the solution is not affected by ferric chloride or potassium dichromate (Bulow's reaction). By the actiofi of excess of phenylhydmzine on the triketone or on tbe previous compound two substances are obtained and may be separated by treatment with benzene a t ordinary temperatures ; the one crystallises in yellow needles melts at 223" and has not yet been further investi- eated.The second comDound is soluble in benzene. and consists u I CPh >C*N,*Ph ; it crystallises from NPhGPh of benzenazotriphen y lpyrazole ~ alcohol in orange-red prisms and melts at 156-157*. Diphenyltri3cetunanilide NPh:CPh.CBz(OH) is formed by treating the triketone with two parts of aniline a t the ordinary temperature ; it crystallises from benzene on the addition of light petroleum in yellow concentric needles melts at 99-100" and gives rz blue colora- tion with siilphuric acid and benzene. On boiling the triketone with alcoholic solution of aniline the dianilide C(OH),(CPh:NPh) is ob- tained crystdlising from beczene in yellow pyramids which melt at 148". Diphenyltrinitrosoprupar~e OH-N:C(CPh:N*OH j is obtained as a white crystalline powder from nitrosodibezlzylmethane and hydroxyl- amine; i t is insoluble in water but readily dissolves in alkalis and organic menstrua and melts at 185-186".A second compound is320 ABSTRAOTS OF OHEMICAL PAPERS. formed i n small quantitF ; this crystallises in plates melts at 141" is insoluble in alkalis and has not yet been further investigat,ed. Attempts to prepare other triketones from acetophenone benzoyl- acetone acetylacetone and ethyl acetoacetate have been nnsuccesstul. Cresolcinnamic and Metacresolglycollic Acids. By A. OGLIALORO and 0. FORTE (Gazzettn 20 505 -513).-The cresol- cinnamic acids were prepared by heating the corresponding sodium cresolglycollates with benzaldehyde and acetic anbydride. Orthocresolcinnamic acid is obtained piire by decomposing its barium salt.It crystallises from a dilute alcoholic solution in small white prisms melts at 167-168" and is very soluble in-warm alcoliol moderately in ether chloroform and benzene. The barium salt (C16H1303)2Ba f H,O dissolves very sparingly in hot water and may be obtained crystallised by evaporating the soiution. The silver salt C16H,303Ag decomposes at4 100". The methyl salt Cl6HI3O3Me crys- tallisev from dilute alcohol i n colourless plates melts at tjl" and dissolves T-ery freely i n alcohol and ether and moderately in light pet<roleum and chloroform but is insolnble in water; a brominated derivative Cl7H1,Br6o3 may be obtained by adding bromine to satura- tion to the methyl alcoholic solution of this compound and heating the dixtnre for a few hours.It crystallises in brilliant yellow scales and melts a.t 231". ~~etucresolgZycrJllic acid C9Hl0O9 is prepared by melting a mixture of metacresol and chloracetic acid in molecular proportion and adding a quantity of aqueous soda (sp. gig. = 1.3) quadruple that of the cresol taken. It crystallises from boiling water i n minute white needles and melts at 102". The barium salt (C9H903),Ba + 6H20 crystallises from an aqueous solution in nodules consisting of very fine white needles. Metacresolcimamic acid crystallises in white needles melts at 155" and dissolves freely in alcohol and ether. The silcer salt is white and anhydrous and is not altered by exposure to light. The bai-ium and the methyl salts are uncrystallisable compounds the latter is a viscid substance yielding a brominated derivative C17Hl,Br20J which crystallises in colourless rhoinbic tables and melts at 109".Paracresolckw.m?nic acid crystallises in white needles melts at 159-160" and dissolves in alcohol ether and benzene. The acid cannot be completely purified but a silrer salt of the theoretical com- position may be isolated. 'I'he bn~iurn mrignesiurn and methyl salts are uncrgstallisable ; the last is a viscid product and yields a brumin- a:ed derivative C,,Hl6Br,O3 which crystallises from methyl alcohol in brilliant colourless rhombic tables melting a t 124-1%5". J. B. rr. S. B. A. A. Sulphides of &Naphthol. By S. OKUFROWICZ (Bey. 23 3355-3373) .-/j-Naphthol sulphide or ,3-11yc?roxpaplithyl sulphide s(C,,H6*OH) is prepared by the action of either sulphur dichloride or of sulphur and lead oxide on &naphthol.The a-sodium derivative S(CloH6*ONa) + GH.,O is obtained by dissolving the sulphide in sods ; it crystnllises in coloiirless con- centric needles is readily soluble in water o r alcohol and has anORGANIC OEEM18TRP. 32 1 a1 kaline reaction. The comesponding calcium and b a ~ i u m salts are ( olourless and crystalline and like the salts of the heavy metals are very sparingly soluble in water. The diethyl derivative S( CioHs*OEt) is prepared by the action of the calculated quantity of ethyl iodide and potash on the sulphide; it crystallises from benzene in long slender wax-like lustrous needles melts at l89" and is not acted on by silver nitrate or mercaric oxide. 0-Napbthylamine and /+naphthol are formed by the action of ammonia on B-naphthol sulphide whilst /?-naphthol is the sole product when the sulphide is treated with cuprous chloride or silver chloride.By the action of silver nitrate or of mercuric oxide on the sulphide a compound is obtained which crystallises from dilute alcohol in stellate groups of ruby-red plates and melts at 164" ; the yield is 25-30 per Tent. of the sulphide employed. This substance has the formula C20Hl&302 and is not acted on when boiled with either soda or glacial acetic acid ; when heated to goo' it yields hydrogen sulphide and /?-naphthol whilst by reduction with zinc-dust and glacial acetic acid ,d-naphthol sulphide is regenerated. By the actiori of potassium dichrornate and sulphuric acid part of the sulphide is completely oxidised.and part remains unchanged ; with dilute nitric acid sp. gr. 1.18 phthalic acid is the sole product. @-Naphthol sulphide is decomposed by concentrated nitric acid ; but on dissolving the clielhyl derivative in 10 parts of glacial acetic acid adding 5 parts of fnming aitric acid arid cooliiig well with ice dinityo- nqhthyl ethyl ether CloH,(NO,),-OEt [OEt (NO2)* = 2 1' 4 1 is obtained and may be piiritied by treatment with benzene ; it crystal- lises from dilute alcohol in long slender pale-yellow silky needles melts at 215" and is not acted on by aqueous soda. The yield is SO per cent. When heated with dilute nitric acid at 160-170" dinitro- naphtbalenedicarboxylic acid [(COOH) (NO,) = 1 2 3 61 is produced. Dinitramidoiaaphthtcle?ze [NH (NO,) = 2 1' 4'1 is formed by heating the above ethyl derivntire with concentrated alcoholic am- monia at 22G-225" ; it is very sparingly soluble and crystallises from toluene in slender yellow needles ivhich blacken at about 250° but do not melt.When /3.ethoupaphthyl sulphide is trented with coucen- trnted nitric acid at very lo^ temperatures t,he pi-ocluct after washing with ice waler dissolved in benzene and the solurion cooled ethoxy- dinitrotiapht7qZ sulphide S[ C,,H,(NO,).OEt] is deposited in slender golden-yellow needles which melt at 235". After some time a further deposit is obtained from the mother liquor; this is dissolved in ether and crystallises on the addition of light peixoleuni in slender pale- yellow needles ; it melts at 202" and is readily soluble in alcohol or benz- ene both at ordiriary temperatures and on warming.This substance has the formula C24H,oN,S,06 and is probably a clinitro-derivative. @-Naphthol bisulpllide or B-hydyozyn@&l bisulphide is obtained by heating /?-naphthol with sulphur at 175-180' for 24 hours; after purification it crystallises from benzene in slender yellow needles melts at 169" and is very sparinglj soluble it1 ordinary menstrua. When322 ABSTRACTS OF OHEMIGAL PAPERS. heated to 360"; it decomposes into hydrogen sulphide and &naphthol ; it is soluble in dilute and gives a red colour with concentrated alkalis. The yield is 10 per cent. The same compound together with a con- siderable quantity of the monosulphide is also formed by the action of sulphur chloride a t 0" on p-naphthol dissolved in benzene; the yield is about the same as before.The best results are obtained by heating a .solution of the sulphide with half the molecular proportion of sulphur bromide for an hour on the water-bath; in this manner 20 grams of P-naphthol yielded 5 grams of pure bisulphide. /3-Ethoxy- naphthyl bisulphide S2( C,oH,*OEt) is prepared in a similar mannei. to the corresponding monosulphide derivative ; it crystnllises from alcohol in greyish needles and melts at 158.5'. The diacetate S,(CloHn*OAc)s forms ft yellow hard crystalline mass which melts at about 140" and is soluble in ether alcohol benzene and glacial acetic acid. The dibenzoate S2(CIOH6*OBz)2 crystallises from benzene i i i greenish plates 01' prisms and melts at 187".On heating the bisulpbide with recently reduced copper at 230-240" it yields /3-dinaphthol m. p. 212" ; the bisulphide is not alhered by boiling with copper and xylene or cumene. a-Naphthol trisukhicle SJ(CIOHB.OH)? is obtained by the action of sulphur chloride on a-naphthol and is a pale yellow amorphous sub- stance which blackens at 220". and is very Tettdily soluble in dilute aqueous soda but almost insoluble in organic media. The corre- sponding benzoate S3(C10H6-OB~)2 is a greyish powder melting a t 194". When benzene is mixed with 0.5 part of sulphur chloride and 0.05 part of iodine heated in a sealed tube for 100 hours at 115-125" and the product boiled with benzene toluene carbon bisulpbide and xylene succeesively a yellow hard amorphous mass remains which is slightly soluble in xylene and has the formula SsPhz.J. B. T. Ethereal Oil of Asafcletida. By F. W. SEJ~MLER (Bey. 23 3530-3533).-Up to the present it has not been found possible to separate crude asafoetida into its constituents by fractional distillation but the author finds that this may be readily carried out under diminished pressure. Thus under 9 mm. t w o specimens of crude oil of sp. gr. 0.9843 at 22" and 0.9789 at 12" respectively gave on repeated fractionation four chief fractions distilling below 65" at The fraction distilling below 65" obtained from both specimens had the same qualitative composition but the constituents were pre- sent in different quantities thus causing a difference in the speciSc graviky. On treatment with potassium in a vacuum until no more gas is evolved and then distilling a colou rless pleasant-smelling oil is obtained which has the composition CloH ; it is a mixture of two different terpenes one of which yields it liquid and the other a solid dibromide. It is contained ready formed in the oil and may also be obtained from the fraction distilling below 65" by adding mercuric chloride unt,il no further precipitate is formed and distilling in a current of steam.The first sample of oil mas thus found to contain 6 per cent. and the second 8 per cent. of the mixture of terpenes. 80-85" 120-130" 133-145".323 ORQANlC OHEMISTRY. The fraction 133-145" was treated with sodium i n a vacuum anci on distillation under 9 nim. pressure a colourless oil passed ovel- a t 123" which had n pleasant lavender-like odour a sp.gr. of 0.9241 at 15" and the composition C15H,. It belongs therefore to the group of sesqniterpenes and forms a hydrochloride C16Hu,2HC1. These two fractions consist chiefly of substances free from sulphur the compounds containing the latter being found in the second and third fractions which are at present being more closely investigated. Indian Geranium Oil Geranaldehyde and Geranic Acid. By F. W. SEMMLER (Bey. 23 3556-3557 ; see also Abstr. 1890 951).- In the previous paper it was shown that geraniol on treatment with chromic acid and distillation in a current of steam yields a11 aldehyde CloHlbO which may be termed yeranaldehyde. If the re- sidue after removal of the aldehyde is treated with phosphoric acid and again distilled in a current of steam a small quantity of an oil is obtained which has an acid reaction. It may be prepared much more readily by making an emulsion of 6 grams of geran- aldehyde in 500 grams of water gradually adding a solution of 13.5 grams of silver oxide in dilute ammonia acidifying with a slight excess of phosphoric acid and distilling in a currelit of steam.The distillate is neutralised with soda evaporated to drpess the residue extracted with boilirig absolute alcohol and the latter expelled from the filtrate. The residue is taken up with water and precipitated by means of silver nitratc as the siZver salt ; this has the composition C,,H,,O,Ag. Geranic acid is a thin oil. The alcohol and aldehyde also occur in other oils of which a more de- H.G. C. tailed account will he given later. (Compare also'foIlo~~-ing abstract.} H. G. C. German and Turkish Rose Oil. By T. POLECE and C. EC&T (Ber. 23 3554-3535 ; see also Markovnikoff this vol. p. 219).- The first product which passes over in the distillation of German rose oil is ethyl alcohol about 5 per cent. of which is present. Terpenes could not be identified. After removing stearoptene the German rose oil was distilled under diminished pressure when it passed over almost entirely a t 110-120" (14 mm.). Its boiling point a t atmo- spheric pressure was found to be 215". The Turkish oil behaves in n similar manner both eleoptenes being laevorotatory the German variety having a sp. gr. of 0.8837 at ll" and the Tuikish 0.8H13 at 12". The analyses of the liquid portions of both oils indicated the formula CloHlSO.This compound has the characteristics of a primary alcohol with two ethylene linkages both with regard to the molecular re- fraction and its behaviour to.wards bromine. Its sodium derivative chloride iodide arid benzoate have been analysed. On oxidation i t yields first an aldehyde C10H160 and then an acid Cl,EL,,O2. Phos- phoric anhydride and zinc chloride abstract the elements of water forming a mixture of two different terpenes C10H16 which differ con- siderably in their boiling point. If the action takes place below O" the higher boiling terpene is.strongly. dichroic. The otily products of further oxidation found were carbonic aiihydride formic acetic and oxalic acids.324 ABSTRACTS OF OHEMIOAL PAPERS.The properties of the liqnid constituent of both the German and Turkish oils correspond exactly with those of geraniol the chief constituent of Indian geratiium oil (Semmler Abstr. 1890 931 and preceding abstract) and a direct coiuparison of the aldehydes has shown their actual identity. The eleoptene of rose oil therefore also contains an open chain of carbon atoms which on elimination of water unite to form R closed chain. Phenolic Acid from Camphor. By P. CAZENEUVE (Compt. rend. 111 743-745) .-Monochlorcamphor is treated with six times its weight of concentrated sulphuric acid a t 50" for 30 hours and the product is poured into cold water. After some time the liquid is filtered heated saturated with barium carbonate and concentrated. Amethylcamphophenolsulphone (Abstr.1890 11.53) and the barium salt of the new acid crystallise together. They can be separated by crystallistihion f roll alcohol of 70° in which the barium salt remains dissolved and i t can afterwards be purified by crystal- lisntion fmm water. The barium salt crystallises in nacreous plates and when treated with sulphuric acid it yields smethylcamphophenolsulphonic acid 08*CsH120-S03H isomeric with thc sulphone a colourless syrupy uiicrystnllisable liquid with a bitter astringent acid taste and an odour recalling that of solutions of oak-bark. It is very soluble in water alcohol and ether has no action on polarised light and distils partially without decomposition under reduced pressure. Solutions of the barium salt gave a magnificent blue coloration with ferric chloride.If the salt is boiled with acetic anhydride for 15 minutes it yields an acetyl derivative OAc*C9H1?0*S03H the barium salt of which has no action on ferric chloride. When ti-eated with potassium hydroxide the original phenolic acid is formed. C. H. B. Action of Camphoric Anhydride on Benzene. By E. BURCKER ( f j u l l . SOC. Chirn. [ 3 ] 4 112-113).-Under conditions similar to those by which benzoylpropionic acid is formed camphoric an- hydride and benzerie react in presence of aluminium chloride to form a coinpound C1&IZ003 which is separated from its sodium salt by truatment with hydrochloric acid as very light scales; it is soluble iii alcohol chloroform ether and acetic acid but only sparingly in benzene and almost insoluble in water.It melts at 125-126" but if this temperature is passed it no longer solidifies on cooling but remains as a syrup and decomposes at a higher tem- perature without boiling. 'l'he compound behaves as a monobasic acid. Solutions of the alkaline hydroxides dissolve it and the salts formed by it with cobalt nickel copper and silver crgstallise easily. With phenylhydrazine i t yields a yellow crystalline derivative. Further work is being car?*ied on to determine its constitution. Crystalline Principle from the Bark of Diospyros virginiana. Bj- W. SCELEIF ( J . Yhamz. [S] 22 469-471 ; from Amer. J. Yharm. 1890 390).-Thc powdered root is extracted with light petroleum by which a Tellow solution is obtained yielding a waxy residue on evaporation. The powder is then treated with ether and the solution H.G. C . T. G. N.ORUANIC CHENISTRY. 325 distilled when a deep-red crystalline residue is left; this is dissolved in hot alcohol and treated with an alcoholic solution of lead acetate which removes the colouring matter only. After fiitration the liqnid is treated with hydrogen sulphide again filtered and the still reddish alcoholic solution is digested with animal charcod on the water-bath nnd concentrated by distilling off the alcohol ; the crystals which separate are purified by repented recrystallisation from alcohol unti I the dry product has a yellowish-grey colour. The crystalline mass t h u s obtained sometimes contains crystals 0.2 mm. long; these are soft and waxy in appearance when moist. The dry substance is light brown in colour and granular in texture with a peculiar odour and a slightly astringent taste.I t is soluble in alcohol ether and chloroform very little soluble in waler and not at a11 in light petroleum. At 2.58" it takes a deeper tint and at 262" it melts with appaient decomposition. The compound has a neutral reaction ; it does not dissolve on boiling with dilute hydrochloric acili o r in dilute potash solution ; it burns on platinum foil without leaving any re- sidue. Its alcoholic solution is not precipitated by alcoholic solution of lead acetate or of ammonia. It diesolGes in glacial acetic acid. Its composition corresponds with the formula C3rcHeiOlo. By A. LADEXBURG (Ber. 23 3555-3556) .-In reply to Stoehr's criticisms of the tiuthor's previous paper on this subject (Abstr.1890 1432) Ladenburg states that the facts from which his conclusions were drawn were obtained in personal communications from Stoehr and that as there stated the trnt,h of those statements is now being experimentally investigated. By E. NOELTING and E. TRAUTMANK (Eel.. 23 3654-3683).-Quinoliiie is dissolved in 10 parts of siilphuric acid (100 per cent.) and treated with the theorelical quantity of fnmiug nitric acid also dissolred in sul ph uric acid ; enough fuming sulphuric acid containing 20-25 per cent. of sulphuric anhydride is added to combine with the water con- tained in the nitric acid and also with that formed during the reaction ; the mixture is either gently heated or allowed to remain for several days at ordinary temperatures ; in this manner only the t w o mononitro-d eriva tives are formed.NitroparatoZuquinoZine CSNH5Me-NO2 [Me NOa = 3 41 is pre- pared by the action of nitric acid on paratoluquinoline in presence of snlphuric acid ; it crystallises from aIcGho1 in pale-yellow needles melts at lJ6-117" and is readily soluble in organic menstrun. The salts are crystalline but readily undergo dissociation in presence of water. The proof of the above formula consists in the fact that the corresponding amido-derivative does not yield methylphenmthroline by the action of glycerol and picric acid. The rnethiodide crystnl- lises from alcohol in long yellow needles ; on allowing these to remain in contact witoh the mother liquor rhombohedra are formed ; froni water the compound is deposited in colour1e.s rhombohedra which become yellow at 100" ; both forms melt at 189-190" AmidoprLratoiuquinoline is prepared by the reduction of the above nitro-derivative with iron and acetic acid ; it crystdliscs from water J.T. p-Picoline. H. G. C. Derivatives of Toluquinoline and Metaxyloquinoline.326 ABSTRAOTS OF OHEMIOAL PAPERS. or dilute alcohol in yellow needles and melts at 145"; the yield is 90 per cent. of theory. The hydrogen salts are red whilst the iiormal salts are almost colourless but are red i n aqueous solution. The acetyl derivdive crystallises from water in whit.0 needles melts at 160° and yields colourless salts with acids. Hyc@zyparatoZuquinoline CSNH,Me*OH is prepared by the action OE sodium nitrite on the amido-compound ; it crystallises from alcohol in flat needles melts at 230° sublimes without decomposition and is not volatile with steam.The samc compound is also obtained by the action of fuming sulphuric acid at 90" on paratolnquinoline; the resiilting sulphonic acid being then fused with potash. It fcrms well- characterised salts with acids and alkalis and yields a hydroxyazo- derivative with diazobenzene chloride which is deposited from alcohol i n small red needles melting at 176". ~T~troso-ltydroxyparatoluquinoline 01' o~!/pai'utoEuquinoliiae oxime C9NH4Me(NOH)0 is obtained by the action of nitrous acid on the hydroxy-derivative at low temperatures ; it crystallises from water in yellow needles and from alcohol in yellow plates which deeom- pose above 200' without melting. The hydrochloride is sparingly soluble in hydrochloric acid and crystallises in yellow needles ; the sodium salt is deposited in small yellow plates.The nitroso-corn- pound yields a stable green dye with iron inordanted cloth this property is probably due to the presence of a salt-forming group in the peri-position [4 1'1 to nitrogen ; thus whilst the three ortho- hydroxytoluquinolines (see below) and orthoquinone osimes give dyes with mordants paraquinone oximes only do so if they contain the NOH group in the position 1. O1.th o ? z i t r ~ 1 l l yd7.oa.ypwc1tol I1 q ? h 01 L'?LC N0,*C9NH,Me*OH [NO OH Me = 1 3 41 is prepared by the oxidation of the oxirne with potassium ferricyanide and crystallises from dilute acetic acid or alcohol in yellowish-brown plates which decompose while melting.Ortholi~jdrox~~nzetntoluqzlilzolilze C,NH,Me*OH [OH Me = 1 21 is prepared from amidorthocresol [OH NH Me = 1 2 61 glycerol and picric acid ; i t cr.ystallises from dilute alcohol in long needles melts at 73-74' is volatile with steam and in contact with copper oxide colours the flame peen ; the yield is SO pel* cent. ATittmso-orthoxy~netatoZuquinoZhe C9NH,Me(NOH)0 [0 Me NOH = 1 2 41 is prepared by the action of sodium nitrite ou the pre- ceding compound and it is deposited from alcohol or dilute acetic acid in yellow needles ; it decomposes at about 200" without melting and ltas no tinctorial properties. Soluble salts are formed with acids and bases. ~-~trorthoh~drozymeta~oluquinoline is obtained from the preceding componnd by oxidation with potassium ferricyanide in alkaline solution ; it crgstallises from alcohol in red needles and from benzene in yellow needles melts at 192-1193" yields salts with acids and bases and dyes mordanted cloth.Orth(,hydro~~7YLethylqzcinoline CsNH,Me*OH [OH Me = 1 41 is prepared from amidoparacresol [OH NH Me = 1 2 41 ; i t crystttllises from dilute alcohol iu long colourless needles melts atORGANIC CHEMISTRY. 327 132-124O and gives a yellow dye with aluminium mordants; the yield is 65 per cent. of theory. Nitroso-orthoxymethylquinoline CgNH4MeO:NOH [0 NOH Me = 1 3 41 resembles the pre- viously described isomerides and dyes mordanted cloth ; on oxida- tion it yields the corresponding nitro-derivative which crystallises from alcohol in slender yellow needles melting at 205-206" ; yellow colonrs are obtained with aluminium mordants.NitropnratoZuquinoZi?ie C9NHJMe*NO2 [Me NO2 = 3 41 is ob- tained from nitroparatoluidine it crgstallises from alcohol and melts at 116-117" ; the yield is 65 per cent. The corresponding mnido- acetyl and hydroxy-derivatives have been prepared and closely resemble the previously described iso- ruerides. Orthonitroparatoluquinoline CgNH5Me*N02 [NO Me = 1. 31 is prepared from nitroparatoluidine [NH NO Me = 1 2 41 and crystallises from water in pale-yellow needles melts at 122" and does not combine with methyl iodide ; the yield is 60 per cent. The salts crystallise readily but dissociate with water. Orthamido- paratoluquinoliiLe is prepared from the preceding compound by reduc- tion with ammoniuin sulphide ; it crystallises in slender needles melts at 62-64" sublimes without decomposition and is volatile with steam.The hydrochloride forms orange needles. The cccetyl derivative is obtained from water or dilute alcohol in large plates melting at 91-92". It yields salts which readily crystallise. The hydroxy-derirative is prepared by means of the diazo-reaction and is identical with the compound obtained from toluquinolinesulphonic acid [SOsH Me = 1 31 bv fusion with potash. The nitroso- compound CSNH,Me(NOH)O [0 Me NOH = 1 3 41 is very sparingly soluble and crystallises in brown plates which decompose itt 200" and do not dye. The nitro-derivative could not be obtained. Orthnmidochlorn~aratoluquinoline C9NH4MeC1*NH2 [NH Me C1= 1 3 41 is formed together with amidotoluquinoline by the reduc- tion of tbe nitro-compound with tin and hydrochloric wid ; i t c r p tallises from alcohol in silky lustrous needles melts at 129-130° and does not combine with diazo-compounds.The monacid salts are orange-yellow and readily undergo dissociation. The hydrochloride is sparingly soluble. The acefy 1 dei-ivative is deposited from dilute alcohol in lustrous needles melting at 136-137". Nitr.orthotoZzLquiizoZine. CgNH7Me*N02 [Me NO = 1 21 is pre- pared by the nitration of orthotoluquinoline. and crystallises in pale- yellow needles melting at 93". It is volatile with steam does not combine with methyl iodide and on heating with alcoholic potash gives a violet colour changing to red and finally to dirty brown on exposure to air.The yield is almost theoretical. The same com- pound is synthetically prepared from nitrotoluidine [NH2 Me NO2 = 1 2 .j]. The salts readily undergo dissociation. 4,~nido~thotoZuq~~inoEine is obtained by reduction of the preceding compound with iron and acetic iicid,and crgstallises from water or dilute alcohol in long yellow needles melting a t 143". The hydrochloride is Ted the dihytlrochloride yellow. Methy~hena~~tl~roline CyNH4Me<CH:bH [Me CH N = 1 3 4J [NH2 NO2 Me = 1 3 41 ; N=CH328 ABSTRACTS OF CHEMICAL PAPERS is obtained by the action of glycerol and sulphuric acid on the amine ant1 is deposited from light petroleum in sninll crystals melting at 95-96". It is identical with the compouud obtained by synthesis from mctatoluylenediamine.AcetaiIiidorthofolirqu.i?z(ilL'ne ci-ystallises from water in silky lustrous needles and melts at 187". HSdroxFarthotoluquinoline from the amide crystallises fkom dilute alcohol in colourless needles and melts a t 262-263' on rapidly heating. A compound identical with this has previoixly been prepared from orthotol uiclinesulphonic acid [SO,H NH? Me = 1 3 43. With diazobenzene chlorkle a h yd.l.ozyaso-clerivative is fortned crystallising from alcohol in red needles melting at 1.?8-139" and soluble ill aqueous alkalis. The witroso-compoond C,NH,Me(NOH)O [Me NOH 0 = 1 3 41 crystallises from alcohol in yellowish-brown plates decomposes above 200" without melting and gives " lakes .' with the heavy metals. The nitro-derivative is formed on oxidation and is deposited in orange needles which melt at 181-1$2" :iiicl do not dye.i-lzo~thotoZuquitroli~ze. N,(C8NH5M~:)f? [Me N = 1 41 is formed together with amidotolu qu inolin e by the recluc t ion of ni tror tho tolu - quinoline with iron and liydrochloric acid ; it c~ystallises from glacial acetic acid in orange needles and melts a t 260". The hydrochloride is readily obtained in red crystals. On reduction with stannous chloride or alcoliolic ammoniiim sulphide n compound is formed which is insoluble in water yie!ds red salts aiid has not yet been further investigated. Azoxyorthotoiz~qui~zol;lze ON,( C9NH,Me) is formed together with the azo-derivative and niay be separated by crystallisation from hydrochloric acid in which it is tolerably soluble; it may be pre- pared directly by the incomplete reduction of nitrotoluquinoline. and crystallises from alcohol in slender yellow needles melting at 201".The hydrochZoride is deposited in very slender lemon-yellow needles ; all the salts are readily dissociated. When heated with 10 parts of sulphuric acid at 110-113" a compound is formed which is probably lLydroxyazotoZuquinoZi~e ~:II~HjnIle.K,.C9NHjnile.0H [Me 0 H N = 1 3 41 ; i t is insoluble in alkalis as is also the corresponding corn- pound [Me N = 1 4 ; Me N OH = 1 3 41 from amidotolu- quinoline and hydroxytoluqiiinoline. Nitrometaxyloq~~i~Loline CgNH,Me2*NOJ [Me LMe NO = 1 3 41 is obtained by nitratiug metaxyloquinoline ; it crystallises from alcohol in long yellow needles melts a t 107-108" is scarcely volatile with steam and does not combine with methyl iodide.The salts are decomposed by water. The constitution of the compound is shown by its synthesis from nitroxylidine "El Me Me NO = 1 2 4 51 ; it gives no coloration with alcoholic potash. Bniido- metaxyloguiszo Zine is formed by the reduction of the preceding compound with iron and acetic acid or stannous chloride and hydrochloric acid ; it crystallises from diiute alcohol in long yellow needles and melts at 91". The acetyl derirative is deposited from water in colourless needles which melt at 201". Hydro,rymetnxyZoqiiinoZine from the amido-compound and nitrous acid crystallises from chloroform in white plates and melts at 197-198". On snblirnation it is obtained The picrate melts at 252-253".'OR3ANICl OHEMISTRY. 329 in small needles and salts are formed with acids and hases. hydrochloride crystaliises in yellow needles. The J. B. T. 2-Methylquinaldine. By E. RIST (Ber. 23 3483-3487) .-The author has already shown (Abstr. 1890 1324) that the so-called metamethylquinaldiae obtained by Diibner and v. Miller from par- aldehyde and metatoluidine(Abstr. 1884,183) and which mighi there- fore have either the meta- 9r ana-constitution is converted by oxida- tion into the quinaldinecarboxylic acid prepared by DBbner and v. Miller from metamidobenzoic acid and aldehyde. The hydrochloride of the latter acid forms small characteristic tablets sparingly soluble in cold readily in hot water whilst the platinochloride 4(C,,H,N02,HCl),PtC14 crystal lises in reddish-yellow monosymmetric prisms readily soluble in water.Its silver salt CIIH8NO2Ag crystal- lises from hot water in microscopic crystals soluble in ammonia and nitric acid. To ascertain whether these compounds are really 2-derivatives the author subjected Gerdeissen's 2-amidoquinddine (Abstr. 1889 520) to Sandrneyer'~ reaction. The ordinary procedure cannot be adopted in this case as the compound appears to form a stable nitrite. The mixture must be diazotised below 0") allowed to yemain and then added to the freshly prepared cuprous cyanide on the water-bath in small quantities and with vigorous shaking. As soon as gas ceases to come off the hot liquid is filtered saturated with soda and the precipitate recrystalljsed from water. The nitrile thus obtained forms silky needles melting a t 82" and crystallises with approxi- mately 2 ifiols.H,O wliich are given off on drying over shlphuric acid the melting point then becoming 104". It is volatile in a current of steam soluble in the ordinary solvents and in acids and may be distinguished from the otherwise hirnilar 2-amidoyainoline by the fact that i t yields ft colourless or pale-yellow solution with alkalis. On hydroljsis it is converted into a quinaldinecarboxylic acid which is identical w i t h the acid already described. It follows therefore tbat both this acid and the methylquinddine from which it was prepared have in reality the met%- and not the ana-constitution. H. G. C. Constitution of p-Quinaldinesulphonic Acid. By B. R!CHARD (Ber. 23 348$-3490).-Uy the adion of sulphuric acid on quin- aldine Dobner and v.Miller obtained a mixture of three sulphonic acids two of which were shown to be ortho- and para-quinnldine- sulphonic acids whilst the constitution of the third known as the @-acid was not ascertained (Abstr. 1884 183). In order to deter- mine its constitution the author converted it by the usual reactions into the corresponding nitrile and carhoxylic ncid both of which were found to be identical with the 2qanoquinaldine and quinaldine-2- carboxylic acid described by Rist. (see preceding abstract). 'l'he acid from which they are prepared must therefore be quinaldine-2- sulphonic acid. H. G. C. Condensation of Metanitrobensaldehyde with Quinaldine. By w. WARTANIAN (Bey. 23 3644-3653).-Metanitrobenzaldehyde VOL.ZX. z330 ABSTRAOTS OF CHEMIOAL PAPERS. is heated for 3-4 hours on the water-bath with rather more than 1 part of qninaldine. zinc chloride being added from time to time in small portions ; after pnritication and crystallisation from alcohol a product is obtained which melts a t 124-126" and consists of a mixture of metanitrobenzy 1 idenequinnldin e CgNH6*CH:CH*C6H4*Xo2 [CH = 2'; CH NO = 1 33 and of the aldol compound CgNH6*CET2*CH( OH)*C6H4*N02 ; the former substance may be separated by treatment with acetic anhydride at 13.5" ; it is deposited from a mixture of benzene and light petroleum in yellow nodular crptalline aggregates and melts at 139". The hydrochloride forms long,rectangulnr crystals ; the ititrate crystallices in pale-yellow lustrous needles ; tbe picrate is deposited in lemon-yellow interlaced needles the yhatinochloride ( C,7H,2N202)2,H2PtC16 + 1$H20 is crystalline. When reduced with stannous chloride and hydrochloric acid motnmido benziy liden equinaldine C,NH6*C H CH*C6H4*NH2 is produced crystallising from a mixture of benzene and light.petroleum in orange-red plates; i t melts at 158-159" and is insoluble in water but readily dissolves in organic media and is deposited from alcohol in pale-yell( )w needles. On heating the timido-compound with plycerol sulphuric acid. and orthonitrophenol eth~leiiediquirrolin~ C,NH6*CH:CH*CsNH [CH CH = 2' 21. is formed. but could not be obtained in crvstals; it i s readily soluble in alcohol benzene and chloroform. The salts and platinochlorida are amorphous.The meth- iodide rrvstallises from methyl alcohol in golden-yellow needles melts at 225-226" and is insoluble in benzene but readily dissolves in hot waher. No dimethyl iodide could be prepared. A homo-additive compound is formed by +he action of bromine on the methiodide in chloroform solution and is deposited from methyl alcohol in slender crystals which commence to decompose at 18G-290° and melt at 210". Eth~/leneq~cinolineq~rinaldine C9NH6*CH:CH*CgNH;Me [ CH = 2' ; CH:Me = 2 2'1 is prepared by the action of paraldehyde on amidobenzylidenequinaldine and forms R yellow plastic mas8 readily soluble in alcohol benzene or ether. The nitrite crystallises from water in stellate groups of reddish-yellow needles which commence to decompose a t 125* and melt at 135-136".The hydrochloride nitrate. slilplmte picrute and platinochloride are all amorpboiis and readily soluble. J. l3. T. 6-Pyrazoledicarboxylic Acids. By MAQUENNE ( Gompt. rend. 111 740-743).-Dinitrotartaric acid not only acts on form- aldehyde and acetaldehyde in presence of ammonia hut the reaction is general and the Ruthor has prepared in this way a number of ~-pyrazoledicarhoxylic acids from the corresponding aldehydes. They are all only slightly ~oluble even in boiling water and are almost insoluble in alcohol but dissolve very readily in alkaline solutions and yield mono-metallic salts which are neutral and crystallisa~ble. Methyl- et h-yl- and isopropy1-~lyoxalinedicarboxylic acids crystallise with 1 mol. H20 in brilliant acicnlar prisms ; the others form crystal-ORQANIC CHEMISTRY.331 line anhydrous powders. Is~butylglyoxalinedicarboxglic acid and its alkaline salts have a sweet taste but this property is wanting in the neighbouring homologues. All the glyoxalinedicrtrboxylic acids decompose at about 300° and yield carbonic anhydride and glyoxalines or p-pyrazoles the decom- position being almost quantitative. This constitutes the best method for the preparation of glyoxalines. Many glyoxalines were prepared in this way and the hexyl-glyoxaline was found to melt at 45-46" and not at 84" as stated by Rsdziszewski. 2-Phenyl-p-pyrazole is solid very slightly soluble in water or in warm benzene (from which it crystallises in lamella) but easily soluhle in alcohol. It melts at 148". and boils at about 340" (uncorr.) which distingnishes i t fi-orn the isomeric 1-phenyl-a-pgrazole descrihed by Knorr which melts at ll" and boils at 246.5".The normal oxalate crystallises from aqueous solutions in anhydrous needles ; the platinochloride is anhydrous and forms orange micro- scopic crystals almost insoluble in cold water. acid. -F u rf urald eh y de does not act on dinitrotrtrtaric acid in the same way as other aldehydes. When the aldehyde and acid in molecular propor.tion react in predence of excess of ammonia a crystalline precipitate f rms and cm be purified by solution i n ammonia and reprecipitatior~ with hydrochloric acid. It resembles the glyoxalinedicarboxylic acids in appearance but has not their general properties and yields no gly- oxaline when distilled.The ammonium salt has the composition C14HI,N208(NH4)2 + 2H20. The acid has the composition CI4HI2N2O8 is formed by the union of 2 moleciileu of furfurddebyde with 1 mole- cule of tartaric acid and probably has the constitution Dif u rju rnmidodih y d rox y turtaric COOH.7 (OH)*N:CH*CjH,O CO 0H.C ( 0 K) *N:C H*CaH30 C. H. B. Caffei'dine. By E. SCHMIDT and M . WERNECKE (Arch. Pham. 228 516-543) .-Caffeidine sulphate was prepared by boiling caffeine with barium hydroxide (Strecker's method) for half an hour only ; white needle-shaped crystals were finally obtained which are easily soluble in water much less soluble in alcohol. By treating the sulphate with barinrii liydi*oxide a little water and chloroform the free base is obtained as a solid crystalline mass with a neutral reaction ; it melts a t about 99".The free base readily decomposes with the formation of ammonia methylamine and cholestrophane. Cufe.i;dine hydriodide obtained by neuhalising the free base with dilute hydriodic acid forms white tabular anhydrous needles easily soluble in hot water somewhat less soluble in hot alcohol insoluble in chloroform &,f&dine hydrochloride obtained by treating the hydriodide in aqueous solution with silver chloride forms long thin somewhat hygroscopic needles. Cnfei'dine nitrate prepared by precipitating the hydriodide solution with silver nitrate forms large white strongly hygroscopic needles. Caffei'dine sulphate when treated with nitric acid yields chlolestrophane ammonia methylamine and carbonic anhydride ; but no ammonia is formed if the mixture is heated for a long time.2 2332 ABSTRAOTS OF CHEXIOAL PAPERS. @xidat,ion of the sulphate with potassium dichroinate and sulphnric acid yields the same products and not diethyloxamide as found by Mnly and Andreasch excepting when the mixture is heated for some time. Oxidation with bromine gives the same compounds as does also treatment with potassium chlorate and hydrochloric acid. Fuming hydrochloric acid corupletely decomposes caffeidine sulphate at 1.50" with the formation of carbonic anhydride formic acid ammonia methylamine and snrcosine (compare Abstr. 1883 69). Derivatives af Morphine. By W. DANCKWORTT (Arch. Pharni. 228 372-595).-Morphine. when heated with excess of acetic chloride yields diacetylmorphine (the tetracetylmorphine of Wright).This compound when boiled w-ith water loses only one acetyl group and a-monoacetylmorphine is formed ; by the addition of hydro- chloric acid this can easily be obtained as the sparingly soluble hydrochloride. The ,kl-morroacetyl (p-diacetyl of Wright) compound was prepared byBecket and Kright's method (this Journ. 1874,1033) but their ycompound was not obtained. The stability of morphine was not found to be increawd by the entrance of the acetyl group as shown by tho reaction of diacetylrnorphine with dilute nitric acid and wit,li bromine although this is known to be the case with codeine and the methyl group. Anhydrous morphine when heated at 100-110" with twice the amount of henzoic chloride yielded di- benzoylmorphine which supports the view that the morphine molecule contains only t w o hydroxyl groups.Polstoi~fi's tritetizoylmorphine could not be detected. By heating oxydimorphinc with acetic chloride tetracety loxydimorpliii I e is obtained which doubtless is identical with Hesse's diacetylpseudomorphine obtained by the action of acetic anhydride on pseudomoiyhine. The entrance of the four acet,yl grcups indicates that four hydroxyl groups exist intact i n the oxjdimorphine and that the hydrogen atoms replaced must have been united wit'h carbon. Apomorphine when treated with excess of acetic chloride yields monacetylapomorphine ; hence only one hydroxyl group is present in apomorpliine the second hydroxyl group c/f morphine during its conversion into apomorphine going to form a molecule of water.Probably tlie alcoholic hydroxyl of morphine is tlw one expelled the phenyl hydroxl having greater stability. This t o some extent will account for the chemical and physiological difference between morphine and apomorphine. J. T. J. T. Cinchonamine. By ARNAUD (Ann. Chim. Phys. [ 6 ] 19,93-131) See this vol. p. 362. Berberine and Hydroberberine. By R. GAZE (Arch. Phawn. 228 6 0 k 6 6 2 ; compare Abstr. 2830 101 2).-Chloroformberberin~ dissolved in a little hot chloroform acd treated with alcohol quickly gives long prismatic crystals of dicliloroforni berberiiie CmHi,NO,,CHCl + CHC13. The crystals soon lose their transparency when preserved and decom pose with evolution of chloroform when warmed. J. T.ORGANIC OEEMISTRT 333 Ecgonine. By U.Mussr (Chem. C'entr. 1890 ii 516 -517 ; from L'Orosi 13 15%158).-The aubhor has already (L'Orosi 11 270-277) recorn mended that since the direct detection of cocaine is difficult the products of its decomposition should be sought ibr in toxicological investigations. With t,his object he has examined t'he behaviour of ecgonine with various reapents. According to Eiiihorn this a1 kaloid is met11 y I t e t rah. y d ~ o p y rid y 1-6- h y di-on y propionic acid C,NH,Me*CH( OH)*CH2*COOH and reacts both as R base and an acid; it crystnllises in colourless lustmus monoclinic prisms with 1 mol. H20 which is lost at 1%~-130". I t is very readily soluble in water less easily i n abso- lute alcohol insoluble in ether chloroform and carbon bisulpliide. Its solutions are neutral and have a somewhat bit,ter taste.It melts at 19c3" with partial decomposition. With pbosyhomolybdic acid i t fornis a yellow precipitate ; with somewhat concentrated gold chloride solution a yellow amorphous precipitate ; with platinic chloride in di I ute alcoholic solution a red-brown crystalline precipitate (CgH15N03)2,H2PtCI which is readily soluble in water and loses hydro- gen chloride when heated forming the salt (C,H,,N03),PtC14. With starinic chloride mercuric cliloride tannin and picric acid it forms no precipitates which distinguish it from cocaine. Especially is the reac- tion with Wenzell's reagent (BOO parts of sulphuric acid and 1 part of potassium pernisnganatc) delicate a clear wine-red coloration being formed which disappears only after some time.I n an experiment with EL rabbit 1.26 grams of ecgonine per kilo. of live weigbt was found to be fatal. After 48 hours tlie entrails were divided into tive parts and each part digested several times at 60° with twice its weight of a!cohol,and the extract concentrated nearly to dryness. The residue was taken up with water and shaken several times with ether in order to extract fatty substances. The aqueous solu t,ion was precipitated with basic lead acetate filtered the lead removed as sulphide the liquid again filtered evaporated co dryness and the residue finally extracted with a little absolute alcohol in which the ecgonine exists as acetate and was readily detected. The alkaloid was found in the heart blood lungs liver,b.r;tin,and spinal cord.. Ergonine SaZts.-( CgH,5N03)2Mg + Y+H20 very hygroscopic yla t,es soluble in water and alcohol insoluble in ether melting at 190".(CgH15N03),Ca is soluble in water and alcohol insoluble in ether. C9H15N03Ag orange-coloured decomposing readily when exposed to the light. Ecgonine a,cefate C9H3[15X03,C2H402 + 2iH20 needle-like hygroscopic crystals melting at 196" very soluble in water aud alcohol insoluble in ether. New Alkalo'id from Chrysanthemum cinerariaefolium. By F. MARINO Zuco (Chem. Centr. 1890 ii 560-561 ; Rand. Acad. Lincei 6 i 571-575).-In addition to the two substances the one a paraffin and the other a homologue of cholestei-01 which the author has alr2ady described (Abstr. 1890 7 5 i ) he has further separated a glucoside and an alkitlo'id from the flowers of CYlwysatrthemum cine- rarimfoZium.Both were obtained from the blossoms by extraction with ether. The glucoside is crystalline but could not be obta.ined J. W. L.334 ABSTHAUTS OF CEEMIOAL PAPLRY. in sufficient qnantit,y for proper investigation. The alkaloid named ckrysanthemine by the author is readily soluble in water and its solu- tion may be concentrated on the water-bath without decomposition whereby the base is obtained as a colourless syrup. The majority of its salts are soluble in water alcohol and ether and are crystalline. The most characteristic of these is the aurochloride which crystal- lises in small goldon-yellow needles very soluble in hot water sparingly so in cold water readily in alcohol and moderately soluble in a mixture of alcohol and ether (1 1).Potassium bismuth iodide forms a yellow precipitate with it and pntassiuni mercury iodide forms a yellowish-white precipit,ate. Platinum chlor- ide tannin and picric and phosphotungstic acids do not form precipi- tates with it. The analysis of the aurochloride agrees with the formula ClaH3003NZ,2A~C14 according to which the formula of Che hydrochloride mould bo CI4H3,,O3N,Cl2. Ulexine and Cytidne. By A. W. GERRARD and W. H. SYMONS (Pharm. J. [3] 20 1017).-The authors enumerate the following differences between ulexine the alkaloid of Ulex europrms already described by them and cytisine the alkaloid of C. laburnum which has been supposed to closely resemble or be identical with the former. Ulexine has the formula -i(CZ,H,N4O2) ; is very hygro- scopic cannot be sublimed even in a vacuum without decomposi- tion and dissolves readily in chloroform.Cytisine bas the formula CznHz,NaO is permanent in air sublimes completciy forming splendid crystals and is almost insoluble in chloroform. The formula given for ulexine differs only by CO from that of nicotine arid by HzO ti-om that of pilocarpine and there is a certain likeriess in the physio- logical action of these alkaloids notwithstanding the differences in their chemical behaviour. Some progressions of properties are traced in the alkaloids from leguminous plants arranged according to the percentage of carbon thus :-sparteine pyridine nicotine cytisine ulexine eserine and pilocarpine ; in this series the physio- logical activity becomes more powerful and the instability greater with decrease in the percentage of carbon.Alkaloids and other Active Principles from Plants Growing in the Dutch Indies.-By M. GRESHOFF (Ber. 23 3537-3550).- I. Carpaine the Alliaload vf Carica papaya L.-The leaves of the papaya (Carica paptryu L.) contain in addition to the caricine and papai'ne discovered by Wurtz and Peckolt an alkaloid which has riot previously been prepared and for which the name cwpaine is proposed. The young leaves are richest in the alkalo'id and contain about 0.25 per cent. ; the sap seeds and roots only contain traces. Caspaine is readily soluble i n alcohol chloroform and ether the freshly precipitated compound being more readily taken up by the latter solvent than when ci*ystallised a fact which is made use of in isolating the alkaloid.It is completely separated from solutions of its salts by sodium carbomte solution but is insoluble in potash aild carinot be extractcd from acid solution. It gives precipitates with Majer's solution iodine phosphomolybdic acid picric acid gold chloride tannin potassium thiocymate &c. melts at ll5* and sub- J. W. L. R. R.ORQANIO OHEMISTRT. 335 limes partly without decomposition. Its hydrochloride crystallises in beautiful lustrous needles and is readily soluble in waher. The base even when dissolved in 100,000 parts of water has a bitter taste and is only poisonous in large doses but small quantities readily kill smaller animals the action taking place on the heart. 11. Investigation of Indian Leguminous Plants.-The plant known as Derris (Yongamia) elliptica Benth.,is largely used in Java in fishing and appears also to be a constituent of the Borneo arrow-poisou. It has'an exceedingly poisonous action on fish a decoction of the roots being fatal even when diluted with 300,000 parts of water.The only active constituent isolated is a resinous substance termed derrid which does not contain nitrogen and is not a glucoside ; it readily dissolves in alcohol ether chloroform and amyl alcohol but is very sparingly soluble in water and potash solution. On fusion with potash it yields salicylic and protocatechuic acids. It occurs almost entirely in the cortex of the root but has not yet been obtained pure. Its alcoholic solution has a slightly acid reaction and a sharp aromatic taste causing a partial insensibility of the tongue which remains for hours. A solution of 1 part i n 5 millions is almost instantly fntitl to fish.A very similar compound is found in the seeds of Ynchyrhixus angulatus Kich. a decoction of which is quickly fatrtl in a dilution of 1 125,000. it is probably identical with derrid but until this has been experimentally proved it may be distinguished as prtchyrhizid. It is very readily prepared from Pachyrhizus which occurs in all tropical countries as the tannin compounds usually so difficult to separate are not found in this. plant. 'l'he seeds also contain a non- poisonous crystalline compound which is readily soluble in alcohol arid has at 3'3" the consistence of butter. 'l'he plant Sophora tomentosa L. formerly renowned as a medicine (" Antzcholerica Burnphii ") contains 8 poisonous alkaloid soluble in ether which is contained in largest quantity in the seeds.Alkalolds have previously been found in S. speciosa and S. angustijolia b u t have not been closely investigated. The cortex of Erythrina (S'teiwtrol;is) Broferoz Hassk. contains con- siderable quantities of an alkdoi'd which may be readily isolated by Stas's method and is easily soluble in ether. Its snlphate may be obtained in crystals from concentrated aqueous solution. I t gives precipitates with many metallic salts and with the usual alkaloid reageuts ; it is a fairly strong poison being fatal to fowls in doscs of 0.025 gram. A poisonous alkaloid likewise exists in Erythrina (Hypuphorus) aubum,brans Hassk. and is best isolated as a metallic double compound.'l'lie leaves of different kinds of cassia are employed in Java as a remedy for herpes; $hey contain a glucoside which yields chryso- phanic acid as a product of hydrolysis. The leaves of Urotolarin retusa L. contain considerable quantities of indican ; the seeds contain an alkaloid which is found in larger quantities in the seeds and leaves of C. strinta L. The base is a strong poison and is probably clodely related to the known alkaloids of other Genistese such as Cytisus Ulex Spartiurn and h p i n u s . The seeds ot Nillettia utropurpurea Benth. contain a poisonous336 ABSTRAOTS OF OEEMICAL PAPERS. glucoside the chemical and toxicological properties of which closely resemble those of saponin. The plant is also employed for poisoning fish.The cortex of Acacia tenerrimc~ Jungh. contains a bitder poisonous alkalojid readily soluble i n ether and chloroform. No alka- loid has previously been found in an acacia. The leaves of Albizziz saponaria Bl. contain cathartic acid whilst the leaves and cortzx contain saponin in quantity. The cortex of Pithecolobium bigsminum Mart. contains 0.8 per cent. of a non-volatile amorphous alkaloid which forms crystalline stilts and separates as a heavy yellow oil on the addition of alkalis to solu- tions of the latter. With 100 parts OE water it forms a turbid liquid which on warmiug assumes the appearance of milk but becomes clear on tbe addition of an acid. The solutions have a burning taste and give the usual alkaloid reactions. It has a strong corrosive action on the skin and is fatal to fish in a dilution of 1 400,000.The same com- pound appears also to occur in P. suman. Benth. III. Apocynece containing Alkaloids occurring in the Dutch Indies.-The leaves cort.ex and seeds of Melodinus hvigutus Bl. all contain a poisonous alkaloid which is present in the largest quantity in the seeds (0.8-1.0 per cent.). It is decomposed by dilute hydrochloric acid but is not a glucoside and gives the ordinary alkaloid reactions in very dilute solutions and with feeble oxidising agents in sulphuric acid solutions gives a greenish coloration which then becomes deep blue and finally orange. Leucorcotis rwgenifolia Dec. yields a poisonous crystalline alkaloid which is readily soluble in ether and shows the general reactions of the alkaloids but gives no colour reactions.The cortex of Rauwolfiu ca?zescens W. yields an alkaloid which gives a beautiful blood-red coloration with nitric acid. Rauwolfia (Ophioxylon) serpentirm and trifolinta which is highly prized in Java RS it drug also contains a crystalline alkaloid which gives the same reaction with nitric acid and its presence may be easilg recognised microscopically in the various parts of the plant by this reaction. The substance recently des aribed as ophioxylin is identical with Duloug’s plumbagin the error being caused by a confusion between Ophioxylon se~pentinu~rz L. and PEunzhago Tosea L. which though very different plants are both termed “‘ Poeleh Pasdak ” in Java. The above alkaloid also occurs in Rauwol$a (Cyrtosiphonia) spectabilis and madurensis. All these species of Rauwo@u contain a brown substance also ; this likewise appears to be an alkaloid and yields a beautiful blue fluorescent solution in ether.The cortex of H u i i t e k corymbosa Roxh. contains 0.3 per cent. of a crystalline alkalo’id whicb a l ~ o forms crystalline salts and gires a beautiful violet coloration with Erdmann’s and Frohde’s reagents. It is a strong poison and has a sharp burning taste even when dilut,ed to 1 10,000. The cortex of Pseudochrosia glomerata Bl. also contains a poisonous crystalline alkaloid and the above fluorescent compound. The cortices of Ochrosia (Lnctaria) acuminata Acksringae and Coccinea are rich in alkaloYd constituents. Three products have heen isolated namely a colourless crystalline alkaloid soluble in ether which is moderately poisonous an alkaloid insoluble in etter but It is constitueiit o€ many Apocyn,ece.ORQANIO CHEMCSTRT.337 soluble in amyl alcohol which is bestl isolated as the rnerourochloride and also the above-mentioned fluorescent compound. These substances also o c c x in the seeds and the sap. The cortex of the stem of Ochrosin (Bleekaria) kalocarpa contains 1.2 per cent!. of alkaloids. Tlre seeds of KopsiaJflrrzida BI. contain no less tJhan 1.83 per cent. of a homogeneous alkaloid which is soluble in ether and readily pre- pared pure and crystalline ; it likewise occurs in Kopsia arbo?-ea Bl. the leaves of which contain in addition a fluorescent substance. Kopsia (Calpicccrpum) Rozburgliii yields quite a different alkaloid which causes tetanus.The seeds and leaves of Kopsia (Culpicarp2cm) alb&run? contain RU alkalo'id as also do Vinca rosea L. and dZsto?ieu (Blaberopus) aillosn. Voacanga (Orchipedn) .fetida jields a bitter alkaloid readily soluble in ether and the flnorescent compound already frequently mentioned. Tabernemontana spZmrocarpa BI. also contains an dkaloid and a wax-like compound which is free from nitrogen and melts a t 18.5". Alkaloids are also present in Rhyncodia (C'ercocoma) macruntha and in Clmnemwpha mncrophylla Don which is of interest inasmuch as these species both belong to the Echifidie the other members of which are free from alkaloids. IV. Cerbera odollaw Hamilt.-The Rap leaves and cortex of this plant have no toxicological action but the seed kernel contains in d d i tion to a non-poisonous fatty oil the compound cerbei in which has a poisonous action on the heart.It resemhles thevetin thevetosin and tanghinin but is identical with none of them. It most nearly rexm bles the last-named substance which is obtained from Tunyliirkz venenifera Poir. the " test-plant " of Madagascar. Ceyberin is fre,e f rorn nitrogen and crystallises well and although decomposed by acids. is not a glucoside. It is insoluble in water but dissolves readily in alcohol chloroform acetic acid and 80 per cent. ether and melts at 165". It gives n violet coloration with sulpliui.ic acid bas a sharp burning but not bitter taste and is very poisonous. The seeds contain another very poisonous substance which is readily soluble in water alcohol and xmyl alcohol but i~soluhlc in chloroform for which the name odollin is proposed.It is not pvecipitated by lead acetate and gives the same colour reaction with sulphuric acid as ccrberin. V. Laurotetanine the Active Cnnstituw t of certain Lawacem.- Many of the Javan varieties of Lauraceae contain in addition to other not yet clearly defined bases a crystalline alkaloid termed luurotet- anine which has a strong tetanic action on animals. It is coiitained in quantity in the cortex of the stem of Litscen chrysocoma Bl. and is sparingly soluble in ether more readily i n chloroform. It is pre- cipitaled by sodium carbonate from solutions of its salts but readily redissolves in an excess of potash or soda and is precipitated by the umal alkaloid reagents.The freshly prepared alkaloid cominenccs too crystallise after some days in stellate groups of ncedles ; it gives a dark indigo-blue coloration with Erdmann's reagent a pale rose-red with pure sulphuric acid and a reddish-brown witth nitric acid. A base which seenm t o be identical with laurotetanine is also found in the varieties of TetrantheTa in Notaphmbe Bl. Aperuh Bl. and Actinoduphne Nees. It is possible also that laurotetanine is identical338 ABSTRACTS OF OHEMICAL PAPERS. with the alkaloid discovered in 1886 by Eykmann in Huasia squarrosa 2. et M. as the author has also found it in 11. firma Bl. Hernandia sonma L. and H. ovigera L. both yield an alkaloid closely resembling the bebeeriue obtained from Nectundru whilst Illipra pulchra Bl. contains laurotetauine.VI. l'he Distribution of Hydrocyauic Acid i n the Vegetable Kingdom. -The leaves of Gymlzema latt$oliurn Wall an Indian Asclepiadea contain large quantities of amygdalin which can however only be obtained in the amorphous condition. The leaves do not contain any enzyme and may therefore be distilled with water or dilute sulphuric acid without any hydrocyanic acid or benzaldehyde passing over. On the addition of emulsin hydrolysis readily takes place. 'l'he fresh bark of many Javan forest trees gives off an odonr of bitter almond oil. It was found that f'yqium parviJiorum T. et B. and P. Zatifoliuna Miq. both contaiu amjgdalin which on botanical graunds was not improbable as the species Pygium is closely related to Ampgclalus. When the fruit of certain Javan Aro'ides (the genera Lasin and Cyrto- sperma) is cut a strong odour of hydrocyanic acid is observed and it was found on investigation that it is present in the free state.it also occurs in the leaves of these plants. It is found however in much larger quantity in a Javan tree known as Pangium e d d e Reinw. the seeds of which after cooking in a certain manner are looked on by the Malays as a valuable food. It' this cooking is insuificient the seeds are a frigbtful poison and are used in Java for killing fisq and insects. I t was found on investigation that all parts of the tree contain free hydrocjanic acid. Thus the leaves on distillation yielded 0.34 per cent. which is equal to 1 per cent. on the dried leaves; in the other parts the proportion although less is still considerable.The amount of bydrocyaiiic acid is not constant old Pangium leaves having been examined which only contained 0.045 per cent. The leaves and seeds of the Pangium contain a substance which reduces ammoniacal silver solution and E'eh ling's solution in the cold arld whose solutions become dark-coloured in the air. Although no crystalline componnd could be obtained with phenylhydrazine it is probably a sugar with which the hydrocyanic acid forms an unstable compound. 'l'he seeds which are originally white gradually become dark the hydrocynnic acid disappearing at the same time. The only poisonous constituent of the genus Hydnocarpus is also hydrocyauic acid. The fatty oils of certain species of Hydnocarpus are used externally in skin diseases their value being possibly due to the antiseptic action of hydrocyanic acid. H.G. C. Coagulation. Preparation of Soluble Casein. By A. BECHAMP (Rull. Soc. Ghim. [ 3 ] 4 181-186).-The author takes exception to the undefined meaning of the word coagulation as applied to the separation oE the proteids from milk under varying conditions and describes the following method for preparing a soluble casein which is not coagulable by heat. Pure acetic acid is dropped into milk just drawn from the cow or goat until the milk turns litmus- paper a pale pink and the coagulum which soon separates out isORGANIC CHEMISTRY. 339 collected and after drying by a filter pump is treated with ether to remove fat; it is then suspended in a volume of' water equal to that of the original milk and containing ammonium carbonate and the mixture is filtered.To the limpid solution thus obtained acetic acid is added exactly sufficient to precipitate the casein which by a re- petition of the above treatment is obtained pure. The rotatory power of this substance in ammoniacal solution is [a] = -130". It is soluble in water 1 litre dissolving on agitatior for 56 hours 1.005 grams and the rotatory power of this solution is [a]j = -117". A paste of casein and water softens at 70-80" and appears to be quite soft at go" tbe water separated from this product contains 2.37 grams casein per litre ; and although the paste hardens on cooling it is soluble in ammonium carbonate solution and on pre- cipitation by acetic acid manifests its original properties.Casein bebaves like a feeble acid its solutions redden litmus and it forms conipounds with the alkali metals and with ammonia which also redden litmns and are neither precipitated by carbonic anlrydride nor by alcohol nor by heating. Calcium caseinate behaves like calcium saccharate in becoming tnrbid on ebullition and in tbe dis- nppeararice of the turbidity on cooling. The author ascribes the incorrect results hitherto obtained to the practice of boiling the milk before adding the acid by which lactalbumin and galactozymase are precipitated as well. These substances are separated from the whey left after removal of the casein by adding to it alcohol of 95" as long as a precipitate falls ; the latter is collected and washed with alcohol of 80° to remove lactose and is then air-dried and suspended in water ; after some time it is filtered and the precipitate is washed with water as long as the washings give a precipitate with alcohol. Lactozymase is separated from the filtrate by the addition of alcohol and a trace of sodium acetate; i t is soluble in water and has the power of determining the dissolution of starch without subsequent hydrolysis ; it is coagulable by heat and then loses this property.Lactalbumin is obtained by dissolving the residue in dilute ammonium carhnate solution and precipitating by acetic acid ; when it is suspended in water and heated to loo" it contracts in volume and is no longer soluble in ammonium carbonate solution. Protei'ds of Milk. By W. D. HALLIBURTON (J. Physiol. 11 448-463).-Attention is drawn in this paper to the following points :- (1.) The principal proteid in milk precipitable by saturation with certain neutral salts or by acetic acid should be called caseinjogen. It may be most satisfactorily prepared free from impurities by a combination of the two methods just mentioned.The term casein should be restrid,ed to the curd formed from caseinogen by the action of rennet. (2.) I n the classification of proteids casein should be grouped with other insoluble proteids like fibrin and gluten formed by ferment activity from pre -existing more soluble proteids. Case'inogen should be classified in a new gronp made t o include it and whey-proteid. These are very similar to the globulins ; the chief difference being T. G. N.3 10 ABSTRAOTS OF CHEMICAL PAPERS.that their solutions are not coagulated by heat like the globulins but only rendered opalescent. This opalescence i f the heating has not been continued too long disappears on cooling. (3.) Lactalbumin id very similar in its properties to serum-albumin. Not only does it differ however from serum-albumin in its specific rotatory power as has previously been shown but in its behitviour on heat-coagulation and in precipitahility by certain neutral salts. (4.) Caseinogen and lactdbumin are the only proteids contained in milk. The proteid described as lactoglobulin does uot exist; i t is owing to tbe error of not recognising t h d the two salts sodium chloride and magnesium sulphat? when both present to saturation precipitate albumin that this proteid has been supposed to exist.The prote'ids variously called lactoprotein peptone and herni- albumose do not exist in milk. This mistake has also arisen from faulty methods of analysis. ( 5 . ) The proteid called whey-proteid which passes into solution simultarieouslj with the forination of the rennet curd is not of the peptone or proteose class b u t should bc included with caseinogen i i i a new class of proteids allied to the glokulins. It differs from casehopen in not being convertible into casein. (6.) When milk turns sour owing to the lactic acid fermentation primary proteoses chiefly proto-proteose art! developed. W. D. H. Note.-Hammarsten in his text-book of Physiological Chemistry recently published also recognises that caseinogen should not be grouped with nlkalii.albuminates as has hitherto been the case. He classifies it with the nucleo-albumins. W. D. H. Action of Lime Salts on Casein and on Milk. By S. RINGER (J. Physiol. 11 464-47i).-Casein preparcd by adding commercial rennet to milk was found to be freely soluble in lime- water ; on the addition of calcium chloride to this solution a com- pound of casein is formed which is more soluble in cold than in hot solutions. A few drops of calcium chloride solution does not cause precipitation at all in the cold but on warming a precipitate forms closely resembling a rennet curd and like it i t contracts squeezing out a whey. On cooling this however it completely redissolves. Larger quantities of calcium chloride cause a precipitate in the cold which increases when the mixture is heated.Sodium chloride in 0.5 1 and 2 per cent. solutions does not modify this action ; whilst lactose greatly aids the action of the calcium salt. Calcium chloride causes no curdling of milk at the atmospheric temperature (loo to lSO) i n this respect differing strikingly from solutions cf casein in lime-water from which 1 to 3 drops of a 10 per cent. solution of calcium chloride precipitates abundance of curd or sets the fluid to a jelly. Calcium chloride however abundantly precipitates curd from milk with the assistance of heat the smaller the quantity of calcium chloride the higher the tcmperature required. Slight acidity favours sodium chloride and to a less extent potassium chloride and magnesium sulphate hi rider this action of calcium chloride.Hence Similar experiments were then tried with milk.ORGANIC CHEMISTRY. 341 milk differs from casein dissolved in lime-water in respect to the action of sodium chloride. Lactose which greatly favours tbe clot- ting of a lime-water solution of casein by calcium chloride does not influence the clotting of cass'iaogen as contained in milk. Calcium chloride solution does not clot milk whicb ha8 been pre- viously boiled and then cooled. Hence it is evident that the biph temperature necessary in the experiments does not alter the casehogen and thus enable calcium chloride to precipitate it but that the high temperature is necessary to enable cakium chloride to precipitate (combine with) casefnogen. Casebogen can be prepared as follows :-lo pel. cent.acetic acid is added to milk; the resulting precipitate is washed with distilled water until the washings are neutral and free from calcium salts. The curd is rubbed in a mortar with cnlcinm carbonate and distilled water added ; the casehogen rapidly dissolves and the butter sepa- rates and floats on the top. After some hours the milky fluid below is eiphoried off. Rennet clots tbis solution if a small quantity of calcium cliloride is added but not without. The rennet used (Crosee and Blackwell's) contains a good deal of calcium but tbis is either insuffi- cient or in inappropriate form. But although the Anid does not clot the case'inogen is courerted into casein which reninins in tohition and this is at once deposited on adding calcium chloride eclch drop pro- ducing an abundant deposit insoluble in solut,ion of sodium chloride.Sodium and potassium salts antagonise the clotting of casehogen solutions a s iri the case of milk ; i n the former case they lessen too the subsequent contraction of the clot. If phosphoric acid is essential as Hammarsten etated the minute quantity present in the prepara- tion of rennet must have sufficed as none was added in the experi- ments. Calcium chloride solution precipitated casehogen from its solution without the assistance of rennet; only larger quantities are necessary than i s the case with solutions of casein. Lactose has no eBect OQ the precipitation of casei'nogcn by calcium chloride. Corroborative resnlts were obi ained with case'inogen precipitated by saturating milk with sodium chloride. Among further differences between casehogen and casein the two following may be noted :- (1.) Casein is insoluble in a fairly strong solution of sodium chloride ; casei'nogen is so!uble.( 2 ) Caseinogen precipitated by acetic acid and mixed in a mortar with calcium carbonate is freely soluble in distilled water. Casein similarly treated is insoluble. The process of ordinary curdling in milk by rennet is believed to consist of two parts :- (1.) The change from casehogen to caseh produced by the f ermen t . (2.) The combination of the casein so formed with a lime salt the precipitation of ihis compound being assisted by the lactose but opposed by the sodium and potassium salts of the milk. These salts also lessen the degree CJf contraction of the clot and hence a bulky clot instead of a compact one is obtained.W. D. H.34'2 ABSTRACTS OF CHEMICAL PAPERS. Chittenden Painter. Digestion Products of Gluten-caaeh. By R. H. CHITTENDEN and E. E. SMITH (J. Physiol. 11,420-434).-The methods of investiga- tion are essentially the same as those adopted in the similar researches of Kiihne Chittenden and others. Although it i s questionable whether gluten exists in fresh wheat grains i t is nevertheless true that gluten is formed whenever wheat flour is mixed with water and of this gluten the insoluhle portion characterised by Ritthausen as gluten- case'in is the most important constituent. The percentage composi- tion of this material (the average of analyses of seven preparations) may be contrasted with the numbers obtained by Ritkhausen and with the percentage composition of the case'in of milk as in the following table :- Halnmtlrsten.~ Gluten- case'in. 53 -30 7.07 15 '91 0 -82 Caseln of milk. I 52 -96 7 -05 1.5 -65 0 72 Chittenden and Ritthausen. I Smith. I 52 -87 6 *W 15 *86 1 *17 c ........ H ........ N ......... 8 ......... 52 94 7 *Q4 17 *14 0 -19 On subjecting gluten-case'in to artificial gastric digestion,it was found that solution occurs very slowly probably the result of the prolonged washing with alcohol in its preparation. Artificial pancreatic diges- tion also proceeds slowly but there is a more abundant formation of true peptone as compared with primary cleavage products (proteoses) than is the case with gastric digestion. The soluble products formed in each case bear essentially the aame relation to the parent substance as the albumoses of albumin or fibrin do to the parent protei'd.There are slight differences in minor reactions but no essential difference in the general chamcter of the products formed in this case at least between theanimal and vegetable prote'id. Both yield by the action of peprjin acid 8 proportionately large amount of proteoses and a small amount of true peptone. The gluten-caseosee both in com- position and reactions show the ordinary proteose characteristics and the composition of the individual products (proto- hetero- and deutero-gluten-caseose) aa indicated by the gradually diminished percentage of carbon snggests that they are formed by a gradual process of hydration. Crystalline ViteUin and Vitelloses.By R. H. CHITTENDEN and J. A. HARTWELL ( J . Physiol. 11 435-447) .-This research carried out on the same lines asthe preceding confirms i n the main the work of Neumeister (Abstr. 1887,286) ; i t was judged advisable to repeat the experiments 88 d d i n (crystallised in this research from extracts of squash or pumpkin eeeds by Drechsel and Grnbler's method) is the purest proteid obtainable. Scarcity of material prevented the W. D. H.ORGANIC OHEMISTRY. 343 Vitellin ...................... Proto-vitellose ................ Deutero-vitellose (1) .......... > 9 .. (2) .......... investigation of many points but the general conclusion is that in gastric digestion the changes as in the case of other prote'ids are hydrolytic in nature ; proto-proteose deutero-proteose and peptone resulting from a series of gradual hydrations as indicated by the gradually diminished percentage of carbon.The amount of hetero- vitellose formed was small. Att.ention was particularly directed to the percentage cornposition of the products and the following table collects a few of the averages obtained :- - 51 -60 6.97 18 -80 51 *52 6 '98 18 -67 50 42 6 9 4 18.43 49 27 6.70 18 *78 The results agree very closely with those previously obtained with the globulin body myosin the composition of the myosinoses bearing almost exactly the same relationship to myosin as the vitelloves do to tbe crystallised globulin. A single experiment on tryptic digestion sbowed nothing noteworthy. Crystallisation of Hemoglobin. By S. M. COPE~JAN ( J .Physiob. 11 401-40S).-This i s a full account of experiments a preliminary notice of which has already appeared (Abstr. 1889 1092). Among new points noticed is the factt t h a t some crystals of human hsemo- globin were after the lapse of some months changed into crystals of hsemochrotnogen. Hoppe-Sepler has previously prepared crystalline hmmochromogen (Abstr. 1889 788). T t was found that using the method of adding putrid serum to the blood the hsemoelobin crystals of the squirrel obtained were not the usual hexagons but rhombic prisms. (Compare Halliburton Abstr. 1886 637). W. D. H. Compounds of Hemoglobin with Carbonic Anhydride. By C. BOHR (Chenz. Centr. 1890 ii 521 ; from Centr. PhysioZ. 4 253- 254) .-As already communicated (Abstr. 1890 1450) there are several compounds of hsemoglobin and carhauic anhydride containing varying proportions of the latter b u t showing dissociation curves which are approximately similar.The author now describes the three following :-*,-carbohoeemogZobin wbioh contains about 3.0e.c. of carbonic anhydride per gram at 18" under a pressure o€ 60 mm. of carbonic anhydride ; 6-carhohoemogZobin which contaius about 6.0 C.C. of carb- onic anhydride under the same conditions of temperature and pres- sure ; P-carbohaemoglobin which contains about 1.5 C.C. of carbonic anhydride per gram. It' hsemoglobin is shaken with a mixture of carbonic anhydride and oxygen both the gases are absorbed in the same manner as though each of the gases was present alone. The spectrum of these hemoglobin compounds appear to be t h e same a8 that of oxybemoglobin.The author concludes that the carbonic anhydride W. D. H.344 ABSTRACTS OF CHEMICAL PAPERS. and the oxygen combine differently and independently with the heemo- globin and the possibility exists that arterial blood fully charged with oxygen may nevertheless absorb carbonic anhydride. J. W. L.ORGANIC CHEXISTRY. 281Organic Chemistry.Active Amy1 Derivatives. Rg P. A. GUYE (Compt. rend. 111,74.5-74i).-If the views previously explained (Abstr. lS90 722)are correct any substitution in the group CH,Cl in active amylchloride that keeps the mass of this group higher than that of thenr,altered H Me and Et gronps will yield derivatives with a rota-tory power of the same sign as that of the amyl chloride.Examina-tion of forty amyl derivatives which may be regarded as derivedfrom the active chloride in the way indicated proved that this deduc-tion is correct. C. H. B.Hydrolysis of Halogen Carbon Compounds. By C. CHARRIR(Corapt. rend. 111 747-748).-Ethylene fluoride is obtained as acolourless gas by heating ethylene bromide ak 200" with silverfluoride. It is absorbed by lime water with formation of glycol andcalcium fluoride. The author is endeavouring to obtain ergthrol ina similar manner. He has also investigated the action of haIogenderivatives on boric anhydride at a high temperature. Ethylenebromide and glycerol tribromhydrin yield a considerable quantity ofboron bromide at 250". Carbon tetrachloride yields boron chloridei n large quantity ; tetrachloretbjlene reacts with less energy arid hexa-chlorobenzena yields no boron chloride.Carbon tetrachloride silverfluoride and amorphous boron yield gases containing fluorine,VOL. LX. 282 ABSTRAOTS OF OHEMIOAL PAYERS.chlorine carbon and boron with some deposition of carbon mil boron,and a small quantity of silver.p-Dipropylene. By F. COUTUR~ER (BUZZ. Soc Chim. [3] 4,30-31).-1f pinacone after treatment with sulphiiric acid i R suh-milt& to distillation i t yields in addition to pinacoline a liquid boil-ing at 60-70° which on fract,ionation affords an impure substanceboiling a t 65" ; this when heated with calcium chloride in senled tubes,and subsequently fractionated over sodium yields /3-dipropylene C6H10,which boils at 69.5".It neither forms a compound with cuprouschloride nor with silver nitrate in ammoniacal solution but yields atetrabromide CsHloBr4 which is Poluble in alcohol and in ether; i tmust therefore dij3er in constitution from the isomeric hydrocarbon,boiling at S9" prepared by Favorsky (Abstr. 18M 798) by the action ofalcoholic potaqb on pinacolirie dichloride and probably has the con-stitution CH,:CMe*CMe:CH2. By the action of acetic anLydride onpinacone at 80-90" for several days a crystalline dittcetyl derivativeof pinacone and a small quantity of P-dipropylene are obtained ; the;ield of the diacetyl derivative is further enhanced if the action ismaintained in the cold during several weeks when it may beextracted by dissolving the exrefis of pinscone in water and re-crystallising the residual crystals from ether.Constitution of Fulminic Acid.By R. SCHOLL (Bey. 23,3505 -3519).-Although the author's researches on this subject arenot yet complete he has thought it necessary in view of therecent paper of Holleman (this vol. p. 64) t o publish the resultsobtained up to the present time. From results obtained in hi8 re-searches on the alkylated glyoxime peroxides it appeared not impossibleHy :N*?.HC:N*O that fulminic acid might be glyoxime peroxide itself,Against this supposition however is the fact that phenylglyoximeperoxide does not yield salts (see tbis vol.. p. 316) and that etherealsalts cannot bs prepared from mercuric fulminate. The author alsofinds that it cannot be convertcd into acid derivatives of phenylgly-oxime peroxide but that by the action of acetic chloride the chiefproduct obtained is acetylisocyanic acid CONAc.To carry out thelast-named reaction mercuric fulrninat,e is mixed with light petroleum,and an excess of acetic chloride added. Hydrocyauic acid and a smallquantity of isocyanic acid are evolved and acetvlisocyanic acid passesinto solution. The latter has not yet8 been isolated but that it hasraally the constitution assigned to it is shown by the facts t h a t itunites with alcohol forming ethyl acetylcarbclmate NHAc*COOE t,with ammonia to form monacetylcarbamide H,N*CO*NHSc and withacctrtmide to form symmetrical diacetylcarbamide CO(NHAc)?.Further it is resolved by water into carbonic anhydride and acet-amide. The residue which remains after separating the light petr-oleum solution consists chiefly of mercuric chloride but contains alsosmall quanti ties of acetylcarbalnide and symmetrical diacetylcsrb-omide.The formation of the latter can be readily explained as partof the acetylisocyanic acid i b 6ecomposed by traces of moiature withC. H. B.T. G. NORGANIC CHE3lISTRY. 283formation of acetstniide which then combines with unaltered acetyliso-cpnic acid forming symmetrical dincetylcarbamide. The propertiesof this siihstance agree fally with the deseriptiorr of Schmidt (Ahstr.,2872 718) who does notl however give its melting point which theauthor finds to be 152-153".Attempts were made t o isolate acetylisocyrtnic acic1 by usingnitrobenzene as diluent in the above reaction and carefully fmctiona-ting the product under diminished pressure..A liquid was obtainedboiling at 78-80' whicli is not however pwe acetylisocyanic acid,but appears to contain about 14 per cent. of acetouitrile. Some-what similar results were obtained by Schiitmnberger (C'ompt. rend.,54 154) in attempting to prepare this compound from acetic chlorideand silver isocyanate.The yield of acetylisocyanic acid actually obtained amounted tomore than 50 per cent. of the theoretical and it would thereforeappear that this is the only primary reaction and tohat the otherproducts are all formed by secondary reactions. The formula whichmost readily explains this is Steiner's (Abstr. 1883 1074),namely HO*N:C:C:N*OH but it is difficult to understand how acompound of this constitution containiug two carbon atoms unitedby double linkage should be formed by the oxidation of alcohol.H. G.C.Action of certain Inorganic Salts on the Specific RotatoryPower of Cane-sugar. By K. FARKSTEINER (Ber. 23,3570-3378).-In this paper an account is given of the action of the chlorides of themetals of the alkalis and o€ the alkaline earths on the specific rotatorypower of cane-sngar. The author finds that with a constant relation ofsugar to water the chlorides of strontium barium and magnesiumcause ft decrease in the rotation which coiitinues to diminish as thequantity of salt added is increased. The first action of chloride ofcalcium is to cause a decrease in the rotation which however on theaddition of a certain quantity of the salt.reaches a maximum furtheraddition causing an increase in the rotation which eventnally exceedsthat of the pure sugar solution.If the relation of sugar to tbe salt be kept constant and the quantityof water varied it is found that the addition of water caiises in all casesan increase in the specific rotatory power that is tbe action of thesalts is lessened. The speeitie rotator7 power is almost unai€ected byvarying the quantity of sugar with a constant relation between saltand water. The chlorides of lithium sodium and potassium behavein a similar manner.An examination of the action of the same quantities of differentsalts shows that in the case of strontium calcium and magnesiumthe depression varies inversely with the molecular weight and that theproduct of tbe two quantities is approximately a coilstant.Brlrinmchloride does not tact in the same manner but the chlorides of thealkalis show a similar relation. The relation however only holdswithin each group of chlorides and not for two salts belonging todifferent groups. H. G. C .u 284 ARSTRACTS OF CHlr,MICAL PAPERS.Starch. By C. SCHEIBLER and H. M~TTELML~PR (Bey. 23. 34T3).-A reply to the recent communication of Zulkowsky (this vol.,p. 165) on the same subject.Gummy Exudation from the Sugar Beet. By E. 0. v. LIFP-MANN ( Ber. 23 3564-3566) .-A number of large unripe beet-roots,which had teen nllowed to remain for some weeks in paper werefound at.the end of that time to show D verg remarkable appearance.Without any particular brnisinq being visible a number of resinousdrops had separated out in the furrows which commonly occnr in theroot and had flowed together forming a hard brittle tasteless andodourless mess which could be rtsadily and completely separated frointhe roots. In appearance it resembled the ordinary plant gums; i twas insoluble in cold water and alcohol and on burning evolved thec-haracteristic odour of the carbohydrates leaving only & trace of ash.Tt slowly dissolved in boiling alkalis and was precipitated from theneutralised solation by alcohol. When freshly precipitated it dis-solved in water forming a neutral dextrorotatory eolution. On boil-ing with dilute sulphuric acid furfuraldehyde distilled over andarabinoso and galactose were found in tlie residue; when oxidisedwith nitric acid it yielded mucic acid.From these result& i t wouldappertr possible that the compound in an anhydride of arabinose andgalactose C5H,,05 + C6H& - H20 = C1lHmO,,. The aualysis of thecrude compound agrees fairly closely with this formula as also doesthe quantity o€ furfummide and of mricia acid obtained in the fore-going reaction The lack of material has however put an end tofurther investigation tu no other case of the formation of the gum-like compound has been obeerved even when the m t s have beenspecially bruised. H. G. C.Diisobutylamine Ethyl Oxalate. By H. MALBO'I' (BUZZ. &c.Chim. [3] 4 253).-When an alcoholic solution of oxalic acid isadded to diisobutylamine a white precipitate is formed which consistsof diisobutylamine hydrogen oxalate tirid of diisobntylatnine ethgloxalate resulting from tlie action of the former Rubstatice on thealcohol ; the mixture ia crystallised from boiling alcobol when thediisobutylamine hydrogen oxslate first separates &s brilliant scales,and the ihother liquor on evaporation yields acicular crystals ofthe ethyl salt COOEt.C00*NH2(CaH,)2 ; these are dried oversulphuric acid and are recrystallised from boiling ether.When tlieRubstance is heated with water in a reflux apparatus for several days,diisobutylamine hydrogen oxalate is produced. The author is con-tiuuing the study of tlie compound.Action of Propaldehyde on Alcohols.By S. B.NEH*BIJRY andM. W. BARXUIK (Amer. Chenz. J. 12 319-520; compare Genther,Annalen 126 63).-P~olyZidene diethyl ether CH2Me*C H (OEt) isobtained by heating for 12 hours in a closed flask at 100" a mixtnreof propaldehyde (1 vol.) ethyl alcohol (2 vols.) and glacial aceticacid (8 vol.). The product is Abaken .witoh a strong solution ofcalcium chloride to remove unchanged alcohol dried and submittedT. G. NORGANIC CHEMISTRY. 283to frrlctional distillatien.pressure of 74A rum. and has a specific gravity of 0.8825 at 0".8G-88" aud has a specific gravity of 0.8657 at 0".The puye ether boils at 122.8" nuder RPvopycllideue dimethyl ether obtained in a similar way boils atAction of Alcohol on Acraldehyde. Rg S.B. NEWRURT andR. M. CHAMOT (Arner. Chem. J. 12 521-525).-The yield of isotri-ethylin prepared according to the instructions given by Alsberq(Jahrsber. 1864 495) is very unsstisfatctory and uncertain. The(*ompound is best prepnrcd hy heating a mixture of ncraldehjde( 1 vol.) and ahsolute alcohol ( 3 vols.) at a temperature of 50" forfive days. On shaking the product with a strong solution of calciumchloride ne:irly the whole of i t separates as a n oily layer which isdried and distillea in a vacuum. The purified product is a colourlesvliquid having a fruity odour boiling a t 85" under a pressure o f11 mm. and with deccniposition a t 180-18t" under ordinarypressure and having a specific gravity of C.8959 at 0". That it isisotriethylin or triet hoxgpropane is shown by its behaviour towardsbromine and by analy-is but its properties are diiferent from thoseascribed to that coinpound by Alsberg. The position of the thirdethoxy-group is not cstablished althongh the facts that i t readilydecomposes on boiling and thak the dieerence between the boilingpoint of this substance and that of propplidene diethyl ether (comparepreceding abstract) is nearly the same as that between the boilingpoints of auetal and ethosyacetal point to the third group as occupy-ing the a-position and to the constitution of the compound beingOEt*CHMe*CH( OEt),.G . T. 31.G. 1'. M.Action of Crotonaldehyde on Alcohol. By S . B. NEWBURY andW. S. CALKIN (Ainer. Chem. .J. 12 5%3-525).-Wben mixtiires of(.rutonaldehyde m d alcohol are heated for a considerable time attemperatures up to loo" the substances remain unchanged ;combination however readily takes place when 60 grams of theformer arid 120 grams of the latter are heated i n a closed bottle forsix days at SO" with 30 grams of dry zinc chloride.The product,trietltoaybutane probably having the constitutionCH2Me*CH( i)Et)-C H(OEt),,is a colourless liquid of pleasant friiit,y odour boiling at 88-90",under a reduced pressure of 150 mrn. and with slight decompositionat 190" undor ordinary pressures. The specific gravity of the liquidat 0" is 0.88%. G. T. 31.The Indian Grass Oils. By F. D. DODGE (Amer. Clbern. J. 12,,553-564 ; compare Abstr. 1890 231).-Citrone2tic aldehyde has adensity of 0.8560 a t 20" and a rotatory power expressed by[a] = +Po 50'.Its malecular refraction R a = 47-60 does notcorrespond with that cttlcdated for an aldehyde having a hexntotnicnucleus like the menthol series but agrees with that calculated forthe open chain formula C,Hg*CH:CHCJHs*COH or a similar one ;Lence citronellic aldehyde must be regarded as a homologue o286 ABSTRACTS OF OEIEMlOAL PAPERS.acraldehyde. On distilling the bromine additive product 0btrtinr.dfrom 100 grams of the aldebyde 13 gmms of cymene were obtained.Thia compound however was not formed when the aldehyde wtistreated with iodine and the product distilled but a hydrocarbon boil-i u g near 160" was obtained.CitroiieZlaZ-p?iqhoric acid is prepared as follows :-Phosphoricanhydride ( 5 grams) is covered with dry benzene (20 c.c.) and treatedwith water (@55 gram) dissolved in ether (30 c.c.).A cake of meta-phosphoric acid forms and the greater part of the liquid is theiipoured off. To the rmidue citroncllic anhydride (10 grams) 01-citronella oil (20 grams) is added and the conttrining vessel kept at ~ttemperature of 70" for .Revera1 hours. A concentrated solution ofsodium carbonate is added until the solution becomes alkaline tbeexoess of oil separated and the aqueous solution extracted with ethei..Should the aqueous liquid remain colonred a few drops of hydro-chloric acid are added and the treatment with ether contiiiued;this part of the process is repeated until the solution becomes coloui*-less.Excess of concentrated hydrochloric acid is now. added tbesolution cooled and filtered and the precipitated acid crystallisedfrom warm dilute alcohol. It is sparingly soluble in water fromwhich it crystallises in prisms or long flat needles hut dissolveureadily in alcohol from which on slow evapomtdion of the solvent itcrystallises in square plates melting at 203". It is a monobasic acid ;the potassium salt crystalhes in long needles and is very soluble i uwater ; the sodium salt crystallisea in forms resembling those of thefree acid ; the aniline mlt and the quinoline salt both crystallise inwhite needles the former melting at 1639 The acid is dextro-rotatory and most probably has the constitutionalthough the author has not succeeded in forming similarly consti-tuted compounds from other aldtbhydes.L e w G'rirss Oil.-This substance is of uncertain botanical origin.It resembles citzonella oil insomuch as its cbief constituent is analdebjde which may be isolated by treating the oil with sodiurrihydrogen sulphite. When 1000 grams of the dry sulphite are dis-solved in 5 litres of hot water 1 litre of the oil added whilst thesolution is still warm and the mixture vigorously stirred a pastymass of tho hydrogen sulphite compound separates. On remainingfor tmo or three hours this precipitate dissolves leaving a heavy,aqueous solution containing the aldehyde and a layer of residual oil(300 c.c.) above.In 24 hours the solution is perfectly clear and maybe siphoned off filtered and made strongly alkaline with sodiunihydroxide.The supernatant layer of aldebgde ie separated filtered,and dried when i t forms a yellow oil (yield 63-68 per cent. of thegrass oil taken) of pleatiant citrene odmr and iR slightly volatile i t 1a current of steam. It boils with gradual decompcrerition at 225" hash y gr. = 0.8'368 at 15.5" is probably inactive behaves with silverriitra te plenylhydiazine aniline and paratohidine like citronellicaldehyde ; gives palamethylpropylhetrzene on distillation with yhon-phoric anhydride a d cjinene on distilling with steam the red oilc~H,,-cH< :> YO~OH0 RGANIC CHEMISTI’r Y. 287ohiained by the action of concentrated hydrochloric acid ; on treat-ment with zinc-dust and acetic acid it gives a product which is prob-ably the corresponding alcohol.Analysis of the aldehyde shows thatit is isomeric with camphor CloH,,O. The above-mentioned aqueousliquid containing the aldehyde appears to be not merely a solution ofthe hydrogen sulphite compound in excess of sulphite for a crystallinesubstance having approximately the formulaC ,,H180,2NaH S O1,4Na2S O3,50H,O,can be separated from it and further additions of the aldehyde to thesolution do not cause the whole to precipitate as the sodium hydrogensulphite compound. That portion oE the lemon grass oil which doe&not combine with sodium hydrogen sulphite appears to contain aterpene as well as cymene.Indian Geranium Oil.-Samples of this oil differed greatly in be-haviour when distilled (compare Semmler Abstr.2890 Y51).G. T. M.Action of Dilute Nitric Acid on Acetone. By S. B. NEWBURYand W. R. ORNDORFF (Amer. C’hem. J. 12,517-519 ; compare Uebus,Aiznnlen 100 1 and Lubavin J. Russ. Cheirt. BOG. 1881 329aud 49S).-Acetone (I kilo.) was added to nitric acid of sp. gr. 1-42(1 kilo.) the mixture placed in tall glass cylinders and a few dropsof fuming nitric acid introduced t i t the bottom of each by means of along pipette. I n a few hours bubbles of carbonic anhydride corn-rrienced to iorm and the evolution of gas continued stetkdily forseveral weeks. At the end of two months the liquid which had amarked odour of hydrocyanic and acetic acids was poured into a largedish and allowed to evaporate spontaneously. After several months,crystals of ammonium tetroxalate and free oxalic acid were found iuthe syrupy residue which on further concentration and cooling withice yielded a large quantity of crystals the chief prodnct of thereaction.These crystals agreed in every respect with hydroxyiso-butyric acid OH-CMe2*COOH and the original syrup furnished zinchydroxyisobutyrate when boiled with zinc oxide. The mother liquorcontained the zinc salt of another acid but in quantity too small toadmit of its identification. Neither pyruvic acid nor any other pro-ducts of simple oxidation without a breaking up of the acetone mole-cule were formed in perceptible amounts. The production of hydro-cjanic acid by the oxidation of organic substances has been explainedby Hantzsch (Annalen 222 65) and the formation of hydroxyiso-hutyric acid from acetone hydrocyanic and hydrochloric acids byBtaedeler (ibia.111 3%). G. T. M.Action of Hydroxylamine on Isonitrosoketones. By R.SCHOLL (Ber. 23 3 5 ~ 4 5 8 1 ) . - W hen concentrated boiling aqueoussolutions of Iiydroxylamine hydrochloride and isonitrosoacetone ‘alpmixed the heat developed in the reaction causes the boiling to COWtinue for some time. On neutralising with aqueous soda a yellowishpowder crystallises out from which ether extracts met h ylg ly oxime,The residue is practically insoluble in the common solvents but dis-8olve8 in small quantity in boiling alcohol or water separating fro288 ABSTRACTS OF CHEJlICAL PAPERS.the latter in white matted needles. It becomes brown R t 180-200",and explodes at 238-247' ; it dissolves readily in mineral acids andsolutions of sodium hydroxide and carbonate and is reprecipitated onneutralisation. Its composition as found from analysis and the deter-mination of the molecul&r weight by Raoult's method is CaHgN,03.Ita hydrochloride C6H9Ns03,HC1 is fornied by psssinq hydrogenchloride into the dry substmce suspended in et.her aud forms a hard,crystalline cake which dissolves fairly readily in absolute alcobol,melts at 112-113" and explodes at a higher temperature.lsonitrosoacetophenone reacts with hydroxylamine i n a similarmanner forming phenylglyosime and tt substance insoluble in etherand in all common organic solvents. It dissolves i n soda with ayellow colour and is reprecipitated by acids in white flakes havingtho composition Cl6H,a$O$.It also dissolves in hot hydrochloricacid but separates out unaltered on cooling and is probabiy identicalwith the compound obtained by Miiller and Pechlnann by the actionof hydroxylamine on phenylglyoxal (Abstr. 1890 51).Formation of Zinc Propionate by the Action of CarbonioAnhydride on Zinc Ethide. BV I-t. SCHMITT ( J . pr. Chem. [Z] 42,568-569) .-Wanklyn (AmhaZen 107 125) obtained sodium propion-ate by acting on zinc sodium ethide with carbonic anhydride. Theauthor has succeeded i n synthesising zinc propionate by acting onzinc ethide with liquid carbonic anhydride in cm autoclave a t150-160". At the same time there is a secondary reaction by which~ o m e of the zinc propionate is decomposed iuto diethyl ketone andeinc carbonatc A.G. B.H. G. C.Preparation of Cerotic Acid. By T. MARIE (J. Phnl*m. [ 5 ] 22,343-344).-125 grams of bees'-wax is heated with 3 litres of 9;+"filcohol for two hours. After cooling the alcoholic jelly is ponied offand the treatment w i t h Hlcohol is repeated two or three times andeach time for a longer period until the whole of tho cerotic acid isremoved. The alcoholic portions are united filtered and distilledwith a little potash to retain the volatile acids which have been re-moved from the wax and the distillate serves to dissolve the impuremid upon the filter. This solution being heated to boiling the rnyricincontained forms minute droplets which are deposited on coolingquietly and adhere closely to tho flask.The supernatant jelly ispoured on to a tilter and washed with a small quantity of alcohol.After three such treatments and two crystallisations from alcobol theacid is colourless and melts a t 76-77" ; i t is then almost pure. If con-verted into the lead salt according to Brodie's method ether extractsbut rtn insignificant amount of matter and the regeuerated acid meltsat 7s". J. T.Formation of Ethereal SaIts by Means of Ethyl Chloro-caxbonate. By R. OTTO and W. OTTO (Areh. Phumn. 228 500-516).-When ethyl chlorocarbonate is gradually added to sodium formatecovered with about twice its volume of alcohol carbonic anhydride i Rat once evolved ; after remaining some time at the ordinary temperaORGANIC CHEMISTRY.289ture the liquid contains besides sodium chloride aad ethyl carh-onate ethyl formate and free formic acid. with perhaps somefree hydrochloric acid. To separate the ethyl formiate the solutiotiis supersaturated with sodium carbonate water added iE necessary,and sodium chloride to reduce the solubility of the formate which isthen siphoned off placed over ignited potash and purified by frac-tional distillation. An intermediate carboxy-compound is supposedto be formed during the reaction thus:-H.COCbNa + ClCOOEt =NaCl + HCO*O.COOEt ; this ethylic carboformate is partly decom-posed directly thns :-HCOOCOOEt = CO + HCOOEt (I) andthe remaining part under the action of water from the alcohol givesHCO*O*COOEt + H,O = CO + EtHO + HCOOH (11).If alcoholand water be excluded equation (1) still holds good but theremaining part of the carbuformate is decomposed as follows :-‘LHCO*O*COOEt = Et,CO + CO + (HCO),O (111) the latterimmediately decomposing into formic acid and carbon monoxide.Sodium acetate treated with alcohol and ethyl chlorocarbonatesimilarly yields acetic anhydride and also ethyl carbonate showingthat a reaction analogous to (111) holds good here thus:-23leCO*O*CC;OEt = (MeCO),O + Et,CO + CO,. Calcium pro-pionste sodium isovalerate and sodium stearate yielded analogousethyl compounds. Three monobasic acids of the aroniatic series werenext examined. Sodium benzoate when acted on by ethyl chloro-carbonate in presence of alcohol formed essentially et,hj1 benzoateand benzoic anhydride whilst when water is excluded ethyl carbonateis also formed.Here also an intermediate carboxg-compound,C,H,CO-O.COOEt is supposed to enter into the reaction analogousto the compound formed with formates. Potassium metstolnatejielded ethyl metatoluate and a larger amount of metatoluic an-hydride. Next the sodium salt of an isomeride of the last acid,phenylacetic acid was treated. This yielded &hyl phcnylacetate,but no anhydride and in t h i s respect resembles the fatty series. Ofbibasic acids the potassium salt of oxalic acid yielded scarcely anyethyl oxalate in presence of alcohol owing to the precipitation of thesalt from its aqueous solution by this alcohol. I n the absence ofalcohol a small quantity of ethyl oxalate was formed after some days.With potassium succinate the reaction was very energetic.E thy1potassium succinate was produced and a little ethyl carbonate. Inthe bibasic aromatic series potassium phthalate was employed. Ethylphthalate was formed but much phthalic mid was re-formed.h’inally sodium salicylate yielded a little e t h j l salicylnte and car-bonate and agaiu much of the salicylic acid w a s regenerated.Pimelic Acids.. By C. A. BISCHOFF and K JAUNSNICRER (Bey. 23,3399-3409).-Symmetrical dimethylglutaric acid (m. p. loso) frommethyl iodide and ethyl isobutenyltricarboxvlate is identical withi he “ trimethylsuccinic acid ” from ethyl methglmaloiiate and ethylbromisobutyrate and also with the acid from ethyl methylmalonatsfind methyl iodide as well as with Zelinsky’s acid (compare Abstr.,1890 132).On heating with hydrochloric acid in a sealed tube for24 hours nt 2;?0-250° the para-acid is formed (Eoc. cit.).J. T?!I0 ABSTRACTS OF OHEnlICAL PAPERS.After the separation of dimethylglutaric acid from tho prodnct o lthe action of met'hyl iodide on ethyl isohutenyltricurboxylate,the lower fraction boiling at 209-245" yield8 a compound whichhas the formala CsH,,04 ; two preparations showed the melting points88-92' and 103-1 13O whilst the electrolytic conductivities,[ u ) ~ = 353 are K = 0.0114 and 0.0112 respectively. This acidappears to occupy a position in tbe series intermediate betweennieth,ylsuccinic acid and antidimethylsuccinic acid ; the formnla pointsto its being an isomeric dimethylsuccinic or ethylsuccinic acid.Thepaper concludes with a systematic comparison of the acids obtained :(I) by the oxidation of castor oil; (11) from rtmjlene bromide (tri-methylsuccinic acid) ; (111) from rnethylene iodide and ethyl methyl-mitlonate (dimet,hylglutaric acid) ; (IV) ftom methyl iodide amdet by1 isobutenyltricarboxylate.Ethyldimethylsuccinic Acid. By C. A. BISCHOFF and N.MINY z (Ber. 23 34lO-;J41~).-Et~yZd~~~e~h~Zsu~in~c acid,J. B. T.C 0 0 H* C H E t.CMe2*C 0 0 H,is prepared by heating ethyl orthobromisobutyrate with ethyl sodiumetjhglmalonate i n xylene solution at 180-190" for 21 hours under apresstire of 3 atmospheres the product appears to consist of :Imixture of two ethereal salts; it is hydrolysed with potash and,after purification the pure acid crptnllises from benzene or water inlocg concentric prisms melts at 139" (uncorr.) and is insoluble in lightpehroleum carbon bisulphide and xglene but readily dissolves in ether,acetone chloroform or glacial acetic acid.The electrolytic conduc-tivity is K = 0.0582 [joa = 3511. The barium and silver salts havebeen prepared ; the latter is crystalline and insoluble in water.J. B. T.Tetramethylsuccinic Acid. By K. AUWERS and J. A. GARUKER(Rer. 23 3622-3625).-!f'etrameth ylsuccinimide CsH,2<CO>NH cois prepared by dissolving tetramethylsuccinic acid in aqueousammonia ; the solution is evaporated and the residue heated at 230"for several hours in a sealed tube; the compound crystallises from Rmixture of benzene and light petroleum in flat needles melts at 187",arid may be distilled without decomposition ; i t may also be preparedby heating the auhpdride with aqueous ammonia at 100".Thephen?yZimide C,H,,<CO>NPh is obtained by the action of anilineon the acid or anhydride and crystallises from dilute alcohol or amixture of benzene a,nd light pctroleum in needles melts a t 88" andis insoluble in cold water.By treatitig tlhe acid with phenplhydrazine only one compound isobtained which crystallises in flat lustrous needles melting at124"; it may be volatilised without decomposition and has theformula I > or I >N*NHPb. The anhydridei u the sole product formed by the action of phosphorus pmtachloridecoC bIe2*CO*lfH- CMe,+COCMe2*CO*NPh CMe,*CORGANIC OHEMISTHY.29 1on tetramethylsuccinic acid or its salts. With resorcino1 the acidjields a fluorescein derivative which dissolves in acids with a redcoloration and a green fluorescence. J. B. T.Homologues of Male'ic Acid. By C. A. BISCHOFF (Ber. 23,3414-343;3).-A reply to Anschutz's paper (this vol. p. 176).The affinitj of sodium for oxygen is greater than that of hydrogen,conseyuently in bydrogen sodium carbonate the oxygen of the groupONa is at a greater distance from the carbon atom than that of thegroup OH; in carbonic acid however the oxygen atoms of bothhydroxyl grmps are equally distant from the carbon atom ; hencec.ollisions readily occur and the compound decomposes into waterand carbonic anhydride.The same principle is illustrated byreference to acetaldehyde arid ohloi*al hydrate A comparison isthen institated by means of models between succinic and maleicacids on the one hand and symmetrical dimethylsuccinic and pyro-cinchonic acids on the other ; i t is shown that the hydroxyl groupsapproach as closely as in the case of carbonic acid. As regards theintiuence of the other atoms or groups in the molecule the elimirrs-tion o€ two hydrogen atoms from succinic acid or their displacement,hy two methyl groups facilitates the formation of mbydrides. It isproposed to determine what influence the ethyl and methyl groupshave on the elimination of water from maleic acid.By the actiou of bromine on propenyltricarboxylic acid carbonicanbydride and bydrogen bromide are evolved and the resultingsuccinic acid derivative C0OH.C HMe*CHBr.COOB yields citraconicacid on distillation whilst by the action of bydrocldoric *acid a t160° mesaconic acid is formed.Ethy Imale'ic and ethylfumaric acidsitre prepared in a similar manner from butenyltricarboxylic acid.Uisubstituted maleic acids may be obtained from the correspondingsuccinic anhydrides (compare Bischoff and Voit Abstr. 1890 743).Eth!~lmethyEmaleac anhydride is a colourless oil which boils at 237",is soluble i n potash and is reprecipitared unchanged by hydrochloricacid. Xeronic anhydride is formed in the same way from diethyl-succinic anhydride. .J. B. T.Combination of Malic Acid with Potassium Sodium Molyb-date and with Acid Sodium Molybdate.By D. GERNEZ (Compt.rend. 111 T92-794).-Thc salts were added gradually to a solutionof a defi~iite quantity of malic acid the totcrl volume of liquid beingkcpt constant and the rotatory power was determined in the mannerpreviously described. With potassium sodium molybdate,K,0,2N~0,3M00~,14E,O,the Isevorotatory power at first increases in proportion to the quantityof salt added and attains a maximum when three equikalents of acidare present for each equivalent of salt. Subsequent variations inrotstory power indicate the formation of compounds containingrespectively 3 equivalents of acid and 2 of the salt 3 equivalents ofthe acid and 3.5 of the salt aud 3 of the acid and 6.5 of the salt.With malic acid and ths acid sodium molybdate 3Na20,7N00* th292 ABSTRAOTS OC OEEMIOAL PAPEnS.variations in rotation indicate the formation of a compound of3 equivalents of acid and 1 of the salt and a cornpound of equalequivalents of the acid and the salt the phenomena being analogousto those observed with ammonium molgbdate although the rotatorypowers are somewhat larger. C.B. 13.Ethyl Isobutenyltricarborrylate. By C. A. BISCHOFF (Ber. 23,8395-3399) .-Auwers and Jackson have shown ( Abstr. 1890 1098)that the compound obtained by the action of ethyl methylmalolrateon ethyl bromisobatyrate has the formulaC Me (COOE t),*CH,*CHMe*C OOEt,and when h ydrolysed yields dimethglglutsric acid with elimination ofcarbonic anhydride. The author had howecer previously prepared,in I) similar manner an identical conipound from ethyl isobutenyl-t.ricrlrboxylata and methyl iodide which he considered to bo trimethyl-mccinic acid.Further investigation has shown that " ethyl iso-butenyltricrtrboxjlate " consiRts of two compounds of the formulruCO OEt.CMe,*C B ( COOE t)a COOE t*CHMe*C H;C H (COOE t)?respectively and that on hydrolysis and elimintltion of carbonic:anhydride it yields a mixture of a-methylglutaric acid and dimethyl-mccinic acid which may be separated by fixctional dietillation. Notrimethylsuccinic acid could be isolated from the methyl iodide andethyl isobnt~nyltricar~oxylate product which therefore consist8only of dimethglgliitaric acid. Trimethylsnccinic acid has however,previously been prepared and is known hy the name isopimelic acid(compme this vol.p. 289).andJ. B. T.Action of Nitrous Acid on Amido-derivatives. By E. A.KLOIIBIE (Rec. Trav. Chim. 9 134-154).--The action of nitrous acidon the following compounds has been investigated by the author i norder to determine the influence on the action of the accumulation ofuegakive groups in the amido-derivative.Nitrous acid acts on methyl amidoformate to farm methyl alcohol,with evolution of nitrogen and carbonic anhydride. With the samereagent ethyl methyhmidoformate yields a nitroso-derivative,NO*NMe*COOEt which i R a red liquid of sp. gr. 1.133 at 15" boilingat 70" under a pressure of 27 mm. Methyl methylamidoformate alsoforms a nitrom-compound NO*NMe-COOMe having similar proper-ties to the last-named compound.hlethyl ethylamidoformate inaqneous solutioa is acted on by a current of nitrogen trioxide andforms a nitroso-derivative NO*NEt*COOMe which is a dark-oraugeliquid of sp. gr. 1.143 at 15'.Methyl acetylamidrtforrnate which is obtained by the achion oE ethylmethylcarbamrcte on acetic chloride at a moderate heat is a crystd-line substance which melts at 93" and is very soluble in water,alcohol ether chloroform and cryatttllisee easily from benzene. 0 1 1treating an aqueous solution of thiR substance with nitrogen trioxide,decomposition occnrs according to the equation CH&O*NH*COOMo + HNO = CH,*COOH + N2 + CO -t MeOHORQANJC OHEM ISTRY. 293Methyl imidodiformate NH( COOMe) is prepared by mixingmethyl cirloroformate (1 rnol.) and methjl amidoformate (1 mol.) with 4part,s of tolnene arid acting on the mixture with sodiiim (1 mol.).Afterfiltration of the product the unattacked sodium i s removed from t11eresidue and the mass is treated with dilute sulphuric acid wliichyields up to toluene a crystalline substance melting at 134" ; this isvery soluble in water. alcohol acetone and chloroform slightlysoluble in ether and almost insoluble in light petroleum. Nitrous;wid has no action whatever on this substance neither has i t anyaction on ethyl dimethylamidoformate or on the corresponding methylderivative.Eth!jl methylacetylamiiJoformute cannot be made by acthg onethyl nitrosomethylamidoformate with acetic arihydride or on et.hylniechjlcarbamate with the same reagent; but in presence of ziucchloride the reaction occurs in the latter case.Ethyl metliylcarb-amate (60 grams) acetic anhydride (30 grams) and zinc chloride(4. grams) are heated for some minutes a t tlie boiling point ot'themixture until a yellow coloration is produced; the liquid is ex-tracted with ether and yields on distillation a liquid which boilsat 189' (corr.) and hrls i t sp. gr. 1.083 at 15" its melting point being8-9".Ethyl uiti~osomethylamidoformate NO*NMe*COOEt. This red liquidis dissolved i n all proportions by alcohol ether and benzene and is butslightly soluble i n water although distillable with steam. The analogyin the compmition of this substance to that of ethyl nitromethyl-carbamate led the author to treat it with ammonia which does notreact except in the presence of water when it forms ethyl carbaniateand methyl alcohol with evolution of nitrogen pointing to the xorma-tion of a compound NHMe*NO which immediately decomposes.Aqueous solutions of mono- and of di-methylamine react similarly toform the componnds NHMeeCOOEt and NMe2*COOEt boiling a t 165"and 14'7" (corr.) respectively.Ebhyl ethylcarbarnate reacts on thesubstance with formation of nitrogen carbonic anhydride aiid ethylmethylamidoformate. I n contradistinction to the nitro-derivative,NO,*NMe-COOE t which yields with ammonia an acid nitr~rnii~e,N HMe-NO the nitroso-derivative f urtiishes only decompositionproducts of a corresponding nitrosamine NHMe*NO ; the authorendeavoiired to isolate its potassium and barium salts bnt was an-successful.Mineral acids decompose ethyl nitrosomethylamido-formate with substitution of hydrogen for the group NO ; oxidation iseifected by an acid solution of potassium perwanganate but thenitroso-compound is not converted into the nitro-compound.By reductiou of ethyl nitroso~nethylamidoforriiate with zinc-dustand acetic acid a colourless solution is formed having strong reducingproperties and probably containing the hydrazine NH,*NMe*COOEt ;but this the author was unable to isolate o r to obtain a condensationproduct of with aldehydes. At the same time a small quantity of awhite powder which melts at 127-128" and sublimes at 180" isobtained ; this appears to be ethyl dimethyltetrazoriedicarboxjlat,e,N,(NMe.COOEt),. This substance is also formed when the liquidresulting from the reduction of a solution of the zlltroso-compouudNitrous acid does not act on this substance294 ABSTRACTS OF OHEMIOAL PAPERS.is oxidised by potassium permanganate ferric chloride or brominewater the last reagent affording the better yield.It is soluble i nalcohol benzene acekone or acetic acid but is insoluble i n water,ether light petroleum or solutions of the aqueous hydroxides orthe mineral acids.By similar reactions methyl nitrosoamidoformate yields tbe tetr-azone N2(NMe*COOMe)2 which melts at 184" ; and methyl nitxoso-methylamidoformrtte the correspondinq derivative N2( NEt*COOMe)?,me1 ting at 88-89'. The author concludes with theoretical specula-tions as to the rationale of the reactions.T. G. 3.Reduction of Glycuronic Acid by Sodium Amalgam. By H.THIKRFELDER (Zait. physiol. Chew. 15 71-i6 ; compare Abstr.,1%7 717 ; 18P9 337).-Pure sodium glyciironate was dissolved infive times its weight of water in a loosely-stoppered flask and a littla2.5 per cent. sodium amalgam added when hydrogen was evolved ;the liquid was then neutralised by sulphui*ic acid and more amalgamadded; after some weeks all the glycuronic acid had disappeared.The liquid w w filtered acidified with sulphuric acid and excess ofalcohol added ; the sodium sulphate thus prccipitated was filtered off,and the filtrate evaporated to dryness on the water-bath with thenddition of barium carbonate. The residue was taken up wiih water,filte-red concentrated acidified with salphuric acid and extracted witha mixture of alcohol and ether.The extract was evaporated to a syrup,when after a Fthort time small colourless crystals were deposited ;on recrystallisation from water rhombic crystals 1 cm. long wereobtained. Details are given relating to the measurement of the ci-ptals.The substance has a slightly swept taste is readily soluble in water,hut only sparingly in alcohol. It melts at 178-180" and has thecomposition CsHl2O7. Its barium calcium and potassiuni salts wereexamined. Examination of the solubilities and circular polarisation(the free acid is optically inactive) excluded gluconic and gdactonicacids. It does not reduce Fehling's solution so it cannot be nisnniticacid.Similar considerations lead to the conclusion that i t is noteither of the three niannonic acids so it is not the same as anyknown acid with the formula C,H,,O,; the nature of the new acidmust therefore be the subject of renewed investigation.W. D. H.Action of Methyl Iodide on Furihrylamine. By M. ZENON1(Guzzetta 20 513-557).-Furfurylamine may be readily preparedin considerable quantities by reducing furfuraldoxirne with alcoholand sodium. The yield is 20 per cent. When a solution of furfuryl-amine (1 part) in twice its volume of methyl alcohol is heatedwith methyl iodide ( 5 parts) the product after purification is awhite crystalline powder which melts at 118-12Uo and has thecomposition C,A,,ONI. This substance has the general properties ofthe iodides of the organic bases.It is soluble in water a.nd alcohol,and is reprecipitated from the aqueous solotion on addition of potash:The correspond- Its constitution is probably CH<CH:Q*CH2*NMe,ICH.ORGANIC CHENTSTHY. 2 95ing hydmx;de is formed by the action of moist d v e r oxide on theiodide and mag be obtained as a deliquescent crystalline mass whichabRorbs carbonic anhydride from the air. The ch2oride is obtainedby treating the iodide with fresh moist silver chloride. It is ~1 deli-quescent crystalline compound. The aurochloridp C8H140NCl AuCI,,platinochloride and picrate are yellow crvstnlline compounds ; thelatter melts with decomposition at about 180".On distilling the hydroxide an alkaline liquid having a11 odourresembling that of trirnethylamine and an oily product which isresinified by hydrochloric acid pass over.Action of Acid Chlorides on Bases in presence of Alkalis.B y C.ScaoTrEN (Ber. 23 3430-3431).-Polemical remarks onMarckwald's paper (this vol. p. 181).S. B. A. A.Pyromncic and Dehydromucic Acids. By M. ZENONI (Gazzetfn,20 517-580).-The author further confirms the results obtained byOliveri and Peratoner (Abstr. 1890 1242) ; both the solid product ofthe distillation of mucic acid and the mother liqoor after mfficieiltpurification yielding ordinary pyromucic acid melting at 132-13.3".I n the course of the experiments a considerable quantity of a reddish-yellow residue consisting of debydrornucic acid. was obtained. Thiscompound would appear to be more particularly formed when mucicacid is distilled at a low temperature.'l'he methyl salt of this acid,C,H20,Mez crystallises from water in large white needles and meltsat 112".The hydrazone CIOH1*CO*N2H2Pb obtained by heating the theore-tical quantities of pyromucic acid and phenylhydrazine crystallisesin white needles and melts at 142-143" ; its solution i n concentratedsulphiiric acid is coloured deep violet on the addition of ferricchloride. S. B. A. A.I t i s not affected by treatment with bromine or nitric acid.Bromobenzonitriles. By M. SCHOPFF (Ber. 23 3435 -3440).-The best method of preparing these nitriles is to distil the correspond-ing brorriobenzoic acids wikh lead thiocyanste. The yield of nitribappears to be better the lower the melting point of the acid,01.thobro.mo2,pn,.onitriZe is formed by distilling orttiobromohenzoicacid ('20 grams) with lead th'ocyanate (36 grams) and purifying theproduct by steam-distillation. It crystnllises in white needles meltsat 51" arid boils at 251-253" (uncor.) under 754 mm.pressure. Itis easily soluble in hot water and alcohol and has a characberisticodour resembling that of benzaldehgde and benzonitrile. The yieldamounts to 4.5 per cent. of the theoretical. Orthobromobenzonitrilecan also be obtained by distilling orthobromobenzamide with phos-p boric anhydride.Ortlrobromobenzoic chloride prepared by the action of equal weightsof phosphorus pentachloride and orthobromobenzoic acid is a colouy-less liquid which b d s at 241-243" (uncorr.) under 757 mm.pressure,and gradually solidifies after tt time. It has a n odonr resembling thatof benzoic chloride but less pungent. It is slowly decomposed hgcold water more quickly by hot water and reacts very energeticall296 ABSTRACTS OF OHEMlOAL PAPERS.with ammonia. Orthob?.onzl,be?azamids prepared by treating thechloride with finely powdered ammonium carbonate a t the tempera-ture of the water-bath cry~trtllises from hot water or alcohol i u long,hard needles melts at 156" when heated rapidly and sublimesabove 100".Metnhromobenzonitrile is obtained by distilling metwbromohenzoicacid with lead thiocyanate and is extracted from the distillate witliether after the uiirtltered acid has been neutralised with dilute am-monia.Parnbromobenronit ri!e is best prepared from parabromo benxamid eby distillation with phosphoric anhydride and purif~cation of the pro-duct by steam-distillation.Owing to the high melting point of para-bromobenzoic acid only 3.3 per cent. of the theoretical Field isobtained on disbilling it with lead thiocyanate. It crystdlises fromhot water o r alcohol in slender white needles melts a t Il3" is some-what less volatile with steam than the ortho-compound sublimes 111white needles and boils a t 235-237" (uncorr.).When orthobromobenzonitrile is nitrated and the product hydro-lysed it is converted into orthobromometanitrobenzoic acid meltingat 179 -18UO. Parabromobenzonitrile when treated in the same way,yields parabromometanitrobenzoic acid melting at 193".The nitra-tion is best effected by means of a mixture of potassium nitrate andsulphnric acid. By employing f uniing nitric acid the nitrile remainsunaltered.Orthobromo.171~taniirr,benzonitrile crystallises from water in needles,melts at 117" and is volatile with steam.ParctbromometaiLitrob~!l~zoiLitrite crystallises in white needles meltsat 120" i R not so volatile with steam as the ortho-compound dissolveseasily in hot water aloohol and acetone less easily in chloroform andbenzene and is insoluble in light petroleum. The amide is aloneformed i f the parabromometanitrobenzonitrile is allowed to remainin the nitric acid mixture for tl Abort time. The amide forms colour-less needles melts at 156" and is not volatile with steam.It crystallises in needles melts at 38O and boils at 22.5".E. C.R.Action of Methylchloroform on Phenol in presence of Potas-sium and Sodium Hydroxides. By P. BIGIKELLI (Chem. Cent?..,1890 ii 620 from Ann. C%m. Farm. 12 65-68).-With the objectof genrralising the reaction between chloroform and phenol illpressnce of potash by which hydroxyaldehydes are produced theauthor substituted methy1chloroforni for chloroform when if the re-action were similar hydroxybenzyl methyl ketone should be produced.Instead of this a substance of the formula C14HE,,0? is formed whichthe author regards as diphenyletbylidene ether CH,:C(OPh),. I t isvery soluble in ether and melts at 95-96'. It does not dissolve inpotash neither does it react with phenylhydrazirie. With brominewater a compound of the formula CI4H,,Br2O2 is foiwied without anyhydrogen bi-omide being produced.It crjstallises in plcttes whichmelt at 125".A secoiid substance is formed in the above reaction a liquid whichdiBtila vvit,h steam ; after drying over siilphuric acid the analysisp v e the formula C,H,O which agrees with that of orthobydroxyORGANIC ChEMISTRY. 297acetophenone. It does not however appear to combine with phenyl-hydrazine or with hydroxylamine. By treating it in methyl alcoholsolution with sodium amalgam a crystalline substance smellingstrongly of oil of roses was obtained.Tetrachlorophenol. By L. HUGOUNENQ (BUZZ. SOC. Chim. [3] 4,8-9 ; compare Abstr. 1890 2il).-Tetrachlornnisoil is heated withhydriodic acid of sp.gr. 1.5 (4 paris) in sealed tubes at 145-148"for 20 hours and from the solution of the prodiict in aqueous sodatetrachlorophenol is precipitated on the addition of hydrochloric acid,and after washing and drying is crystallised from light petroleum.Thus prepared it forms white needles melts a t 152" is sublimable,and boils a t 278" with decomposition. Tebrachlorophenol is insolublein water but dissolves in organic solvents; the alcoholic solutiondecomposes carbonates and seems not to be poisonous. A mixture ofnitric and sulphoric acids decomposes the substance with formationof chloronitroquinones. The aut hoi* has prepared the acetyl deriva-tive C6HC14Ac and the ammonium silver lead and copper salts.J.W. L.T. G. N.Constitution of Thymoquinone and /?-Hydroxythymoqui-none Derivatives. (By G. MAZZAHA Qnzzettn 20 481-485) .-In a previons paper (see Abstr. 1890 Y65) the preparationo f 13-hydroxythymoquinone from carvacrol [Me 0 Pr OH =1 3 6 4 51 was described. To charncterise this compound morefully the anilide and toluidide [NHPh or NH*C6H4Me = 21 wereIwepared by boiling the alcoholic solution of the quinone with aniline,01' toluidine respectively. The anilide crystdlises from alcohol inminute deep-hlue scales dissolves in alkaliue hydroxides forming aviolet solution and melts a t 185-187" whilst the isomeride derivedfrom a-hydroxjthymoquiiione melts at 135". The toluidide t h ocrjstallises i n blue scales which melt however at 196-197" ; whereasthe corresponding isomeride melts at 165'.I t is noticeable that in compounds derived from thymol the melt-ing point is lowered in passing from the nitro- to tlte dinitro-dei.ivatives and from the hydroxyt hymoquinone to either the anilideor toluidide whilst the reverse occurs in the corresponding com-pounds from cnrvacrol.The author regards it as finally estqtliahed that the B-bromo- andp-bromohydro-thymoquinone tire really a-derivatives [ Br = 21.Thymoquinone Dioxime.By F. KEHBMANN and J. MESSINQER(Ber. 23 3557-356t).-As already shortly mentioned (Abstr.,1890 140;3) thymoquinono dioxime C6T32Pr3.Me(NOH)2 may beobtained by the action of hydroxylamine on thymoquinone monoxime(nitrosothymol). In order to prepare it a hot saturated alcoholic:solution of the latter is hiled with double the theoretical quantity ofliydroxylamine bydrochloride the acid set free being nearly neutral-ised from time to time.The rebulting crystalline powder is dis-solved in warm soda precipitated by acetic acid and recrystn.llisedfrom boiling alcohol. It forms yellowish-white granules n. hich areS. B. A. A.VOL. LX. 298 ABSTRAOTS OF OHEMIOAL PAPERS.insoluble in water and ammonia sparingly soluble in cold alcoholand acetic acid and readily in solutions of the caufitic alkalis formingRalts which are decomposed by carbonic anhydride. It becomesbrown at 200" and decomposes with evolution of pas a t 255". Itssolution in soda has the cQlonr of an alkaline solution of potassiumferricyanide andon the addition of very concentrated alkali the sodiumsalt separahes out in golden-yellow prismatic crystals which are verysoluble i n water.The dioxime is not identical with the yolgthymo-quinone dioxime described by Liebermann and Ilinski (Abetr. 1886,239).When an alkaline solution of potassium ferricyanide is added to aRimilar solution of thymoquinone dioxime a green flocculent precipi-tate of dinitroscscumene separates. It has an odour resembling that ofiodine and of thymoquinone and is volatile with steam. undergoingconsideraldle decomposition at the same time. It is soluble in alcohol,ether and acetic acid with an intense green colour the solutions alsompidly undergoing decomposition. In the dry state it is fairlystable and melts a t 72" to a greenish-yellow liqiiid which tbeusolidities and again melts a t 130° with decomposition.The authorsregard i t as most probable that the compound has the formula,When boiled with nitric acid of sp. gr. 1-35 it is converted iiitoparadinitrocumene C6H2MeP~( NO,) which crystallises from hotdilute alcohol in large colourless thick prisms melts a t 77-78" andis readily soluble in alcohol ether acetic acid and benzene. Whenreduced with tin and hydrochloric acid it8 yields paradio;midocumene,which may be more readily obtained from thymoquinone dioxime bysuspending it in alcohol warming with an excess of stannous chlorideand hydrochloric acid evaporating the alcohol diluting with water,and adding aqueous Rod%. The base is extracted with ether andthe solution agitated wit.h concentrated hydrochloric acid as longas separation of the hydrochloride takes place.The latter is dis-solved in the least possible quantity of hot water and concentratedhydrochloric acid added i t then separates in well-developed colour-less four-sided plates which are quite stable in the air whereas thefree base readily undergoes oxidation. The diamidocnmene hydro-chloride obtained by Liebermann and Ilinski (Zoc. cit.) is identicalwith the foregoing but the latter investigators do not appear to haveobtained it quite pure.On boiling paradiamidocumene hydrochloride wit,h acetic anhydr-ide and anhydrous sodium acetate i t yields the diacehjl compound,C,,H,,,N,O crystdlising in slender white silky needles and meltingill 260".H. G. C.Cholesterol. By K. OBERM~~LLER (Zeit. physiol. Chem. 15 37-48 TWO forrnulse C,6H,0 and C2,HM0 (Reinitzer Abstr. 1888,1076),have been asmibed to cholesterol (cholesterin). The chief object of theprzsent research was by the analysis of certain cholesterol compounds,to determine which is the correct one. The general result of thOR(3ANIC CHEXISTRP. 299analyses is that Reinitzer's formula is correct. The Collowing c3m-pounds were prepared :-Potassium cholest.roxide CnHUOK was prepared by placing potas-sium in an ethereal solution of cholesterol. I t agrees i n all its pro-perties with Reinitzer's sodium cbolesteroxide.Cholesteryl propionate C1,H15*C3HS02 was prepared by heating a,mix t8ure of cholesterol with propionic anhydride on the water-bathfor half-an-hour ; on cooling it sets to a fatty mass ; tbis is extractedwith ether and the propionate precipitated from the extract bytillcoho1 in the form of rhombic plates ; melting point 98".It is easilysoluble in ether benzene arid carbon bisulphide sparingly soluhlc inalcohol. After fusion. there is on cooling a play of colours observed,blue green orange and red in the order named by reflected light;the complementary colours are seen by transmitted light. I n orderto use this reaction as a test for cholesterol the latter must first beobtained in a pure condition ; it may be most readily freed from thefats with which i t is usuallv mixed by the method of saponificationbefore described (Abstr.1890 1474).Cholesteryl benzoate C,7H4b*C,H502.-This is best prepared by theaction of benzoic chloride on cholesterol ; and this preparation maybe used for the quantitative estimation of cholesterol. The crystalsare plates which show two melting points namelg 145'and 178". Acompound with similar propertieR was prepared from isocholesterol.Cholesleryl phthalate CsH,(COO*Cz,H,5)2 was prepared by herttinqphthalic anhydride and cholesterol at 180" and crystals obtained bythe addition of alcohol to a hot ethereal solution. It is sparinglysolnble in cold ether ; melting point 282.5".Chotesteryl benzy Z ether. CziH45*O*C7H7 prepared by heating sodiumcholesteroxide and benzyl chloride at loo" mas crystallised from analcoholic-ethereal solutim in thin plates me1 ting at 78".Cholesferyl propionate dibromide.C27H&r2*C3R50z.-This additiveproduct is similar to that prepared previously by Wislicenus andMoldenbaaer c27Bd6Brz0 (AnmaZen 146 178) by the action ofbromine dissolved in carbon bisulphide on pure cholesterol and tothat prepared by Reinitxer (Wiener Momtsh. 1888 Heft 5 ) by theaction of bromine on cholesteryl acetate. This substance is impor-tJant as the relation between carbon and bromine gives a key to theformulft of cholesterol. Cholesteryl bromobenzoate C7HQBrO2~CZ,H4~,was also prepared and analped. W. D. H.Derivatives of Diphenylamine. By 0. ERNST (Ber. 23 3423-3430) .-Amidochlorodiphenylamin~,NHPh*CsH,Cl*NH [NHPh NHZ C1 = 1 2 51,is prepared by t.he reduction of the nitro-compound with stannonschloride tin and hydrochloric acid in alcoholic solut,ion ; it crystal-lises from alcohol iu long colourless needles melts at 99" and isreadily soluble in ether benzene and cbloroform.The picratecrpstallises in yellowish-brown plates.N HPh*C,H,Cl*NHAc,The acetyl derivative,x . 300 ABSTRACTS OF CHEMICAL PAPERS.is formed bg the action of the calculrtted quant,it,v of acetic anhydrideat ~uV mil crystallises from alcohol in silky lustrous needles whichmelt at 150".Eth~nylo~thamidochlo~od~pph~nyl~~m~ne CMeGN -> CsBJCI is ob-tained on boiling the amido-compound with excess of acetic anhydride ;it crystnllises with difficulty in small coloiirlcss needles. The plafino-chloyicle crystallises from alcohol in long brown needles.Phen~lux~midoahlo~obe~~~ene N < E y > CaB3C1 is prepared by theaction of nitrous acid on orthamidochlorodiphenylamine ; it crystal-lises from alcohol in colourless lustrous needles and melts a t 1%".By the cxidation of an acid solution of amidochlorodipheriylamin~m-itrh ferric chloride a violet-red (lye is produced the hydrochloride ofwhich crystallises in yellowish-green metallic lustxous needles ; thepicrate is deposited in dark-green needles ; the sulphafe resembles theIlydr+ochloride.The free base is obtained by the action of ammonia011 the salts as a brownish-red crjstallitie precipitate.On heating orthamidochlorodiphenylamine mit,h an equal mole-cular proportion of aniline hydrochloride at ZOO" a deep-blue colouringmatter is formed ; dilute solutions exhibit.a coprer-red fluorescence.The addition of ammonia changes the colour to reddish-violet witliyellow-red fluorescence. A similar substance is formed by heatingorthamidoc.hloro~iptienylarnine bydrochloride alone. This compoundprobably bclongs t o the fiuorincliue group but its constitution likethat of the previonq dye is unknown.NPhDzIiitropl(enylusnidotoluyZallline C6H,(N0,),.N~-1csH~~e.NH,[NH (NO,) = 1 2 4; NH NH = 1 21,i s prepared by the action of dinitrochlorobenzene on orthotolaylene-diamine ; it crystallises from alcohol in brownish-yellow needles meltsat 147" m d is iiisoluble in water but readily dissolves in benzene or(Moroform. The compound is soluble in acids with a pale-yellowcolour.J)initroy,lienylazimiclotoluene N<$H3Me>N*C6H3(N0,)z - is ppe-pared by the action of nitrous acid 011 t,he previous compound; itc.rystallises from ~lcohol in small pale brownish-yellow needle<,melts at.186" and is insoluble in ether but readily dissolves in benzene,chloroform or glacial acetic acid.Dinitroplim yZ-,9-naphthylumine C,oH7*NH*C6H3(N02)2 [NH (NO?),= 1 2 41 is prepared from dinitrochlorobenzene and /3-naphttiyl-amine ; i t is somewhat sparingly soluble in alcohol from which it isdeposited in brick-red crystals and ~nelts at 179".Dinitr~hen.yl-p-naphdhoi C,,H,*O*CsH,(NO& [ 0 (NO,X = 1 2 41,is obtained from P-naphthol as a pale-yellow viscid liquid whichsolidifies after some time and crystallises from alcohol in stellategroupa of pale-yellow needles melting at 95".The corresponding diatnido-derivatives are prepared by the redoc-tion of these t h e e n i t ro-compounds ; d.ia~iidopkenylaii~idotoluyEamiriORGANIC CHEMISTRY.30 1and diamidophPnyt-P-n(~p~l~ylani~ne yield azo-derivatives on oxidatior,,but diamidophenyl-P-naphthol does not yield any colouring matter.Action of Phosphorus Pentachloride on Hydroxyazobemene.Ry K. HEUMANN and R. PAGANINI (Ber. 23 3550-3354).-Theaction of phosphorus pentachloride on hjdroxyazobenzene was firstexamined in 1870 bg Kekulh and Hidegh (BPY. 3 235). who obtaineda compound which they believed to be hydroxgazohenzene,J. B. T.N*Ph0<hc6H4*0HThe reaction was also examined by Wallach aud Belli and Wallachand Kiepenheuer (Abshr.1880 5.56 ; 1889 393) who also found theformula CI2H1,,N2O2 and showed that the substance is reconverted bysodium in alcoholic solution into hydroxyazobenzene but that I tdoes not yield an ncetyl compound and is insoluble in alkalis. Thelast two properties are not in filvour of the above constitutionalformula and the authors have therefore reinvestigated the reaction.They find that when equal parts of hydroxyazobenzene and phosphoruspentachloride are warmed on the water-bath until evolution ofhydrogen chloride ceases and the product no longer dissolves inalkali with a dcep-yellow coloixr a mixture o€ two compounds isobtained which may be separated by the difference in their solubilitiesin alcohol. The one agrees in all its properties with the so-called11 y droxgaznxybenzene and crystallises from acetone i n golden-y ellowplates melting a t 148".It was however found to contain phosphorus,the empirical formula being CjgH?,N6O4P which agrees equally wellwith the figures for carbon hydrogen and nitrogen gi-i-en by tbe inves-tigators named above. Jts ready conversion into hydroxyazobenzeneis due not to a reducing action b u t t o the alkali present as zinc-dustand alcohol are without action on it. It is therefore beitzeneazophenyl1. hosphute PO(O*C6H4*N:NPh)3 and may also be prepared by acting 0 1 :the potassium salt of hydroxyazobenzene with phosphorus oxychloride.The second product of the reaction crystallises in broad orangs-yellow needles melts a t H8' and siiblinies in golden plates.It isidontical with the pnrnclilorazrobenzene prepared by Heumann andMentha (Abstr. 1886 874) from paramidoazobenzene.Thiophenylhydrazine. By J. RUHL (Ber. 23 3482-3483).-Thiophetqlhydrazine S( CRH,*NH*N H?)? may be readily obtainedfrom thioaniline by diazotising adding sodium hydrogen sulphite,and reducing with zinc-dust. On the addition of concentrated hydro-chloric acid the lrydrochloride separlctes out as a sparingly solublesalt which IS collected pressed dissolved in water and treated withalkali which precipitates the free base in small plates. The latter*after washing with cold water is recrystnllised from the hot liquid,and separates in yellowish lustrous plates which on drying form i hmass resembling paper.It melts at 115" decomposes at 130° issparingly soluble in cold more readily in hot water easily in alcoholand reduces Fehling's solution in the cold. Its hydrochloride andsulphate foim white powders.H. G. C302 ABSTRACTS OF CHEMICAL PAPERS.T biophenylh ydra zine readily corn bines with 2 m 01s. ben zaldeh y de,forming the crystalline hydrazone S(CsH,*N2H:CHPh) ; i t a h corn-bines with phenylcarbamide.Diamylphenylhydrazone. By S. G RIMALDI (Chern. Centr. 1€!90,ii 553; trom L'Orosi 13,19+-193).-1n manner similar to tbat usedfor the preparation of nonylmethylphenylhydrazone (Abstr. 1890,1394) the author has now prepared its isomeride diamyZyhenyZh?ydr-azone from diamyl ketone which was obtained by the dry distillationof calcium capronate. The ketone combines readily with phenyl-hjdrazine the elimination of water commencing at ordinary tern ye-mtures and considerable development of heat occurring during theprocess.Dinmyl~henylhydrazorLe C( C,H,,),:N.NHPh is an oily,slightly-red liquid having a strong agreeable odour bnt burningta te. It is neutral insoluble in water soluble in ether alcohol,chloroform &c. ; sp. gr. = 0.93896 at 0". It remains fluid at -9*5O.Isomeric Forms of Orthonitrophenylglyoxylic Hydrazone.By A. KRAUSE (Ber. 23 3617-3622 ; compare Pelidin Abstr. 1890,1117).-The hydrazone is converted into an isomeric form (m. p.188-189") by the action of aqueous potash in the cold ; soda is how-ever without action. Both compounds yield lead salts from which,on treatment with sulphuric acid the original substances are regene-rated.Isatic hydrazone together with a little aniline is formedirom each compound on reduction with stannous chloride.By heating the hydrazone with sodium ethoxide and twice themolecular proportion of ethyl iodide in a sealed tube for three hour3at 13U-l4O0 the ethyl salt is obtained crystallising from alcohol illvellow prisins melting at 126-128". No diethyl derivative could beprepared.When treated with hydrochloric acid the hydrazone decomposesinto ammonia aniline and resinous matters.Metanitrophenylglyoxglic hydrazone is dissolved in alcohol andtreated with aqueous potash ; a sparingly soluble salt is formed whichis allowed to remain for 24 hours ; on the additioo of hydrochloricacid evolution of gas takes place and a green insoluble compound isobtained which melts at BP-285".The aiithor considers t h a t from these results the formnlse previouslyadvanced for the tKo orthonitro-derivatives are no longer probable,atid be suggests that the isomerism of the compounds may be of astereometric nature similar to that of many oximes and explicableby the same hypotheses.Phenacyl Sulphide.By J. TAFEL and A. MAURITZ (Bey. 23,3474-34753 .-In a paper recently published by Delisle (Anualen,260 250) the latter bas described acetotryl phenyl sulphide and hasannounced his intention of preparing other ketonic sulphides. Theauthors have idready obtained plzenacyE suZphide S(CH,*COPh) andin view of the above paper of Delisle now publish the results ofthvi r i n res tigati on.Pheiiacyl sulphide is readily prepared by dissolviiig 100 parts ofH.G. C.J. W. L.J. B. TOR0 ANIC OHEXISTRI'. 303bromacetophenoue in 400 parts of alcohol and adding a solution of12 parts of sodilim in 400 parts of rrlcohol saturated with hydrogensulpbide cooling well during the addition and subsequently heatingfor a short time on the water-bath. I t crystallises frotn alcohol incompact colourless prisms melts at 77" is very slightly solublein hot water readily in alcohol acetic acid cbloroform and benzene,and also dissolves in cold concentrated sulphuric acid with a pliowcolour. I t is coloured yellollr by boiling alkalis and reduces Fehling'ssolution without deposition of cilpric sulphide.On treatment withan alkaline solution of hydroxylainine it yields the dioxini e,S ( C H2.C P h NOH),,which is recrystallised from acetic acid. It melts at 151" and issparingly soluble in water light petroleum and benzene readily inalcohol ether and acetic acid.S(CB2*CPh:N2HPh),,obtained by heating the sulphide with phenylhydrazine a t 100",crystallises from alcoh(J in slender colourless needles which becomeyellow in the air; it melts at 146-147'. It is readily soluble inbeuzene and chloroform almost insoluble in water and dilute acids,but dissolves in cold concentrated sulphnric acid with a yellowish-green colour.When bromncetophenone is boiled with alcoholic soda it yields acrystalline corn pound of as yet unascertained cocstitution whichseems to have the formula C16Hrd02Br.The dihydrazone,H.G . c'.Metaparadiamidobenzoic Acid. By A. ZEHRA (Ber. 23,3625-3635).-[N H C = 1 'L 41 Difurar~,ylquiiLoxalinemetncal.b-oxylic acid (? 'C'H30):N>c~H3*coOH is prepared by the action offurile on metaparadiamidobenzoic acid in glacial acetic acid sohltion ;it crystallises from alcohol in pale-yellow needles softens at 235" andmelts at 245". The compound is insoluble in benzene but dissolvesi u dilute ammonia or alkaline cltrboriat,es ; with bydrochloric acid ityields a yellowish-red colour whilst the sulphuric acid solution ischerry-red and the original substance is precipitated unchanged onthe addition of water. The barium saZt (CJ3~N204)2Ba crytjtallisesiu Dale-vellow needles.C(CdH3O):NK JDiphenylquiitoxalinemetacarboxylic acid ~pb:N>C6H,*coOH prc- CPh:Npared from diamidobenzoic acid and benzile crystallises from glacialacetic acid or alcohol in yellowish plates or needles softens at 280" andmelts a t 288".It is very sparingly soluble in organic media butdissolves in alkaline carbonates aud hjdIochloric acid. The bariiisrisalt (C2,H13N202),Ba + 3H,O crystallises from dilute alcohol in small,white needles. The ethyl salt is deposited from alcohol in whiteneedles melts at 151" aud is insoluble in ammonia.Dirnet h y 1 q uiii ma 1 inemetacar boz y lic acid > C~H,*COOH is CMe:804 ABSTRAOTS OF CHEMICAL PAPERS.prepared from diamidobenzoic acid and diacetyl ; it crystnllises fromalcohol in small white needles softens at 250" and melts at 257-260'with decomposition.It is readily soluble i n alkaline carbonates andhydrochloric acid but more sparingly in benzene or ether. Thesilver solt CI1H9N2O2Ag is obtained in small white insoluble needles.> CsH,.C OOH FMe=NC(0H):N Methyl h y drox y q uinoxd inerar box y lic acid,prepared from diamidohcnzoic acid and pyruvis acid resembles theprevious compound and crystallises in white needles which blackenat 330" without melting. The barium s d t (CloH;N203)213a + 3H20,is deposited in pale-yellow needlee.Met h'yl pl~enylenedicarboxynaetayrzradicn?.bamat~,C6H3( NH*COOMe),*COOH,is obtained from diamidobenzoic acid and methyl chloroformate ; i tcrystallises in lustrous needles softens at 300" and melts a t 35.0" withgas cvolution; it is insoluble in water but dissolves in alkalinecarbonates.Cadamidornetapheny lcarboxy lic acid CO < NH > C6H,*C0 0 H pre-pared from diamidobenzoic acid nod carbonyl chloride is deposited insnlall needles or plates which are scarcely altered at 360" ; it is verysparingly soluble except i n alkaline carbonates.Diacet y lmetapnradiamido benroic a.c*id !&H,( NH Ac) ?* C 0 OH cry s t a1 -lises from alcohol in small white needles melts at 218" with evolu-tion of gas and is sparingly soluble in dilute hydrochloric acid.Fo~myZparamidobe.nzoic acid COOH*C,H,*NH*COH [N C = 1 41,is prepared by dissolving paramidobenzoic acid in concentrated formic:acid ; i t crystallises from alcohol in short white needles and melts a t268' with decomposition.Metaniti.oformylparcimidobenzoic acid isformed by the action of fuming nitric acid on the previous compound ;it8 crystallises from alcohol in pale yellow needles and melts at 221"with evolution of gas.The silver salt is gelatinous.NH~~ethenylamidin~henylenemetacarboxylic acid,is prepared by the reduction of the nitro-compound and crystallisesfrom dilute formic acid in white needles which decompose a t 325"without melting. The hydrochloride sulphate and nitrate are crystal-line. 5. B. T.Substitution of the Anilido-group for Halogen Atoms in theBenzene Nucleus. By M. SCHOPFF (Ber. 23 3440-3445).-Th~behaviour of aniiine towards parabromometanitrobenzoic acid hasrtlreadg been described (compare Ahstr.1890 374). The authorfinds that a similar reaction takes place between auiline and ortho-bromomefanitrobenzoic acid and the corresponding ortho- and para-nitriles and amides and the sodium salts of the acids.~efalzitro-orthanilidobenztn'c acid N H PhCsH3 (NOz) GOOH pre-pared by the action of aniline on orthobromometanitrobeuzoic acid IORGAN10 UHEMISTRT. 305obtained in small straw-coloured needles by precipitating its alco-holic solution with water ; i t melts at 247 -248". 'l'he anliydroussodium salt in obtained as a brick-red compound by adding thetheoretical quantity of sodiuni to a solution of the acid in absoluterilcohol; i t absorbs moisture from the air and theu crystallises inyellow needles containing '2 mols.HzO which are lost over sulphuricacid. The barium calcium lead copper silver and mercury saltswere also prepared. The rthyl salt of the above acid crystallises fromalcohol in yellow plates and welts at 121".Mctariitrr~nraniliclobeiazonitrzle NHPh*C6H3(N0,)*CN is obtainedhy carefully heating the bromonitrile with aniline for a short time ;it crystallises from alcohol in short brick-red needles or plates andfrom hot water in needles melts a t 126' and is easily soluble inalcohol acetone cbloroforrn and benzene less soluble in lightpetroleum. Nitrariilidobenzanilide and nitrmilidobenzamide areformed in this reaction if the heating is prolonged as the hydrogenbromide liberated in the formation of the anilidonitrilc hydroljsesi t to amide.These two compounds are easily separated as the formeris only slightly the latter easily soluble in hot alcohol. Metanitro-paranilidobeiizamide crystallises in yellow needles melts a t 187" andby the further action of aniline is converted into metanitroparanilido-benzanilide.MetarLiti.o-o?.thaniZidobenzon,itri~e NH Ph*C6H3(NO2)*CN is sparinglysoluble in hot water but easily soluble it1 alcohol ; by precipithonwith water i t is obtained in lemon-yellow needles which melt a t370". Unlike the para-compound it is not hydrolysed by prolongedheating with the hydrogen bromide formed in the reaction.E. C. R.Derivatives of Parabromometanitrobenzoic Acid. ByA. GROHMANX (Uer. 23 3445-3450) .-Pal.abro)nometanitrob~nzoicchlwide NOL*C6H,Br*COCI obtained by the action of phosphoruspen tachloride on pnrabromometmitrobeiizoic acid forms yellowish-white needles melts a t 51-53" and is soluble in benzene acetone,and chloroform slightly soluble in light petroleum.When thiscompound is gently warmed with aniline parabrotnometanitrobenz-anilide is formed ; at a higher temperature and in presence of excessof aniline metanit roparanilidobenzanilide is formed. Purabromometa-witrobenzniiilide crystallises from a,lcohol in beautiful orange-yellowcrystals belonging to the monosymmetric system and melts at 156".It is soluble in alcohol ether benzene carbon bisulphide chloroform,and acetone sparingly soluble in light petroleum arid insoluble i nwater Metariitroparanilidobenzanilide forins leafy crystals melts n t216" and is soluble in alcohol benzene chloroform acetone andacetic acid but insoluble in light petroleum.Parabromometctnl'trobenzamide is best prepared by warming thechloride with ammonium carbonate.It crystallises from alcohol incolourless needles melts at 156" (compare preceding abstractl) and issoluble in alcohol ether and awetone insoluble in water lightpetroleum chloroform benzene and carbon bisulphide. Metanitro-PclrarnitlobenzanLitie obtained by heating the bromnmide with alcoholi306 ABS'IRAOTS OF CHEMICAL PAPXKS.ammonia at 180° crystallises in lemon-yellow needles melts at 227",and is soluble in acetone acetic acid sparingly in alcohol andinsoluble in water benzene light petroleum and chloroform.By the action of ammonia or aniline on ethyl parahromometanitro-benzoate the halogen i s displaced by the amido- or anilido-group ; theethoxy-group remains urinltered.Ethyl metariitroparamidobenzoate melts a t 3 45' and is soluble inalcohol benzene chloroform acetone ether acet io acid and a.uiIine,irisolnble in light petroleurn.Ethyl rnetanitroparanilidobenzoate meltsat 125" (compare Abstr. 1890 374).Toluidonitrobenzoic Acid and NaphthylamidonitrobenzoicAcid. By E. HEIDEXSLEBBN (Ber. 23 3451-3458) .-Metarritypara-(ortho)toZiiidobenzoic acid C,H4Me*NH*C6Hl,(N O,)*COOH is preparedhy heating equal weights of orthotoluidine bromonitrobenzoic acid,and glycerol in a reflux apparatus until the liquid 011 cooling solidi-fies to a brown mass. I t crystalliscs from dilute alcohol in bright-brown needles melts at 219-211° and ip easily soluble in alcohol,chloroform benzene acetic acid and ether.The sodium Fdlt! pre-pared by adding sodium to tlie alcoholic solution of the acid crystal-lises in beautiful dark-red needlcs. The ethyl salt forms bright-yellow plates melts at lW" and is easily soluble in alcohol ether,chloroEorm and benzene.E. C. R.Metamidopwra (orttio) to luido benzoic acid,is prepared hy heating the nitro-acid with alcoholic ammoniumsulphide at 120". It crystallises from dilute alcohol in white needles,melts a t 167" rapidly colours in the air and dissolves in alcohol,acetone and benzene. The ethyl salt is prepared by reducing thecorresponding nitro-compound with alcoholic ainnionium sulphide ;i t melts at 115" and is easily soluble in alcohol ether abd chloroform,slightly soluble in benzene.Met anitropcLra( para) toluidobenzoic acid,has already been described by M.Schopff. The sodium salt formsbeautit'ul da1.k-red needles. The ethyl salt crystallises in beautifuldark-yellow shining plates melts at 115- and is easily solable inalcohol ether and benzene.Jletumidopara(para)toluidobenzoic acid,c6 H ,IMe*N H*C,H,( N H2)*C OOH,crystallises from dilute alcohol i n bright yellow needles melts a tl85*5" and is easily soluble in alcohol and acetoile insoluble in water.Tho ethyl salt crystallises in colourless needles which turn blue OIAexposure to air melts at 145" and dissolves easily in alcohol ether,aud chloroform sparingly in benzene.Azimidopara( para) to1 uidobenzoic a?cid is obtaiaed by acting onmetamidoparn (para) toluidobenzoic acid (3 grams) dissolved in abso-lute alcohol (20 c.c.) with amjl nitrite (4 c.c.) and a few drops oORGANIC CHEMISTRY.307concentraked hydrochloric acid. It crystallines from alcohol inbeautilul rose-i*ed needles and melts at 271". The nitrazimido-compound is obtained by dissolving the azimido-componnd in fumingnitric acid and precipitating with water. It forms a yellowish-white,non-crystalline powder and melts at 253".0 rthamidop7ienylpara (para)tohyl amine C6H4Me*N H*C6H4*NH2 isobtained by distilling the amido-acid under diminished pressure andmag be purified by precipitation from its aqueous solution withammonia. It crystallises from water in colourless plates wbich reddetion exposure to air melts at 74" arid is easily soluble in alcohol ether.,chloroform and benzene.When dissolved in hydrochloric acid,oxidation takes place and the solution becomes red.Melanitropara-p-nnphthylamidobenzoic acid,C,H,*NH*C,H,( NO2>*COO H,is best prepared by heatiog a mixture of parabromometanitrobenzoicacid (1 part) /3-naphthylamine (2 parts) and glycerol (3 parts) toboiling in a reflux apparahs. The compound when pure isbrick-red arid is soluble in alcohol acetone and acetic acid lesgsoluble in benzene and chloroform and insoluble in water. Thesodium salt is a red amorphous powder soluble in water. The ethyls I l t crystallises from ether in beautiful bright-yellow needles meltsat 127-5 and is soluble in alcohol acetone acetic acid and chloro-form.Metanitropara-a-nnphth.ylamidohenzoic acid is prepared in the sameway as the ,%acid.I t forms a red-brown amorphous powder and iseasily soluble in dilute alcohol kc. and somewbat soluble in hotwater. The scdium salt forms a dark-red amorphous powder. Theethyl salt crystallises in beautiful red-brown plates melts at log",and is e d y soluble in alcohol benzene acetic wid and chloroform.M~tamidopara-a-nuphthylwmic~obenzoic acid,C,,H,.NH*C,H,(NH2)*COOH,prepared by reducing the nit.ro-acid with alcoholic ammoniumsulphide crystallises in white needles which become red on exposureto air decomposes at go" and is easily soluble in alcohol bcanzene,ether and chloroform insoluble in water.E. C. R.Nitration of Hydroxybenzoic Acids by Nitrous Acid. ByA. DENINGER (J. pr. C'hem. [ d ] 42 550-553).-When salicylic acidis nitrated with nitric acid the nitro-acid of m. p. 228" is the chiefproduct that of m. p. 144" being obtrtined in small quantity only. Bythe following methods each cau be obtained practically free from t.heother.Asymmetrical metanitro~alicylic acid [m. p. 228" ; COOH OH NO,= 1 2 51 is obtained by mixing salicylic acid (100 grtms) andsodium nitrite (130 grams) with water (150 grams) and slowlyadding 1.2 litres of sulphuric acid (sp. gr. 1.5%) so that the tempe-rature may not rise above IS0 vigorous stirring being kept up duringthe process. After some four hours the liquid is warmed to 50308 ABSTRACTS OF CHEMICAL PAPERS.and after several hours more the solid is filtered and recrystallisedfrom water.Consecutive metanitroiJalicylic acid (m.p. 144") is obtained by mixingsalicylic acid (100 grams) and sodium nitrite (170 grams) with water(150 grams) and adding 1 litre of sulphuric acid (8p. gr. 1-52) at 60"all at once so that the temperature may rise quickly a s otherwisemuch of the acid oE m. p. 228" will be formed. The solution of thed i d mass in water must be heated with animal charcoal for sometime to eliminate orthonitrophenol.Metanitroparahydroxybenzoic aciii (m. p. 185') is obtained by mix-ing parahydroxgbenzoic acid (100 grams) and sodium nitrite('LOO gramsj with water (ZOO grams) addiug 1 litre of siilphuricacid (sp.gr. 1.52) at 40" and heating for a long time on the water-bath. When sodium nitrite and cold sulphuric acid are added to theparahydroxy-acid no nitro-acid is formed ; but if the nitrite andsulphuric acid are nrixed first and the hydroxybenzoic acid then added,the jield of nitro-acid is abundant ; this shows that the formation ofni trosylvulphuric acid is necessary a conclusion proved by substitat-ing this acid for the mixed sodium nitrite and sulphuric acid vithgood results.Ortho- and Meta-cresotic Acid. By R. NIETZKI and F. RUP-rEnT (Ber. 23 347tj-3480).-0rthocresotic acid unites with diazo-benzene chloride in the usual manner forming an azo-dye whichis readily converted by reduction with stailnous chloride into amid-cwthocresatic acid.On the addition of concentrated hydrochloric acid,the hydrochloyide separates a s a precipitate which is readily solublei n water although but sparingly in hydrochloric acid and may bereadily purified by dissolking in water and precipitating with acid.0 1 1 diwolving it in aqueous sodium carbonate and sat,uratinp withRcetic acid the free amido-acid is obtained in smdl colourlessplates which are very sparingly soluble in the common solvents andmelt with decomposition above 300°. According to Jncobsen ortho-cresotic acid has tlie constitution [OH Me COOH = 1 2 61 andas the azo-group almost invariably replaces the hydrogen atom in thepara-position to the hydroxyl gmup it is probable that the amiclo-group in the above acid occupies the position 4.When arnidoi thocresotic acid is treated with acetic anbydrideand sodium acetate it yields a cliircetyl compound which is verysoluble and difEcult to purify.On warming it with dilute alkali theacetyl group in combination with the hydroxyl is eliminated and onthe addition of an acid the monacetyE derivative is precipitated in small,colourless needles melting at 275". On treating the amido-acid withriitrous acid a very stable diazo-compound is formed which may borecrysrnllisedfrom hotwater; on reduction,it yields a hydrazine deriva-tive. On distilling the acid with quicklime or sodium carbonate. it yieldsparamidorthocresol t h u s confirming the above assumption with regardto the position of the amido-group.When acetylamidocresotic acid is nitrated in acetic acid solution,the carboxyl group is eliaiinatcd and its place taken by the nitro-group. The tccetylamidon itrucresol thus formed crystsllises fromPhenol cannot be nitrated like this.A. G. BOttQANlC CHERL 1 STRY. 309alcohol in thick yellow needles which melt at 217"; on boilinq wit,hdilute sulphuric acid i t yialds the corresponding amidonitrocresol.This separates from alcoholic solution in long brownish-red needlesmelting at 118" and forms beautiful red crystalline salts with alkalis.On treatment with nitrous acid it yields a diazo-compound cry~tallis-ing in yellow needles which may be dried at 70-80" but explode at ahigher temperature. It is almost unalterpd by boiling alcohol but thediazo-group may be removed if a moderate quantity of alkali be addedt,o the boiling solution.'the nitrocresol t h u s formed is identical withthe one obtained by Hofmann and v. Miller which hRs the constitution[Me OH NO = 1 2 31 showing that the nitro-group has inreality 1 aken the position previously occupied by the crtrboxyl.Metacresotic acid was treated in exactly the same manner as theortho-compound. The antidometacresotic cr.cid obtained from it formssmall colo:irless plates which melt at 265". From analog? the mostprobable constitution is [OH:Me NH, COOH = 1:3:4:6],and thisis proved by the fact that on distillation with sodium carbonate,it yieldsyararnidometacresol which is converted by oxidation into toluquinone.On treatment with nitrous acid amidometacresotic acid yields Rd iazo-compound similar to that obtained from the ortho-compound ;this also yields a liydrazine on reduction. The diacetyl and moo.ncetyE compounds are also obtained i n a similar manner.The lattermay also be nitrated with eliminatioti of the carboxgl group b u t inthis case a dinitro-compound is obtained which forms thick yellowcrystals melting a t 225" arid has acid properties forming a potassiumsalt which crystallises in beautiful red needles. On warming w i t bdilute sulphuric acid it yields anzidodinitrocresoE which crystallisesfrom alcohol in ruby-red needles melting at 160" and has both acidand basic properties. On heating with acetic anhydride it yields adiacefyl derivative melting at 17;".Wheu amidodinitrocresol is treated with nitrous acid i t yields a veryexplosive diazo-compound crystallising in yellow plates.The diazo-5roup may be removed by boiling with alcohol in weak alkaline soln-tion ; the dinitrocresol thus obtained crystallises in orange-red needlesmelting at 99". The constitution of the latter can only be representedby one of the following formult-e if i t be assumed that one nitro-grouptakes the place of the carboxpl in the amido-acid,I. [OH NO Me NO = 1 2 3 61,Of these the former is the more probable as compounds in which theIiitro-groups occupy the adjacent position are usually unstable ;moreover on reduction it yields a diamido-compound which does notform an azine or quinoxaline on treatment with orthodiketones.Saligeninoxyacetic Acid.By P. BIGIXELLI (Chem. C'enfr. 1890,ii 623-624 ; from An%. Clrim. Farm. 12 69-72).-Saligeninozy-crcetie acid OH*CH2*C6Hp*O*CH~*COOH is prepared by warming sali-genin with chlorncetic acid in presence of sodium hydroxide. Themixture is first warmed on the water-bath and finally over the flarnadirectly. The mass is then dissolved in a little water and the acid11. [OH Me (N02)2 = 1 3 5 61.H. G. C310 ABSTRACTS OF CHEMlCAL PAPERS.liberated by the addition of sulphuric acid. The acid may be recrys-tallised from water and is thus obtained in white lustrous platesmelting at. 120". The solutions of the sodium and potassium salts areprecipitated by lead acet.ate calcium chloride and silver nitrate butnot by barium chloride. The lead and ca-lcium salts are powdery ;the silver salt has the formula C9H,0,Ag + 2H,O.It loses 1 mol.H20 readily but retains the second molecule somewbat persistently.By treating the silver salt with methyl iodide an ethereal salt of theformula C,,H,O is obtained which probably has the constitutionalformula OB~CH2*C~H,*O*CH2*COO*CH~L*C6H4*O*CH2*COOMe.I€ salipeninoxyacetic acid is heaied in a current of dry air a t100-108 it loses 1 mol. H20 and becomes converted into a caramel-like substance of the formula CYH803 and melting at 140'. It isinsoluble in all ordinary menstrua and dissolves only i n soda 01'potash. J. W. L.8Thionylamines a New Class of Compounds containingSulphur. By A. MICHAELIS and R. HERZ (Ber. 23 348&3482).-It has already been shown by Michaelis (Abstr.1890 617) th3tthionyl chloride readily acts on primary and secondary asymmetricalhpdrazines forming compound,s in which the hydrogen atoms of tlieNH group are displaced by the SO2 group. The authors find t h a tthe same reaction takes place even more readily with the simplenruido-compounds. The action of this reagent on aniline has alsobeen examined by Schiff (Anrden. 102 111) and Bottinger (Abstr.,1878 863). The mthors proceeded in a similar manner to the last-named dissolving 20 g r a m s of aniline in double its volume of drybenzeiie and adding 20 grams of thionyl chloride also diluted withbenzene when separation of a solid substance and developinent of heattakes place. The viscid mass is then heated in a reflux apparatus whenR further reaction takes place and tho contents of the flask becomethin.After cooling the precipitated aniline bydrochloride is filteredoff and the clear liquid distilled. As soon as the benzene has passedover the thermometer rises to 198-200" and a yellow liquid con-denses which after redistillation is quite pure and as shown by itsanalysis consists of thionylanihe S0:NPh. This boils at 200" has anaromatic and somewhat pungent odour and is slowly decomposed bywater and dilute acids and quickly by alkalis with formation of anilineatid an alkaline sulphate.ThionyZparutoluidine C7H7*N:S0 is prepwed in a similar manner ;it is a yellow liquid which has an aromatic odour boils at 224",and solidifies in a freezing mixture to well-developed yellow crystalsmelting at 7".The reactilm arpears to be quite general the thionyl groap playingthe same rale with primary amines as the nitroso-group does withsecondai y amines.H. G. C.Metethoxyphenylsulphonic Acid. By A. DELfSLE and G. LAGAI( Bw 23 3392-339 4) .-Potassium metethox~phenylgulphonate,OEt*C,H,*SO,K + H20ORGANIC OHEMISTRY. 31 Iis deposited from water in hard octahedrnl crystals and from dilutealcohol in long flat lustrous needles. The harium wZt CeHBSOIBa +4E3,0 crystallises in needles ; the calciuni. salt (C8H9S04)&a + 3H20,is deposited in thin colourless plates. The free acid crptallihes withdifficulty and is readily soluble in water or alcohol. The sulpho-chloride crystallises from ether in hard pale-yellow needles and meltsat 38".The sulphonamide crystallises from water in long whiteneedles and melts at 131". The hydrosulphiJe OEt.C,H,*SH is pre-pared by the reduction of the sulphochloride boils at 238-239" andon warming with suiphuric acid gives a yellow coloration whichchanges successively to red green and blue.Synthesis of Indigo and Allied Dyes. By K. HEUMANN (Ber.,28 ~3431-3435).-Phenylg\gcocineorthocarboxylic acid is preparedby heating anthranilic acid (63 parts) with chloracetic acid (47parts) and water (500 parts) for t w o hours in a reflux apparatus. Itcrptallises from hot water as a yellowish granular maw and meltsat about 200" with decomposition. It is only slightly soluble iu coldwater. The alcoholic solution shows a blue fluorescence.The pre-paration of indigotin from this compound is best carried out asfollows :-Phenylg1ycocineorthoca:boxylic acid (1 p:irt) is fused withpotash (3 parts) and water (1 part) with consbant stirrirrg and themixture heated at 180-200" as long as it deepens i n colour. Themelt is treated with water oxidised with a current of air or withferric chloride and hydrochloric acid and the precipitated indigocollected and washed. The temperature of the reaction is 60-80"lower than is the case when phcnylglycocine is employed (comparethis vol. p. 75).By L. LEDERER(J. pr. Chem. [2] 42 565-567) -The author combats Heurnatin'sclaim for priority in this matter (this vol. pp. 75,206). With regardto Heumann's criticism that the indigo cannot actually exist in themelt the author points out that when indigotin is melted with sodiumhydroxide in a test-tube the melt first becomes yellow and thenorange-red subsequently again giving indigo-blue when treated withdilute sulphuric acid this behaviour is exactly similar to that ofJ.B. T.E. C. R.Synthesis of Indigo from Phenylglycocine.pbenylgly Locine and sodium hydroxide wheu meked together.A. (3. B.Action of Methyl Iodide on Hydro-a-methylindole. By C.ZATTI and A. FERRA'rINI (Chem. Centr. 1890 ii 554; from Bend Acad.Lincei 6 i 463-466) .-By boiling hydro-a-methglindole (1 pa.rt) withmethyl iodide (3 parts) for 20 minutes in a reflux apparatus an oilis formed which is insoluble in the excess of iodide. After distillingoff the methyl iodide the oily substance solidifies and may be re-crystallised from alcohol.It is of a slightly red colour smells ofindole and melts at 200-202". It is the iodide of an ammoniumbase Cs&<g2Z>CHMe and dissolves in water and alcohol. Bythe action of moist silver oxide the free base may be obtained. Thelatter ie crystalline and absoisbs moisture and carbonic auhydrid312 ABSTKACTS OF (YEEhlPCAL P IPEKS.from the air.chloride the chloride is formed which is also hygroscopic.the aurochloride and platinoch loride may be prcpared.By agitating the iodide with freshly precipitated silverFrom it,J. W. L.Indazole Derivatives. By 0. N. W m E. N~~LTING and E.GRANDWOEGIN (Ber. 23 3635-3644) .-The conversion of nitro-toluidine [Me NH NO = 1 2 41 into the corresponding phenolby means of the diazo-reaction io only complete under cerkain specialconditions for example by the addition of sodium nitrite to the basedissolved in hot hydrocbloric acid ; i n ordinary circumstance8 moreor less nitroindazole is formed probably on account of the closeproximity of the methyi and diazo-groups.fluNitroindazole NO,*C,H,<i/">NH [CH NH NO = 1 2 41 N-is prepared by dissolving nitrotoluidine (30 grams) in 60 grams of con-centrated snlphuric acid dilut,ed with 1 litre of water; the solution iscooled mixed with 14 grams of sodium nitrite dissolved in 200 C.C.of waier mid slowly warmed on the water-bath ; it is finally boiled fora short tJnie and on cooling a mixture of nitroindazole and nitro-cresol is depouit.ed ; this may be separated by repeated crystallisationfrom water or xylene ; the pure product is obtained in white lustrousneedles which melt at 181" and in small quantities may be volati-lised without decomposition.The sodium. salt crystallises in yellowneedles. The silver salt is also yellow. The methyl ether,CHN- NO,*C,H,< I >NMe is obtained by the action of methyl iodide~find alcoholic potash on nitroindazole or the mixture of this and thecresol; it crystallises from benzene in pale-yellow flat needles meltsnt l59" is insoluble in light peti-oleurn and yields azoxy-derivatives011 prolonged heating with alcoholic potash. The correspondingderivative of iiitro-orl hocresol cr-ystallises from light petroleum incolourless needles melting at 74". Acetylriitroii1,dazclZe crystallisesirom alcohol iii lustrous needles melts at 139-140" and sublimeswithout decJm posi ti on.By the action of aqueoiis bromine on nitroindazole a nioncibromo-derivative is formed which is deposited from benzene in small,yellow prisms and from alcohol in small needles which melt at 229".The sodium salt crystallises in red needles.No satisfactory results were obtained by the oxidation of nitro-i ndnzole.Nitroindazole niay be reduced by the action of stannous chloride inacid solution ; it is however preferable to employ ammonium sulphide.Amidoindnrole NH,*C6H3< I >NH crystallises from water inwhite plates or needles ; the former contain water of cryst,al!isation,whilst the latter are anhydrous and melt at 210". The hydrochlorideis deposited from alcoholic solution in white needles decomposes at230" without me1 ting and is readily soluble.By the action of sodium nitrite on a salt of ttmidoindazole hydrozy-CHN-ORQANIC CHEMISTRY. 313C HN-indazole OH*C,H,< I >NH is obtained; i t is deposited fromwater in colourless crystds melts iit 215-216" ( ? 265-266") andsublimes without decomposition.Irdazole is prodnced by elimina-tion of the amido-group from nniidoindnzole and is fonnd to beidentical with a specimen prepwed according t o the method of E.Fischer and Knzel. No indazole could be obtained from ortho-toluidine by the method described above. J. B. T.Derivatives of Beneidinemetasulphonic Acid.By A. ZEHRA(Ber. 23 3459-3464).-Sodium dicrcetylbenzidinemetaszdphonate,NHAc*C6H&H3(NHAc)*SO3Na is prepared by heating sodiumbenzidinesulphonate with somewhat more than an equal weight ofacetic anhydride. Unlike most alkali salts of acetamidosulphonicacids i t is sparingly soluble in cold water but etzsily soluble inhot water from which it crystallises i n beautiful long colourlessneedles.iMetadinitrodiacetylbenzidinexetasulphonic acid,NO,*CsH3(NH Ac)*CGH~(NHAC) (NO,)*SO,H,obtained by treating a solution of the above compound in concen-trated sulphuric acid cooled to +So with a mixture of concentratednitric and sulphuric acids has an orange-yellow colour and isestzemely soluble in water and alcohol. The potassiurtz salt crystal-lises from hot water in yellow needles.By heating with dilutesulphuric acid (1 Z ) the ncetyl groups are eliminated and meta-c~initroben=idine?,.e~~.~~~l?~h~~il~ acid,NO,*C,jH (NH?) *CGH (N H2) (NO,) S 03H,is obtained as a dark-red granular mass very slightly soluble in bothhot and cold water but somewhat soluble in dilute mineral acids.The potassium salt crystallises in bright-red needles and is onlyslightdy soluble in hot and cold water; the ammonium and sodiumsalts show the same behariour. The tetrazo-compound yields with&naphthol a blue-black dye of coppery lustre which does not dyecotton aiid dyes wool in an acetic acid bath a garnet-red; withP-naphtholdisulphonic acid R. it gives a beautiful reddish-violet,and with P-naphtholdisulphonic acid G.a violet-black dye.~ ~ ~ e t a d i a m i d o ~ ~ ~ ~ z i d i r i e m ~ t a s u l p h o n ~ c acid,C6H3 (NH,),.C,jH,!NH,),.SO,H,is obtained by reduciiig the nitro-compound with tin and hpdro-chloric acid. The hydrochloride is extreiuely stable and is easilysolable in hot water slightly so in cold water. Sodium nitrate whenadded to the acid solution causes the precipitation of fine yellowflocks consisting probably of the azimide but owing to the smallquantity it could not be examined. Ferric chloride instantly darkensthe solution and precipitates tl black compound. Platinic chloridedoes not form a double salt but acts as an oxidising agent. Thepicratc crystsllises in bright-yellow needles and is sparingly soluble inVOL. LX ?314 ABSTRACTS OF CE€EMICAL PAPERS.alcohol and water.with the potassium salt of croconic acid the azine,When a hot acid solution of the diamine is treatedis formed ; this when dry has a black colouy and green metallic lustre,and is very slightly soluble in water but more soluble in dilutealkali from which the potassizcm salt is precipitnhed in black micro-crystalline needles on the addition of concentrated potash.An aqueoussolution of the azine is completely decolorised by barium cbloride,and a heavy black compound separates. E. C. R.Fluorene Hydrides. By P. A. GUYE (BdZ. SOC. Chim. [ 3 ] 4.266-268 ; compare Abstr. 1889 720).-Fluorene (3.6 grams) phos-phorus (3 grams) and hydriodic acid sp. gr. 1.7 (9 grams) wereheated in sealed tubes at 250-260" for 6-7 hours and the liquidresulting from the extraction of the product with ether was frac-tionated over sodium.Two hydrides were obtained a decahydride,C,,H, which boils at 254-256" under a pressure of 727 mm. andwhich is still liquid at -15" but crystallises above -73" and isoxidised on contact with air and an octohydride Cl3HI8 boiling atd72-275" having properties similar to the former. Both thesehydrides are soluble in ether and benzene and have an odour likethat of diphezlylmethane. In addition to these hydrides a sample offluorene containing traces of phenanthrene yielded phenanthreneoctohydride boiling below 300". T. G. N.Oximes of Halo'id Benzophenones. By R. DEMUTH and M.DITTRICH (Bey. 23,3609-361 7).-Parachlorobenzophenone preparedfrom chlorobenzoic chloride and benzene when acted on by hydroxyl-amine and excess of alkali in the cold yields two oximes whichmay be separated by fractional crystallisation from alcohol ; theone melts at 155-156" instead of 149" as previously stated byBeckmann and Wegerhoff (Abstr.1889 1066) and is termed thea-oxime. The second or p- and more soluble modification is de-posited from dilute alcohol in square prisms melting at '35". No otheroxime could be isolated. Both compounds dissolve completely althoughwith some difficulty in aqueous alkalis. The p-oxime is convertedinto the a-modiiication by heating for about three hours on the water-bath but no change occurs on boiling with alcohol. Both compoundsyield chlorobenzophenone when heated with hydrochloric acid foreight hours at 100".a-,4cetyl~artcchlorob enaophenone crystallises from alcohol in rhombo-hedra and melts at 147-148". The /3-acetyE derivative is readilysoluble in alcohol from which it is deposited in long slender needles,and melts at lOFi-106".The hydroximes are regenerated from bothcompounds by the action of alcoholic potash.a- Pal-achlorobenzophetmne benzyl ether is obtained by treating thehydroxime with benzyl chloride and sodicm ethoxide and crys talliseORGANIC OEEMSTRY. 315from alcohol in short prisms melting at 74-75'. The corresponding/3-derivative is deposited from alcohol in long flst needles and meltsat 98-99'. Both compounds yield benzyl iodide when heated withhydriodic acid.~~tadi1,rornoberLzophelzolLe is best prepared by heating benzophenonewith the calculated quantity of bromine t$ogether with a little iodineand water in a senled,tubs for €oar hours at 1.50" ; a f h r purification,the product crystnllises from alcohol in broad lustrous needles andmelts at 141"; the yield is 40 per cent.On gently he Ltiny with solu-tion of hydroxylamine hydrochloride an oxime is obtained which issparingly soluble in alcohol and crystallisev i n slender needles ; theyield is quantitative. The ketone is regenerated by the action ofhydrochloric acid. No other oxime could be separated and only theone compound is formed on treating the ketone with hydroxylamineand excess oE alkali in the cold. All attempts to transform the oximeinto a second modification were fruitless.From these results itwould appear that the power of forming two oximes is dependent onthe symmetry or otherwise of tho molecule.Action of Nitrogen Tetroxide on Aromatic Hetoximes andon Glyoximes. By R. SCHOLL (Ber. 23,3490-3505).-The authorhas previously shown (Abstr. 1888,443) that aliphatic ketoximes whentreated with nitrogen tetroxide i n ethereal solution are convertedinto pseudonitroles. The aromatic ketoximes behave in a somewhatsimilar manner but the compounds obtained appear to correspondnot with the fatty pseudoni troles but with the dinitro-compoundsobtained by the oxidation of the latter.When benzophenonoxime (6 grams) is dissolved in ether (120grams) and nitrogen tetroxide (3.5 grams) added a brown solutionis formed which after remaining for 10 minutes is shaken withsoda solution to remove nitric and nitrous acids dried wiih calciumchloride and allowed to evaporate in a vacuum.The product of thereaction is thus obtained in large colourless seemingly monosymme tricplates which may be purified by the addition of water to the hot alco-holic solution. It has the composition CLBH10N204 melts at 78-78.5",decomposes with evolution of brown fumes at 98" and is soluble inthe common organic solvents. The simplest slipposition is that it isdiphenyldinitrornethane CHPhZ(N0&. That the nitro-groups havenot entered the benzene riiig is shown by the fact that on reductionit yields benzophenonoxime and benzgl hydrylamine CHPhz*NHz ;the formation of the first-named compound is not howecer altogetherin favour of the supposition that ths above substance is a dinitro-compound and it is not impossible that both this compound and alsothe corresponding fatty dinitro-compounds may have a constitutionexpressed by the general formula Xz:C:N<0,N02 which agrees withfht formula recently suggested by V.Meyer (Abstr. 1888 702) forthe pseudonitroles namely XZ:C:N*O*NO2. For the sake of simplicity,however these substances may for the present be regarded as dinitro-compounds .Acetophenonoxime is acted on by nitrogen tetmxide in the sameJ. B. T.031316 ABSTRACTS OF CHEMICAL PAPERS.manner but the oil obtained contains acecophenone which conld notbe sepmated.On heating to 60° the oil clecomposes with evolntionof nitrous fumes.Nitrogen t etroxide acts 011 sldoximes in quite a different manner ;SL sirnplc oxidation taking place with formation of peroxides thus,benzaldoxime yields diphenyZg1yoxime peroxide Ph'F:hf'? already Ph.CN.0'described by Reckmann (Abstr. 1889 %30) under the name azodi-benzenjl peroxide. The reaction is also :jimilar to the formation ofdiphenyldinitrosacyl (dibenzoylglyoxin~e peroxide) by the oxidationof nitrosoacetophenone with nitric acid (Hollemann Abstr. 1889 49).As it apeeared not impossible from the autlior's esperiments t h a t I Ifulminic acid has theconstitution H(?:"*(? (see this vol. p. %2),HCX-0the oxidation of the glyoxinies has been more closely investigated.Methylethylglyoxime is readily oxidised both by alkaline potassiumferricyanide and by nitrogen tetroxide the latter giving the best yield ;the prodact of oxidation is a colourless refractive pleasant-smellingliquid which boils at 115-116" (uncorr.) under 16.5 nim.pressure,and is miscible with the ordinary opganic solvents but is only sparinglysoluble in water and insoluble in alkalis. Its nnalysis agrees withthe formula C,H,N,O and on distillation at the ordinary pressuresi t is partly decomposed into isocyanates a11d is therefore in all prob-ability methyZethylglyo:cii77 e peroxide The correspondingdimethylglyoaime pwoxide is readily obtained by oxidising dimethyl-glyoxime with nitrogen tetroxide in cthereal solution. It) closelyresembles the foregoing but boils practically witliont decompositionat 222-223" under 726 mzn.pressure.The oxidation of monornethylglyoxime does not proceed as smoothlya s in tbe two previous cases an oil being obtained which is soluble inwater but very readily decomposes. It yields a -yellow compoundwith soda which also quickly becomes resinous. When the action ofnitrogen tetroxide is allowed to continue for some time a crystallinecompound of the formula CJ&N306. is also obtained wbich hasMe?:X*?EtC:N*O'Me? :Ni?-'NOz*C:N*O' probably tbe constitntionMore stable products are obtained from monop henylgljosime.This is best prepared by the action of a boiling solution of hydroxyl-amine hydrochloride on the crude sodium salt of isonitrosoaceto-phenone obtained by Claisen and Manasse's method (Abstr.11&7,944). The oxidation cannot be carried out in alkaline solution as theperoxide is at once decomposed by alkalis but nitrogen tetroside inetbereal solution readily effects the change. The resulting solution,after washing with water is evaporated the residue extracted w i t hchloroform and purified by precipitating its chloroform solution 1% i thlight petroleum or its acetic acid solution with water. Analysis anddetermination of the molecular weight by Raoult's method showcd itsformula to be CsHGN202 which agrees with the expected consti tuORGANIC CHEMIS'L'RI'. 317It has a bitter taste melts with decom-Ph7:N.YHC3J-O't ional formula,position at 89-95" is readily soluble in ether acetone chloroform,and acetic acid more sparingly in alcohol sand insoluble in lightpetroleum. On recrystallising from alcohol it is partially convertedinto benzaldehyde and the odour of the latter and of phenylcarb-amine is also observed on boiling it with water.With concentratedhydrochloric acid it yields hydroxylamine. All attempts to displacethe hydrogen atom by metals have been without success.H. G. C.Ethers of Benziloximes. By M. DITTRICH (Ber. 23 3589-3608) .-Attempts to prepare the methyl ether of ybenziledioximeaccording to the method of Japp and Klingemann resulted iu theformation of products identical with those from P-benziledioxime,showing that the y-oxime had become converted into the more stable,%modification by the action of the alkali.The hydrochloride offi-benzildioxime methyl ether softens atl 130° and melts at 14O-14dc,instead of 130" as previously given.a-Benziloxime methyl ether is prepared by the same method andcrystallises from alcohol in lustrous plates; it melts at 62-63" isreadily soluble in ordinary media and does not combine with hydro-chloric acid. No isomeric compound could be detected.yBenziZoxime methyl ether is obtained as an oily liquid which boilsat 219-220" under a pressure of 40 mm. ; the distillate solidifies oncooling and may be crystallised from alcohol from which it is de-posited in prisms melting a t 64-65" ; by distillation under ordinarypressure it is decomposed and it does not combine with hydrochloricdcid. The a-ether is unalteredby boiling with hydrochloric acid but on heating with this reagent ina sealed tube for several hours at loo" it is con-rerted into the y-modi-fication; by treating the latter compound in the same manner a t120-130" it decomposes into benzile and ammonium chloride.Determinations by Raoult's method with benzene as solvent showthat the methyl ethers of benxiledioxime have identical molecular,weights.By the action of a-methylhydroxylamine on benzile a t ordinarytemperatures a compound is obtained which crystallises from dilutealcohol melts at 64" and closely resembles ybenzilemonoxime methy iether in appearance and behaviour.p - ~ e t h y Zhydrozylurnine NHMe-OH is prepared by heating P-benzile-dioxime methyl ether with hydrochloric acid ; the hydrochloride isdeposited i n long prismatic crystals which melt at 85-90" andreadily reduce alkaline copper solution.Neither the free base northe hydrochloride reacts with benzile at ordinary temperatures whilston warming and in preseace of excess of alkali the base is completelydecomposed. On heating the dibenzyl ethers of a- and P-benziledi-oxime with hydriodic acid benzyl iodide is eliminated proving thatthe compound contains the group LNOH. By the action of a-benzyl-hydroxylamine on 7-benzilemonoxime benzyl ether at 130- 150° a,dibenzyl ether of a-benziledioxime melting at 153-154" is formed.No isomeric ether could be isolated318 ABSTRACTS OF OHEMICAL PAPERS.Tbe same compound is also prepared from a-benzyl bydroxylamiue anda-benzilmonoxime proving that the a-dibenzyl ether contains twoZNOC,H groups and it is assumed that the metbyl ethers have ananalogous constitution.Similar experiments with p-benzylhydroxylamine gave negnti T-eresults.Methyl iodide does not react with the non-basic methyl ether ofa-benziledioxime whilst by beating the second modification (q) withmethyl iodide at loo" it yields a-benziloxime metbyl ether.Ontreating this same dimethTl ether (a2) with hydriodic acid at 200',methyl iodide and ammonia me formed.Tbese results show that the two a-benziledioxime methyl ethers arenot geometrical isomerides but are structurally different ; it. is sug-gested that wliilst the non-basic modification (a,) bas the formulaRO.N:CPh.CPh:EOR the second (Q) contains the groups ZNOR and <XR ; the above experiment with hydriodic acid tells however.-somewhat against this view.Benzile is formed by the action ofamyl nitrite a t ordinary temperatures on a- or ybenzileoxime ;a-benziledioxime is converted to a considerable extent into thep - e x i m e ; the latter by similar treatment yields crystals of anoxidation product which melt at 1 1 4 O and give phenyl cyanste ondistillation. J. B. T.By R. DE NEUFVILLF and H. F. PECHMAXN(Ber. 23 33i5-3387) .-Tlibenzoylmethane is dissdved in chloro-form and treaitd with bromine in molecular proportion mixed with3 parts of chloroform; during the addition of the bromine a.stream of dry air is drawn through the liquid in order to removehydrogen bromide ; the residue obtained after evaporation of thechloroform consists of dibenzo?jEbromometha?se CBBrBz ; it crystal-lises from chlcrofom on the addition of light petroleum inlustrous needlts melts at 93" and gives no coloration with ferricchloride.Dilmroylcarbinyl acetate CHBz2*OAc is prepared by theaction of rtnbydrous potassium acetate on the bromide ; it crptalliscsfrom dilute alcohol in needles melts at 94" is insoluble in water 01'light petrolenm and gives a brown coloration with ferric chlopide ;the yield is 80 per cent. Dibenzoylbromocal-binyi acetate CBz,Br*OAc,is obtained by the action of bromine on the pet-ious compound ; it isreadily soluble in the ordinary media and is deposited from chloro-form on the addition of light petroleum in white crystals which melta t 101-102" ; by beating the compound either alone or in solution,acetic bromide is eliminated and the triketone is formed.Dibenro?lldibromonzetliane CBr2Bz2 is prepared by the action ofdibenzoylmethane on twice the molecular proportion of bromine ; itcrystallises from alcohol and melts at 95".The compound is com-pletely decomposed by the action of alkalis whilst small quantities oftriketone are formed on boiling an alcoholic solution with fiilrer oxide,carbonate or nil rate ; an acetic acid solution of potassiuni acetatecauses a similar reaction. Nitrosodibe~~zo2~lmethane CBz,:N*OH isformed by treating dibenzoylmethane with amyl nit<rite ; it crystal-DiphenyltriketoneORGANIC CHEMISTRY. 319lises from a mixture of chloroform and light petroleum melts at 146',and is soluble in alkalis with a yellow colour.Diphenyltriketone or dibenzoy 1 ketone CO ( CO*CsH5) is prepared byheating dibenzoylcarbinyl acetate or by the action of nitrous acid onnitrosodibenzoylmethane ; it crystallises from anhydrous light petro-leum in golden-yellow needles melts at 69-70" and boils Lct 247-248"under a pressure of 60 mm.and a t 289" under a pressure of 175 mm. ;is very hygroscopic and readily dissolves in all solvents except water.'' Diphenyltriketone hydrate," dibewomethylene glycol CBZ,(OH)~ isformed as a white flocculent precipitate on dissolving the ketone inalcohol or glacial acetic acid and adding water ; it melts at go" and isalso formed by boiling dibenzoylbromocarbinyl acetate with glacialacetic acid or by the action of potassium acetate on dibenzoyldibrumo-methane.Chemically the hydrate resembles the ketone ; both give abrilliant blue coloration on the addition of sulphuric acid to a benzenesolution. The hydrate readily dissolves in alkalis with the formationof phenylbenzoylhydroxyacetic acid OH*CPhBz*COOH which has notyet been isolated. After the solution has remained for some time thiscompound is decomposed by the further action of the alkali; partyields benzoic acid and phenylhydroxyacetic acid wliilst carbonicanhydride and benzoin are produced from the remainder.On treating the triketone with phenylhydraziue in molecular' pro-portion at ordinary temperatures a compound is deposited whichcrystallises from a mixture of chloroform and light petroleum i naggregates of almost colourless needles melts at 1:35" and acquiresa red colour after remaining in contact with tbe air.The snb-stance bas the formula C,,HI6N,O2 but i t is uncertain whether itis really a phenylhjdrazone ; it dissolves in concentrated sulphuric:acid with a yellow coloui* but the solution is not affected by ferricchloride or potassium dichromate (Bulow's reaction). By the actiofiof excess of phenylhydmzine on the triketone or on tbe previouscompound two substances are obtained and may be separated bytreatment with benzene a t ordinary temperatures ; the one crystallisesin yellow needles melts at 223" and has not yet been further investi-eated. The second comDound is soluble in benzene.and consists u I CPh>C*N,*Ph ; it crystallises fromNPhGPhof benzenazotriphen y lpyrazole,~ alcohol in orange-red prisms and melts at 156-157*.Diphenyltri3cetunanilide NPh:CPh.CBz(OH) is formed by treatingthe triketone with two parts of aniline a t the ordinary temperature ;it crystallises from benzene on the addition of light petroleum inyellow concentric needles melts at 99-100" and gives rz blue colora-tion with siilphuric acid and benzene. On boiling the triketone withalcoholic solution of aniline the dianilide C(OH),(CPh:NPh) is ob-tained crystdlising from beczene in yellow pyramids which melt at148".Diphenyltrinitrosoprupar~e OH-N:C(CPh:N*OH j is obtained as awhite crystalline powder from nitrosodibezlzylmethane and hydroxyl-amine; i t is insoluble in water but readily dissolves in alkalis andorganic menstrua and melts at 185-186".A second compound i320 ABSTRAOTS OF OHEMICAL PAPERS.formed i n small quantitF ; this crystallises in plates melts at 141" isinsoluble in alkalis and has not yet been further investigat,ed.Attempts to prepare other triketones from acetophenone benzoyl-acetone acetylacetone and ethyl acetoacetate have been nnsuccesstul.Cresolcinnamic and Metacresolglycollic Acids. By A.OGLIALORO and 0. FORTE (Gazzettn 20 505 -513).-The cresol-cinnamic acids were prepared by heating the corresponding sodiumcresolglycollates with benzaldehyde and acetic anbydride.Orthocresolcinnamic acid is obtained piire by decomposing its bariumsalt.It crystallises from a dilute alcoholic solution in small whiteprisms melts at 167-168" and is very soluble in-warm alcoliol,moderately in ether chloroform and benzene. The barium salt,(C16H1303)2Ba f H,O dissolves very sparingly in hot water and maybe obtained crystallised by evaporating the soiution. The silver salt,C16H,303Ag decomposes at4 100". The methyl salt Cl6HI3O3Me crys-tallisev from dilute alcohol i n colourless plates melts at tjl" anddissolves T-ery freely i n alcohol and ether and moderately in lightpet<roleum and chloroform but is insolnble in water; a brominatedderivative Cl7H1,Br6o3 may be obtained by adding bromine to satura-tion to the methyl alcoholic solution of this compound and heatingthe dixtnre for a few hours.It crystallises in brilliant yellow scales,and melts a.t 231".~~etucresolgZycrJllic acid C9Hl0O9 is prepared by melting a mixtureof metacresol and chloracetic acid in molecular proportion andadding a quantity of aqueous soda (sp. gig. = 1.3) quadruple that ofthe cresol taken. It crystallises from boiling water i n minute whiteneedles and melts at 102". The barium salt (C9H903),Ba + 6H20,crystallises from an aqueous solution in nodules consisting of veryfine white needles.Metacresolcimamic acid crystallises in white needles melts at 155",and dissolves freely in alcohol and ether. The silcer salt is white andanhydrous and is not altered by exposure to light. The bai-iumand the methyl salts are uncrystallisable compounds the latter is aviscid substance yielding a brominated derivative C17Hl,Br20J whichcrystallises in colourless rhoinbic tables and melts at 109".Paracresolckw.m?nic acid crystallises in white needles melts at159-160" and dissolves in alcohol ether and benzene.The acidcannot be completely purified but a silrer salt of the theoretical com-position may be isolated. 'I'he bn~iurn mrignesiurn and methyl saltsare uncrgstallisable ; the last is a viscid product and yields a brumin-a:ed derivative C,,Hl6Br,O3 which crystallises from methyl alcohol inbrilliant colourless rhombic tables melting a t 124-1%5".J. B. rr.S. B. A. A.Sulphides of &Naphthol. By S. OKUFROWICZ (Bey. 23,3355-3373) .-/j-Naphthol sulphide or ,3-11yc?roxpaplithyl sulphide,s(C,,H6*OH) is prepared by the action of either sulphur dichlorideor of sulphur and lead oxide on &naphthol.The a-sodium derivative S(CloH6*ONa) + GH.,O is obtained bydissolving the sulphide in sods ; it crystnllises in coloiirless con-centric needles is readily soluble in water o r alcohol and has aORGANIC OEEM18TRP.32 1a1 kaline reaction. The comesponding calcium and b a ~ i u m salts are( olourless and crystalline and like the salts of the heavy metals arevery sparingly soluble in water. The diethyl derivative,S( CioHs*OEt),,is prepared by the action of the calculated quantity of ethyl iodideand potash on the sulphide; it crystallises from benzene in long,slender wax-like lustrous needles melts at l89" and is not acted onby silver nitrate or mercaric oxide.0-Napbthylamine and /+naphthol are formed by the action ofammonia on B-naphthol sulphide whilst /?-naphthol is the soleproduct when the sulphide is treated with cuprous chloride or silverchloride. By the action of silver nitrate or of mercuric oxide onthe sulphide a compound is obtained which crystallises from dilutealcohol in stellate groups of ruby-red plates and melts at 164" ; theyield is 25-30 per Tent. of the sulphide employed.This substancehas the formula C20Hl&302 and is not acted on when boiled with eithersoda or glacial acetic acid ; when heated to goo' it yields hydrogensulphide and /?-naphthol whilst by reduction with zinc-dust andglacial acetic acid ,d-naphthol sulphide is regenerated. By the actioriof potassium dichrornate and sulphuric acid part of the sulphide iscompletely oxidised.and part remains unchanged ; with dilute nitricacid sp. gr. 1.18 phthalic acid is the sole product.@-Naphthol sulphide is decomposed by concentrated nitric acid ; buton dissolving the clielhyl derivative in 10 parts of glacial acetic acid,adding 5 parts of fnming aitric acid arid cooliiig well with ice dinityo-nqhthyl ethyl ether CloH,(NO,),-OEt [OEt (NO2)* = 2 1' 4 1 isobtained and may be piiritied by treatment with benzene ; it crystal-lises from dilute alcohol in long slender pale-yellow silky needles,melts at 215" and is not acted on by aqueous soda. The yield is SOper cent. When heated with dilute nitric acid at 160-170" dinitro-naphtbalenedicarboxylic acid [(COOH) (NO,) = 1 2 3 61 isproduced.Dinitramidoiaaphthtcle?ze [NH (NO,) = 2 1' 4'1 is formed byheating the above ethyl derivntire with concentrated alcoholic am-monia at 22G-225" ; it is very sparingly soluble and crystallises fromtoluene in slender yellow needles ivhich blacken at about 250° but donot melt.When /3.ethoupaphthyl sulphide is trented with coucen-trnted nitric acid at very lo^ temperatures t,he pi-ocluct after washingwith ice waler dissolved in benzene and the solurion cooled ethoxy-dinitrotiapht7qZ sulphide S[ C,,H,(NO,).OEt] is deposited in slender,golden-yellow needles which melt at 235". After some time a furtherdeposit is obtained from the mother liquor; this is dissolved in ether,and crystallises on the addition of light peixoleuni in slender pale-yellow needles ; it melts at 202" and is readily soluble in alcohol or benz-ene both at ordiriary temperatures and on warming.This substancehas the formula C24H,oN,S,06 and is probably a clinitro-derivative.@-Naphthol bisulpllide or B-hydyozyn@&l bisulphide is obtained byheating /?-naphthol with sulphur at 175-180' for 24 hours; afterpurification it crystallises from benzene in slender yellow needles,melts at 169" and is very sparinglj soluble it1 ordinary menstrua. Whe322 ABSTRACTS OF OHEMIGAL PAPERS.heated to 360"; it decomposes into hydrogen sulphide and &naphthol ;it is soluble in dilute and gives a red colour with concentrated alkalis.The yield is 10 per cent. The same compound together with a con-siderable quantity of the monosulphide is also formed by the actionof sulphur chloride a t 0" on p-naphthol dissolved in benzene; theyield is about the same as before.The best results are obtained byheating a .solution of the sulphide with half the molecular proportionof sulphur bromide for an hour on the water-bath; in this manner20 grams of P-naphthol yielded 5 grams of pure bisulphide. /3-Ethoxy-naphthyl bisulphide S2( C,oH,*OEt) is prepared in a similar mannei.to the corresponding monosulphide derivative ; it crystnllises fromalcohol in greyish needles and melts at 158.5'. The diacetate,S,(CloHn*OAc)s forms ft yellow hard crystalline mass which melts atabout 140" and is soluble in ether alcohol benzene and glacial aceticacid.The dibenzoate S2(CIOH6*OBz)2 crystallises from benzene i i igreenish plates 01' prisms and melts at 187".On heating the bisulpbide with recently reduced copper at230-240" it yields /3-dinaphthol m. p. 212" ; the bisulphide is notalhered by boiling with copper and xylene or cumene.a-Naphthol trisukhicle SJ(CIOHB.OH)? is obtained by the action ofsulphur chloride on a-naphthol and is a pale yellow amorphous sub-stance which blackens at 220". and is very Tettdily soluble in diluteaqueous soda but almost insoluble in organic media. The corre-sponding benzoate S3(C10H6-OB~)2 is a greyish powder melting a t 194".When benzene is mixed with 0.5 part of sulphur chloride and0.05 part of iodine heated in a sealed tube for 100 hours at115-125" and the product boiled with benzene toluene carbonbisulpbide and xylene succeesively a yellow hard amorphous massremains which is slightly soluble in xylene and has the formulaSsPhz.J. B. T.Ethereal Oil of Asafcletida. By F. W. SEJ~MLER (Bey. 23,3530-3533).-Up to the present it has not been found possible toseparate crude asafoetida into its constituents by fractional distillation,but the author finds that this may be readily carried out underdiminished pressure. Thus under 9 mm. t w o specimens of crude oilof sp. gr. 0.9843 at 22" and 0.9789 at 12" respectively gave onrepeated fractionation four chief fractions distilling below 65" atThe fraction distilling below 65" obtained from both specimens,had the same qualitative composition but the constituents were pre-sent in different quantities thus causing a difference in the speciScgraviky. On treatment with potassium in a vacuum until no more gasis evolved and then distilling a colou rless pleasant-smelling oil isobtained which has the composition CloH ; it is a mixture of twodifferent terpenes one of which yields it liquid and the other a soliddibromide.It is contained ready formed in the oil and may also beobtained from the fraction distilling below 65" by adding mercuricchloride unt,il no further precipitate is formed and distilling in acurrent of steam. The first sample of oil mas thus found to contain6 per cent. and the second 8 per cent. of the mixture of terpenes.80-85" 120-130" 133-145"323 ORQANlC OHEMISTRY.The fraction 133-145" was treated with sodium i n a vacuum ancion distillation under 9 nim.pressure a colourless oil passed ovel- a t123" which had n pleasant lavender-like odour a sp. gr. of 0.9241 at15" and the composition C15H,. It belongs therefore to the groupof sesqniterpenes and forms a hydrochloride C16Hu,2HC1.These two fractions consist chiefly of substances free from sulphur,the compounds containing the latter being found in the second andthird fractions which are at present being more closely investigated.Indian Geranium Oil Geranaldehyde and Geranic Acid. ByF. W. SEMMLER (Bey. 23 3556-3557 ; see also Abstr. 1890 951).-In the previous paper it was shown that geraniol on treatment withchromic acid and distillation in a current of steam yields a11aldehyde CloHlbO which may be termed yeranaldehyde.If the re-sidue after removal of the aldehyde is treated with phosphoric acidand again distilled in a current of steam a small quantity of an oilis obtained which has an acid reaction. It may be prepared muchmore readily by making an emulsion of 6 grams of geran-aldehyde in 500 grams of water gradually adding a solution of13.5 grams of silver oxide in dilute ammonia acidifying with a slightexcess of phosphoric acid and distilling in a currelit of steam. Thedistillate is neutralised with soda evaporated to drpess the residueextracted with boilirig absolute alcohol and the latter expelled fromthe filtrate. The residue is taken up with water and precipitatedby means of silver nitratc as the siZver salt ; this has the compositionC,,H,,O,Ag. Geranic acid is a thin oil.The alcohol and aldehyde also occur in other oils of which a more de-H.G. C.tailed account will he given later. (Compare also'foIlo~~-ing abstract.}H. G. C.German and Turkish Rose Oil. By T. POLECE and C. EC&T(Ber. 23 3554-3535 ; see also Markovnikoff this vol. p. 219).-The first product which passes over in the distillation of German roseoil is ethyl alcohol about 5 per cent. of which is present. Terpenescould not be identified. After removing stearoptene the German roseoil was distilled under diminished pressure when it passed overalmost entirely a t 110-120" (14 mm.). Its boiling point a t atmo-spheric pressure was found to be 215". The Turkish oil behaves in nsimilar manner both eleoptenes being laevorotatory the German varietyhaving a sp.gr. of 0.8837 at ll" and the Tuikish 0.8H13 at 12".The analyses of the liquid portions of both oils indicated the formulaCloHlSO. This compound has the characteristics of a primary alcoholwith two ethylene linkages both with regard to the molecular re-fraction and its behaviour to.wards bromine. Its sodium derivative,chloride iodide arid benzoate have been analysed. On oxidation i tyields first an aldehyde C10H160 and then an acid Cl,EL,,O2. Phos-phoric anhydride and zinc chloride abstract the elements of water,forming a mixture of two different terpenes C10H16 which differ con-siderably in their boiling point. If the action takes place below O",the higher boiling terpene is.strongly.dichroic. The otily products offurther oxidation found were carbonic aiihydride formic acetic andoxalic acids324 ABSTRACTS OF OHEMIOAL PAPERS.The properties of the liqnid constituent of both the German andTurkish oils correspond exactly with those of geraniol the chiefconstituent of Indian geratiium oil (Semmler Abstr. 1890 931 andpreceding abstract) and a direct coiuparison of the aldehydes hasshown their actual identity. The eleoptene of rose oil therefore alsocontains an open chain of carbon atoms which on elimination ofwater unite to form R closed chain.Phenolic Acid from Camphor. By P. CAZENEUVE (Compt. rend.,111 743-745) .-Monochlorcamphor is treated with six times itsweight of concentrated sulphuric acid a t 50" for 30 hours and theproduct is poured into cold water.After some time the liquid isfiltered heated saturated with barium carbonate and concentrated.Amethylcamphophenolsulphone (Abstr. 1890 11.53) and thebarium salt of the new acid crystallise together. They can beseparated by crystallistihion f roll alcohol of 70° in which the bariumsalt remains dissolved and i t can afterwards be purified by crystal-lisntion fmm water.The barium salt crystallises in nacreous plates and when treatedwith sulphuric acid it yields smethylcamphophenolsulphonic acid,08*CsH120-S03H isomeric with thc sulphone a colourless syrupy,uiicrystnllisable liquid with a bitter astringent acid taste and anodour recalling that of solutions of oak-bark.It is very soluble inwater alcohol and ether has no action on polarised light and distilspartially without decomposition under reduced pressure. Solutionsof the barium salt gave a magnificent blue coloration with ferricchloride. If the salt is boiled with acetic anhydride for 15 minutes,it yields an acetyl derivative OAc*C9H1?0*S03H the barium salt ofwhich has no action on ferric chloride. When ti-eated with potassiumhydroxide the original phenolic acid is formed. C. H. B.Action of Camphoric Anhydride on Benzene. By E. BURCKER( f j u l l . SOC. Chirn. [ 3 ] 4 112-113).-Under conditions similar tothose by which benzoylpropionic acid is formed camphoric an-hydride and benzerie react in presence of aluminium chloride to forma coinpound C1&IZ003 which is separated from its sodium salt bytruatment with hydrochloric acid as very light scales; it is solubleiii alcohol chloroform ether and acetic acid but only sparinglyin benzene and almost insoluble in water. It melts at 125-126",but if this temperature is passed it no longer solidifies oncooling but remains as a syrup and decomposes at a higher tem-perature without boiling.'l'he compound behaves as a monobasicacid. Solutions of the alkaline hydroxides dissolve it and the saltsformed by it with cobalt nickel copper and silver crgstallise easily.With phenylhydrazine i t yields a yellow crystalline derivative.Further work is being car?*ied on to determine its constitution.Crystalline Principle from the Bark of Diospyros virginiana.Bj- W.SCELEIF ( J . Yhamz. [S] 22 469-471 ; from Amer. J. Yharm.,1890 390).-Thc powdered root is extracted with light petroleum bywhich a Tellow solution is obtained yielding a waxy residue onevaporation. The powder is then treated with ether and the solutionH. G. C .T. G. NORUANIC CHENISTRY. 325distilled when a deep-red crystalline residue is left; this is dissolvedin hot alcohol and treated with an alcoholic solution of lead acetate,which removes the colouring matter only. After fiitration the liqnidis treated with hydrogen sulphide again filtered and the still reddish,alcoholic solution is digested with animal charcod on the water-bath,nnd concentrated by distilling off the alcohol ; the crystals whichseparate are purified by repented recrystallisation from alcohol unti Ithe dry product has a yellowish-grey colour. The crystalline mass t h u sobtained sometimes contains crystals 0.2 mm. long; these are soft,and waxy in appearance when moist.The dry substance is lightbrown in colour and granular in texture with a peculiar odour anda slightly astringent taste. I t is soluble in alcohol ether andchloroform very little soluble in waler and not at a11 in lightpetroleum. At 2.58" it takes a deeper tint and at 262" it melts withappaient decomposition. The compound has a neutral reaction ; it,does not dissolve on boiling with dilute hydrochloric acili o r in dilutepotash solution ; it burns on platinum foil without leaving any re-sidue. Its alcoholic solution is not precipitated by alcoholic solutionof lead acetate or of ammonia.It diesolGes in glacial acetic acid.Its composition corresponds with the formula C3rcHeiOlo.By A. LADEXBURG (Ber. 23 3555-3556) .-In replyto Stoehr's criticisms of the tiuthor's previous paper on this subject(Abstr. 1890 1432) Ladenburg states that the facts from which hisconclusions were drawn were obtained in personal communicationsfrom Stoehr and that as there stated the trnt,h of those statementsis now being experimentally investigated.ByE. NOELTING and E. TRAUTMANK (Eel.. 23 3654-3683).-Quinoliiieis dissolved in 10 parts of siilphuric acid (100 per cent.) and treatedwith the theorelical quantity of fnmiug nitric acid also dissolred insul ph uric acid ; enough fuming sulphuric acid containing 20-25 percent.of sulphuric anhydride is added to combine with the water con-tained in the nitric acid and also with that formed during thereaction ; the mixture is either gently heated or allowed to remain forseveral days at ordinary temperatures ; in this manner only the t w omononitro-d eriva tives are formed.NitroparatoZuquinoZine CSNH5Me-NO2 [Me NOa = 3 41 is pre-pared by the action of nitric acid on paratoluquinoline in presence ofsnlphuric acid ; it crystallises from aIcGho1 in pale-yellow needles,melts at lJ6-117" and is readily soluble in organic menstrun. Thesalts are crystalline but readily undergo dissociation in presence ofwater. The proof of the above formula consists in the fact that thecorresponding amido-derivative does not yield methylphenmthrolineby the action of glycerol and picric acid.The rnethiodide crystnl-lises from alcohol in long yellow needles ; on allowing these to remainin contact witoh the mother liquor rhombohedra are formed ; froniwater the compound is deposited in colour1e.s rhombohedra whichbecome yellow at 100" ; both forms melt at 189-190"AmidoprLratoiuquinoline is prepared by the reduction of the abovenitro-derivative with iron and acetic acid ; it crystdliscs from waterJ. T.p-Picoline.H. G. C.Derivatives of Toluquinoline and Metaxyloquinoline326 ABSTRAOTS OF OHEMIOAL PAPERS.or dilute alcohol in yellow needles and melts at 145"; the yield is90 per cent. of theory. The hydrogen salts are red whilst theiiormal salts are almost colourless but are red i n aqueous solution.The acetyl derivdive crystallises from water in whit.0 needles melts at160° and yields colourless salts with acids.Hyc@zyparatoZuquinoline CSNH,Me*OH is prepared by the actionOE sodium nitrite on the amido-compound ; it crystallises from alcoholin flat needles melts at 230° sublimes without decomposition and isnot volatile with steam.The samc compound is also obtained by theaction of fuming sulphuric acid at 90" on paratolnquinoline; theresiilting sulphonic acid being then fused with potash. It fcrms well-characterised salts with acids and alkalis and yields a hydroxyazo-derivative with diazobenzene chloride which is deposited from alcoholi n small red needles melting at 176".~T~troso-ltydroxyparatoluquinoline 01' o~!/pai'utoEuquinoliiae oxime,C9NH4Me(NOH)0 is obtained by the action of nitrous acid on thehydroxy-derivative at low temperatures ; it crystallises from waterin yellow needles and from alcohol in yellow plates which deeom-pose above 200' without melting.The hydrochloride is sparinglysoluble in hydrochloric acid and crystallises in yellow needles ; thesodium salt is deposited in small yellow plates. The nitroso-corn-pound yields a stable green dye with iron inordanted cloth thisproperty is probably due to the presence of a salt-forming group inthe peri-position [4 1'1 to nitrogen ; thus whilst the three ortho-hydroxytoluquinolines (see below) and orthoquinone osimes give dyeswith mordants paraquinone oximes only do so if they contain theNOH group in the position 1.O1.th o ? z i t r ~ 1 l l yd7.oa.ypwc1tol I1 q ? h 01 L'?LC,N0,*C9NH,Me*OH [NO OH Me = 1 3 41,is prepared by the oxidation of the oxirne with potassium ferricyanide,and crystallises from dilute acetic acid or alcohol in yellowish-brownplates which decompose while melting.Ortholi~jdrox~~nzetntoluqzlilzolilze C,NH,Me*OH [OH Me = 1 21 isprepared from amidorthocresol [OH NH Me = 1 2 61 glycerol,and picric acid ; i t cr.ystallises from dilute alcohol in long needles,melts at 73-74' is volatile with steam and in contact with copperoxide colours the flame peen ; the yield is SO pel* cent.ATittmso-orthoxy~netatoZuquinoZhe C9NH,Me(NOH)0 [0 Me NOH= 1 2 41 is prepared by the action of sodium nitrite ou the pre-ceding compound and it is deposited from alcohol or dilute acetic acidin yellow needles ; it decomposes at about 200" without melting andltas no tinctorial properties. Soluble salts are formed with acidsand bases.~-~trorthoh~drozymeta~oluquinoline is obtained from thepreceding componnd by oxidation with potassium ferricyanide inalkaline solution ; it crgstallises from alcohol in red needles and frombenzene in yellow needles melts at 192-1193" yields salts with acidsand bases and dyes mordanted cloth.Orth(,hydro~~7YLethylqzcinoline CsNH,Me*OH [OH Me = 1 41 isprepared from amidoparacresol [OH NH Me = 1 2 41 ; i tcrystttllises from dilute alcohol iu long colourless needles melts aORGANIC CHEMISTRY.327132-124O and gives a yellow dye with aluminium mordants; theyield is 65 per cent. of theory. Nitroso-orthoxymethylquinoline,CgNH4MeO:NOH [0 NOH Me = 1 3 41 resembles the pre-viously described isomerides and dyes mordanted cloth ; on oxida-tion it yields the corresponding nitro-derivative which crystallisesfrom alcohol in slender yellow needles melting at 205-206" ; yellowcolonrs are obtained with aluminium mordants.NitropnratoZuquinoZi?ie C9NHJMe*NO2 [Me NO2 = 3 41 is ob-tained from nitroparatoluidine itcrgstallises from alcohol and melts at 116-117" ; the yield is 65 percent. The corresponding mnido- acetyl and hydroxy-derivatives havebeen prepared and closely resemble the previously described iso-ruerides. Orthonitroparatoluquinoline CgNH5Me*N02 [NO Me =1.31 is prepared from nitroparatoluidine [NH NO Me = 1 2 41,and crystallises from water in pale-yellow needles melts at 122" anddoes not combine with methyl iodide ; the yield is 60 per cent. Thesalts crystallise readily but dissociate with water. Orthamido-paratoluquinoliiLe is prepared from the preceding compound by reduc-tion with ammoniuin sulphide ; it crystallises in slender needles,melts at 62-64" sublimes without decomposition and is volatilewith steam. The hydrochloride forms orange needles. The cccetylderivative is obtained from water or dilute alcohol in large platesmelting at 91-92". It yields salts which readily crystallise. Thehydroxy-derirative is prepared by means of the diazo-reaction and isidentical with the compound obtained from toluquinolinesulphonicacid [SOsH Me = 1 31 bv fusion with potash.The nitroso-compound CSNH,Me(NOH)O [0 Me NOH = 1 3 41 is verysparingly soluble and crystallises in brown plates which decomposeitt 200" and do not dye. The nitro-derivative could not be obtained.Orthnmidochlorn~aratoluquinoline C9NH4MeC1*NH2 [NH Me C1=1 3 41 is formed together with amidotoluquinoline by the reduc-tion of tbe nitro-compound with tin and hydrochloric wid ; i t c r ptallises from alcohol in silky lustrous needles melts at 129-130° anddoes not combine with diazo-compounds. The monacid salts areorange-yellow and readily undergo dissociation. The hydrochlorideis sparingly soluble. The acefy 1 dei-ivative is deposited from dilutealcohol in lustrous needles melting at 136-137".Nitr.orthotoZzLquiizoZine. CgNH7Me*N02 [Me NO = 1 21 is pre-pared by the nitration of orthotoluquinoline. and crystallises in pale-yellow needles melting at 93".It is volatile with steam does notcombine with methyl iodide and on heating with alcoholic potashgives a violet colour changing to red and finally to dirty brown onexposure to air. The yield is almost theoretical. The same com-pound is synthetically prepared from nitrotoluidine [NH2 Me NO2= 1 2 .j]. The salts readily undergo dissociation.4,~nido~thotoZuq~~inoEine is obtained by reduction of the precedingcompound with iron and acetic iicid,and crgstallises from water or dilutealcohol in long yellow needles melting a t 143". The hydrochloride isTed the dihytlrochloride yellow.Methy~hena~~tl~roline CyNH4Me<CH:bH [Me CH N = 1 3 4J,[NH2 NO2 Me = 1 3 41 ;N=C328 ABSTRACTS OF CHEMICAL PAPERS,is obtained by the action of glycerol and sulphuric acid on the amine,ant1 is deposited from light petroleum in sninll crystals melting at95-96".It is identical with the compouud obtained by synthesisfrom mctatoluylenediamine.AcetaiIiidorthofolirqu.i?z(ilL'ne ci-ystallises from water in silky lustrousneedles and melts at 187". HSdroxFarthotoluquinoline from theamide crystallises fkom dilute alcohol in colourless needles andmelts a t 262-263' on rapidly heating. A compound identical withthis has previoixly been prepared from orthotol uiclinesulphonic acid[SO,H NH? Me = 1 3 43.With diazobenzene chlorkle ah yd.l.ozyaso-clerivative is fortned crystallising from alcohol in redneedles melting at 1.?8-139" and soluble ill aqueous alkalis. Thewitroso-compoond C,NH,Me(NOH)O [Me NOH 0 = 1 3 41,crystallises from alcohol in yellowish-brown plates decomposes above200" without melting and gives " lakes .' with the heavy metals.The nitro-derivative is formed on oxidation and is deposited inorange needles which melt at 181-1$2" :iiicl do not dye.i-lzo~thotoZuquitroli~ze. N,(C8NH5M~:)f? [Me N = 1 41 is formed,together with amidotolu qu inolin e by the recluc t ion of ni tror tho tolu -quinoline with iron and liydrochloric acid ; it c~ystallises from glacialacetic acid in orange needles and melts a t 260".The hydrochlorideis readily obtained in red crystals. On reduction with stannouschloride or alcoliolic ammoniiim sulphide n compound is formedwhich is insoluble in water yie!ds red salts aiid has not yet beenfurther investigated.Azoxyorthotoiz~qui~zol;lze ON,( C9NH,Me) is formed together withthe azo-derivative and niay be separated by crystallisation fromhydrochloric acid in which it is tolerably soluble; it may be pre-pared directly by the incomplete reduction of nitrotoluquinoline. andcrystallises from alcohol in slender yellow needles melting at 201".The hydrochZoride is deposited in very slender lemon-yellow needles ;all the salts are readily dissociated. When heated with 10 parts ofsulphuric acid at 110-113" a compound is formed which is probablylLydroxyazotoZuquinoZi~e ~:II~HjnIle.K,.C9NHjnile.0H [Me 0 H N =1 3 41 ; i t is insoluble in alkalis as is also the corresponding corn-pound [Me N = 1 4 ; Me N OH = 1 3 41 from amidotolu-quinoline and hydroxytoluqiiinoline.Nitrometaxyloq~~i~Loline CgNH,Me2*NOJ [Me LMe NO = 1 3 41,is obtained by nitratiug metaxyloquinoline ; it crystallises fromalcohol in long yellow needles melts a t 107-108" is scarcely volatilewith steam and does not combine with methyl iodide.The salts aredecomposed by water. The constitution of the compound is shownby its synthesis from nitroxylidine "El Me Me NO =1 2 4 51 ; it gives no coloration with alcoholic potash. Bniido-metaxyloguiszo Zine is formed by the reduction of the preceding compoundwith iron and acetic acid or stannous chloride and hydrochloric acid ;it crystallises from diiute alcohol in long yellow needles and meltsat 91".The acetyl derirative is deposited from water in colourlessneedles which melt at 201". Hydro,rymetnxyZoqiiinoZine from theamido-compound and nitrous acid crystallises from chloroform inwhite plates and melts at 197-198". On snblirnation it is obtainedThe picrate melts at 252-253".OR3ANICl OHEMISTRY. 329in small needles and salts are formed with acids and hases.hydrochloride crystaliises in yellow needles.TheJ. B. T.2-Methylquinaldine. By E. RIST (Ber. 23 3483-3487) .-Theauthor has already shown (Abstr. 1890 1324) that the so-calledmetamethylquinaldiae obtained by Diibner and v.Miller from par-aldehyde and metatoluidine(Abstr. 1884,183) and which mighi there-fore have either the meta- 9r ana-constitution is converted by oxida-tion into the quinaldinecarboxylic acid prepared by DBbner and v.Miller from metamidobenzoic acid and aldehyde. The hydrochlorideof the latter acid forms small characteristic tablets sparinglysoluble in cold readily in hot water whilst the platinochloride,4(C,,H,N02,HCl),PtC14 crystal lises in reddish-yellow monosymmetricprisms readily soluble in water. Its silver salt CIIH8NO2Ag crystal-lises from hot water in microscopic crystals soluble in ammonia andnitric acid.To ascertain whether these compounds are really 2-derivatives theauthor subjected Gerdeissen's 2-amidoquinddine (Abstr.1889 520)to Sandrneyer'~ reaction. The ordinary procedure cannot be adoptedin this case as the compound appears to form a stable nitrite. Themixture must be diazotised below 0") allowed to yemain and thenadded to the freshly prepared cuprous cyanide on the water-bath insmall quantities and with vigorous shaking. As soon as gas ceasesto come off the hot liquid is filtered saturated with soda andthe precipitate recrystalljsed from water. The nitrile thus obtainedforms silky needles melting a t 82" and crystallises with approxi-mately 2 ifiols. H,O wliich are given off on drying over shlphuric acid,the melting point then becoming 104". It is volatile in a current ofsteam soluble in the ordinary solvents and in acids and may bedistinguished from the otherwise hirnilar 2-amidoyainoline by thefact that i t yields ft colourless or pale-yellow solution with alkalis.On hydroljsis it is converted into a quinaldinecarboxylic acid whichis identical w i t h the acid already described.It follows therefore,tbat both this acid and the methylquinddine from which it wasprepared have in reality the met%- and not the ana-constitution.H. G. C.Constitution of p-Quinaldinesulphonic Acid. By B. R!CHARD(Ber. 23 348$-3490).-Uy the adion of sulphuric acid on quin-aldine Dobner and v. Miller obtained a mixture of three sulphonicacids two of which were shown to be ortho- and para-quinnldine-sulphonic acids whilst the constitution of the third known as the@-acid was not ascertained (Abstr.1884 183). In order to deter-mine its constitution the author converted it by the usual reactionsinto the corresponding nitrile and carhoxylic ncid both of which werefound to be identical with the 2qanoquinaldine and quinaldine-2-carboxylic acid described by Rist. (see preceding abstract). 'l'he acidfrom which they are prepared must therefore be quinaldine-2-sulphonic acid. H. G. C.Condensation of Metanitrobensaldehyde with Quinaldine.By w. WARTANIAN (Bey. 23 3644-3653).-MetanitrobenzaldehydeVOL. ZX. 330 ABSTRAOTS OF CHEMIOAL PAPERS.is heated for 3-4 hours on the water-bath with rather more than1 part of qninaldine. zinc chloride being added from time to timein small portions ; after pnritication and crystallisation from alcohol,a product is obtained which melts a t 124-126" and consists of a,mixture of metanitrobenzy 1 idenequinnldin e,CgNH6*CH:CH*C6H4*Xo2 [CH = 2'; CH NO = 1 33,and of the aldol compound CgNH6*CET2*CH( OH)*C6H4*N02 ; theformer substance may be separated by treatment with acetic anhydrideat 13.5" ; it is deposited from a mixture of benzene and light petroleumin yellow nodular crptalline aggregates and melts at 139".Thehydrochloride forms long,rectangulnr crystals ; the ititrate crystallices inpale-yellow lustrous needles ; tbe picrate is deposited in lemon-yellow,interlaced needles the yhatinochloride ( C,7H,2N202)2,H2PtC16 + 1$H20,is crystalline. When reduced with stannous chloride and hydrochloricacid motnmido benziy liden equinaldine C,NH6*C H CH*C6H4*NH2 isproduced crystallising from a mixture of benzene and light.petroleumin orange-red plates; i t melts at 158-159" and is insoluble in water,but readily dissolves in organic media and is deposited from alcoholin pale-yell( )w needles. On heating the timido-compound withplycerol sulphuric acid. and orthonitrophenol eth~leiiediquirrolin~,C,NH6*CH:CH*CsNH [CH CH = 2' 21. is formed. but could not beobtained in crvstals; it i s readily soluble in alcohol benzene andchloroform. The salts and platinochlorida are amorphous. The meth-iodide rrvstallises from methyl alcohol in golden-yellow needles meltsat 225-226" and is insoluble in benzene but readily dissolves in hotwaher.No dimethyl iodide could be prepared. A homo-additivecompound is formed by +he action of bromine on the methiodide inchloroform solution and is deposited from methyl alcohol in slendercrystals which commence to decompose at 18G-290° and melt at210".Eth~/leneq~cinolineq~rinaldine C9NH6*CH:CH*CgNH;Me [ CH = 2' ;CH:Me = 2 2'1 is prepared by the action of paraldehyde onamidobenzylidenequinaldine and forms R yellow plastic mas8 readilysoluble in alcohol benzene or ether.The nitrite crystallises fromwater in stellate groups of reddish-yellow needles which commenceto decompose a t 125* and melt at 135-136". The hydrochloride,nitrate. slilplmte picrute and platinochloride are all amorpboiis andreadily soluble. J. l3. T.6-Pyrazoledicarboxylic Acids. By MAQUENNE ( Gompt. rend.,111 740-743).-Dinitrotartaric acid not only acts on form-aldehyde and acetaldehyde in presence of ammonia hut the reactionis general and the Ruthor has prepared in this way a number of~-pyrazoledicarhoxylic acids from the corresponding aldehydes.Theyare all only slightly ~oluble even in boiling water and are almostinsoluble in alcohol but dissolve very readily in alkaline solutions,and yield mono-metallic salts which are neutral and crystallisa~ble.Methyl- et h-yl- and isopropy1-~lyoxalinedicarboxylic acids crystallisewith 1 mol. H20 in brilliant acicnlar prisms ; the others form crystalORQANIC CHEMISTRY. 331line anhydrous powders. Is~butylglyoxalinedicarboxglic acid andits alkaline salts have a sweet taste but this property is wanting inthe neighbouring homologues.All the glyoxalinedicrtrboxylic acids decompose at about 300° andyield carbonic anhydride and glyoxalines or p-pyrazoles the decom-position being almost quantitative.This constitutes the best methodfor the preparation of glyoxalines. Many glyoxalines were preparedin this way and the hexyl-glyoxaline was found to melt at 45-46",and not at 84" as stated by Rsdziszewski.2-Phenyl-p-pyrazole is solid very slightly soluble in water or inwarm benzene (from which it crystallises in lamella) but easilysoluhle in alcohol. It melts at 148". and boils at about 340" (uncorr.),which distingnishes i t fi-orn the isomeric 1-phenyl-a-pgrazoledescrihed by Knorr which melts at ll" and boils at 246.5". Thenormal oxalate crystallises from aqueous solutions in anhydrousneedles ; the platinochloride is anhydrous and forms orange micro-scopic crystals almost insoluble in cold water.acid.-F u rf urald eh y de does notact on dinitrotrtrtaric acid in the same way as other aldehydes.When the aldehyde and acid in molecular propor.tion react inpredence of excess of ammonia a crystalline precipitate f rms,and cm be purified by solution i n ammonia and reprecipitatior~ withhydrochloric acid. It resembles the glyoxalinedicarboxylic acids inappearance but has not their general properties and yields no gly-oxaline when distilled. The ammonium salt has the compositionC14HI,N208(NH4)2 + 2H20. The acid has the composition CI4HI2N2O8,is formed by the union of 2 moleciileu of furfurddebyde with 1 mole-cule of tartaric acid and probably has the constitutionDif u rju rnmidodih y d rox y turtaricCOOH.7 (OH)*N:CH*CjH,OCO 0H.C ( 0 K) *N:C H*CaH30C.H. B.Caffei'dine. By E. SCHMIDT and M . WERNECKE (Arch. Pham.,228 516-543) .-Caffeidine sulphate was prepared by boilingcaffeine with barium hydroxide (Strecker's method) for half an houronly ; white needle-shaped crystals were finally obtained which areeasily soluble in water much less soluble in alcohol. By treating thesulphate with barinrii liydi*oxide a little water and chloroform thefree base is obtained as a solid crystalline mass with a neutral reaction ;it melts a t about 99". The free base readily decomposes with theformation of ammonia methylamine and cholestrophane. Cufe.i;dinehydriodide obtained by neuhalising the free base with dilute hydriodicacid forms white tabular anhydrous needles easily soluble in hotwater somewhat less soluble in hot alcohol insoluble in chloroform,&,f&dine hydrochloride obtained by treating the hydriodide in aqueoussolution with silver chloride forms long thin somewhat hygroscopicneedles.Cnfei'dine nitrate prepared by precipitating the hydriodidesolution with silver nitrate forms large white strongly hygroscopicneedles. Caffei'dine sulphate when treated with nitric acid yieldschlolestrophane ammonia methylamine and carbonic anhydride ;but no ammonia is formed if the mixture is heated for a long time.2 332 ABSTRAOTS OF CHEXIOAL PAPERS.@xidat,ion of the sulphate with potassium dichroinate and sulphnricacid yields the same products and not diethyloxamide as found byMnly and Andreasch excepting when the mixture is heated for sometime.Oxidation with bromine gives the same compounds as doesalso treatment with potassium chlorate and hydrochloric acid. Fuminghydrochloric acid corupletely decomposes caffeidine sulphate at 1.50"with the formation of carbonic anhydride formic acid ammonia,methylamine and snrcosine (compare Abstr. 1883 69).Derivatives af Morphine. By W. DANCKWORTT (Arch. Pharni.,228 372-595).-Morphine. when heated with excess of aceticchloride yields diacetylmorphine (the tetracetylmorphine of Wright).This compound when boiled w-ith water loses only one acetyl group,and a-monoacetylmorphine is formed ; by the addition of hydro-chloric acid this can easily be obtained as the sparingly solublehydrochloride.The ,kl-morroacetyl (p-diacetyl of Wright) compoundwas prepared byBecket and Kright's method (this Journ. 1874,1033),but their ycompound was not obtained. The stability of morphinewas not found to be increawd by the entrance of the acetyl group asshown by tho reaction of diacetylrnorphine with dilute nitric acidand wit,li bromine although this is known to be the case with codeineand the methyl group. Anhydrous morphine when heated at100-110" with twice the amount of henzoic chloride yielded di-benzoylmorphine which supports the view that the morphine moleculecontains only t w o hydroxyl groups. Polstoi~fi's tritetizoylmorphinecould not be detected. By heating oxydimorphinc with aceticchloride tetracety loxydimorpliii I e is obtained which doubtless isidentical with Hesse's diacetylpseudomorphine obtained by theaction of acetic anhydride on pseudomoiyhine.The entrance of thefour acet,yl grcups indicates that four hydroxyl groups exist intact i nthe oxjdimorphine and that the hydrogen atoms replaced must havebeen united wit'h carbon. Apomorphine when treated with excess ofacetic chloride yields monacetylapomorphine ; hence only onehydroxyl group is present in apomorpliine the second hydroxyl groupc/f morphine during its conversion into apomorphine going to form a,molecule of water. Probably tlie alcoholic hydroxyl of morphine istlw one expelled the phenyl hydroxl having greater stability. This,t o some extent will account for the chemical and physiologicaldifference between morphine and apomorphine.J.T.J. T.Cinchonamine. By ARNAUD (Ann. Chim. Phys. [ 6 ] 19,93-131)See this vol. p. 362.Berberine and Hydroberberine. By R. GAZE (Arch. Phawn.,228 6 0 k 6 6 2 ; compare Abstr. 2830 101 2).-Chloroformberberin~,dissolved in a little hot chloroform acd treated with alcohol quicklygives long prismatic crystals of dicliloroforni berberiiie,CmHi,NO,,CHCl + CHC13.The crystals soon lose their transparency when preserved and decompose with evolution of chloroform when warmed. J. TORGANIC OEEMISTRT 333Ecgonine. By U. Mussr (Chem. C'entr. 1890 ii 516 -517 ; fromL'Orosi 13 15%158).-The aubhor has already (L'Orosi 11,270-277) recorn mended that since the direct detection of cocaine isdifficult the products of its decomposition should be sought ibr intoxicological investigations.With t,his object he has examined t'hebehaviour of ecgonine with various reapents. According to Eiiihornthis a1 kaloid is met11 y I t e t rah. y d ~ o p y rid y 1-6- h y di-on y propionic acid,C,NH,Me*CH( OH)*CH2*COOH,and reacts both as R base and an acid; it crystnllises in colourless,lustmus monoclinic prisms with 1 mol. H20 which is lost at1%~-130". I t is very readily soluble in water less easily i n abso-lute alcohol insoluble in ether chloroform and carbon bisulpliide.Its solutions are neutral and have a somewhat bit,ter taste. It meltsat 19c3" with partial decomposition. With pbosyhomolybdic acid i tfornis a yellow precipitate ; with somewhat concentrated gold chloridesolution a yellow amorphous precipitate ; with platinic chloride indi I ute alcoholic solution a red-brown crystalline precipitate,(CgH15N03)2,H2PtCI which is readily soluble in water and loses hydro-gen chloride when heated forming the salt (C,H,,N03),PtC14.Withstarinic chloride mercuric cliloride tannin and picric acid it forms noprecipitates which distinguish it from cocaine. Especially is the reac-tion with Wenzell's reagent (BOO parts of sulphuric acid and 1 part ofpotassium pernisnganatc) delicate a clear wine-red coloration beingformed which disappears only after some time.I n an experiment with EL rabbit 1.26 grams of ecgonine per kilo. oflive weigbt was found to be fatal.After 48 hours tlie entrails weredivided into tive parts and each part digested several times at60° with twice its weight of a!cohol,and the extract concentratednearly to dryness. The residue was taken up with water and shakenseveral times with ether in order to extract fatty substances. Theaqueous solu t,ion was precipitated with basic lead acetate filtered thelead removed as sulphide the liquid again filtered evaporated codryness and the residue finally extracted with a little absolute alcohol,in which the ecgonine exists as acetate and was readily detected. Thealkaloid was found in the heart blood lungs liver,b.r;tin,and spinal cord..Ergonine SaZts.-( CgH,5N03)2Mg + Y+H20 very hygroscopic yla t,es,soluble in water and alcohol insoluble in ether melting at 190".(CgH15N03),Ca is soluble in water and alcohol insoluble in ether.C9H15N03Ag orange-coloured decomposing readily when exposed tothe light.Ecgonine a,cefate C9H3[15X03,C2H402 + 2iH20 needle-like,hygroscopic crystals melting at 196" very soluble in water audalcohol insoluble in ether.New Alkalo'id from Chrysanthemum cinerariaefolium. ByF. MARINO Zuco (Chem. Centr. 1890 ii 560-561 ; Rand. Acad.Lincei 6 i 571-575).-In addition to the two substances the one aparaffin and the other a homologue of cholestei-01 which the authorhas alr2ady described (Abstr. 1890 7 5 i ) he has further separated aglucoside and an alkitlo'id from the flowers of CYlwysatrthemum cine-rarimfoZium. Both were obtained from the blossoms by extractionwith ether.The glucoside is crystalline but could not be obta.inedJ. W. L334 ABSTHAUTS OF CEEMIOAL PAPLRY.in sufficient qnantit,y for proper investigation. The alkaloid namedckrysanthemine by the author is readily soluble in water and its solu-tion may be concentrated on the water-bath without decomposition,whereby the base is obtained as a colourless syrup. The majority ofits salts are soluble in water alcohol and ether and are crystalline.The most characteristic of these is the aurochloride which crystal-lises in small goldon-yellow needles very soluble in hot water,sparingly so in cold water readily in alcohol and moderatelysoluble in a mixture of alcohol and ether (1 1). Potassiumbismuth iodide forms a yellow precipitate with it and pntassiunimercury iodide forms a yellowish-white precipit,ate.Platinum chlor-ide tannin and picric and phosphotungstic acids do not form precipi-tates with it. The analysis of the aurochloride agrees with theformula ClaH3003NZ,2A~C14 according to which the formula of Chehydrochloride mould bo CI4H3,,O3N,Cl2.Ulexine and Cytidne. By A. W. GERRARD and W. H. SYMONS(Pharm. J. [3] 20 1017).-The authors enumerate the followingdifferences between ulexine the alkaloid of Ulex europrms alreadydescribed by them and cytisine the alkaloid of C. laburnum whichhas been supposed to closely resemble or be identical with theformer. Ulexine has the formula -i(CZ,H,N4O2) ; is very hygro-scopic cannot be sublimed even in a vacuum without decomposi-tion and dissolves readily in chloroform.Cytisine bas the formulaCznHz,NaO is permanent in air sublimes completciy forming splendidcrystals and is almost insoluble in chloroform. The formula givenfor ulexine differs only by CO from that of nicotine arid by HzOti-om that of pilocarpine and there is a certain likeriess in the physio-logical action of these alkaloids notwithstanding the differences intheir chemical behaviour. Some progressions of properties aretraced in the alkaloids from leguminous plants arranged according tothe percentage of carbon thus :-sparteine pyridine nicotine,cytisine ulexine eserine and pilocarpine ; in this series the physio-logical activity becomes more powerful and the instability greaterwith decrease in the percentage of carbon.Alkaloids and other Active Principles from Plants Growingin the Dutch Indies.-By M.GRESHOFF (Ber. 23 3537-3550).-I. Carpaine the Alliaload vf Carica papaya L.-The leaves of thepapaya (Carica paptryu L.) contain in addition to the caricine andpapai'ne discovered by Wurtz and Peckolt an alkaloid which hasriot previously been prepared and for which the name cwpaine isproposed. The young leaves are richest in the alkalo'id and containabout 0.25 per cent. ; the sap seeds and roots only contain traces.Caspaine is readily soluble i n alcohol chloroform and ether thefreshly precipitated compound being more readily taken up bythe latter solvent than when ci*ystallised a fact which is made useof in isolating the alkaloid.It is completely separated from solutionsof its salts by sodium carbomte solution but is insoluble in potash,aild carinot be extractcd from acid solution. It gives precipitateswith Majer's solution iodine phosphomolybdic acid picric acid goldchloride tannin potassium thiocymate &c. melts at ll5* and sub-J. W. L.R. RORQANIO OHEMISTRT. 335limes partly without decomposition. Its hydrochloride crystallises inbeautiful lustrous needles and is readily soluble in waher. The base,even when dissolved in 100,000 parts of water has a bitter taste andis only poisonous in large doses but small quantities readily killsmaller animals the action taking place on the heart.11. Investigation of Indian Leguminous Plants.-The plant knownas Derris (Yongamia) elliptica Benth.,is largely used in Java in fishing,and appears also to be a constituent of the Borneo arrow-poisou.Ithas'an exceedingly poisonous action on fish a decoction of the rootsbeing fatal even when diluted with 300,000 parts of water. Theonly active constituent isolated is a resinous substance termed derrid,which does not contain nitrogen and is not a glucoside ; it readilydissolves in alcohol ether chloroform and amyl alcohol but is verysparingly soluble in water and potash solution. On fusion withpotash it yields salicylic and protocatechuic acids. It occurs almostentirely in the cortex of the root but has not yet been obtained pure.Its alcoholic solution has a slightly acid reaction and a sharp aromatictaste causing a partial insensibility of the tongue which remains forhours.A solution of 1 part i n 5 millions is almost instantly fntitl tofish. A very similar compound is found in the seeds of Ynchyrhixusangulatus Kich. a decoction of which is quickly fatrtl in a dilution of1 125,000. it is probably identical with derrid but until this hasbeen experimentally proved it may be distinguished as prtchyrhizid.It is very readily prepared from Pachyrhizus which occurs in alltropical countries as the tannin compounds usually so difficult toseparate are not found in this. plant. 'l'he seeds also contain a non-poisonous crystalline compound which is readily soluble in alcohol,arid has at 3'3" the consistence of butter.'l'he plant Sophora tomentosa L. formerly renowned as a medicine(" Antzcholerica Burnphii ") contains 8 poisonous alkaloid soluble inether which is contained in largest quantity in the seeds.Alkaloldshave previously been found in S. speciosa and S. angustijolia b u thave not been closely investigated.The cortex of Erythrina (S'teiwtrol;is) Broferoz Hassk. contains con-siderable quantities of an alkdoi'd which may be readily isolatedby Stas's method and is easily soluble in ether. Its snlphate maybe obtained in crystals from concentrated aqueous solution. I t givesprecipitates with many metallic salts and with the usual alkaloidreageuts ; it is a fairly strong poison being fatal to fowls in doscs of0.025 gram. A poisonous alkaloid likewise exists in Erythrina(Hypuphorus) aubum,brans Hassk. and is best isolated as a metallicdouble compound.'l'lie leaves of different kinds of cassia are employed in Java as aremedy for herpes; $hey contain a glucoside which yields chryso-phanic acid as a product of hydrolysis.The leaves of Urotolarin retusa L.contain considerable quantitiesof indican ; the seeds contain an alkaloid which is found in largerquantities in the seeds and leaves of C. strinta L. The base is astrong poison and is probably clodely related to the known alkaloidsof other Genistese such as Cytisus Ulex Spartiurn and h p i n u s .The seeds ot Nillettia utropurpurea Benth. contain a poisonou336 ABSTRAOTS OF OEEMICAL PAPERS.glucoside the chemical and toxicological properties of which closelyresemble those of saponin.The plant is also employed for poisoningfish. The cortex of Acacia tenerrimc~ Jungh. contains a bitder,poisonous alkalojid readily soluble i n ether and chloroform. No alka-loid has previously been found in an acacia. The leaves of Albizzizsaponaria Bl. contain cathartic acid whilst the leaves and cortzxcontain saponin in quantity.The cortex of Pithecolobium bigsminum Mart. contains 0.8 per cent.of a non-volatile amorphous alkaloid which forms crystalline stilts,and separates as a heavy yellow oil on the addition of alkalis to solu-tions of the latter. With 100 parts OE water it forms a turbid liquid,which on warmiug assumes the appearance of milk but becomes clearon tbe addition of an acid. The solutions have a burning taste and givethe usual alkaloid reactions.It has a strong corrosive action on theskin and is fatal to fish in a dilution of 1 400,000. The same com-pound appears also to occur in P. suman. Benth.III. Apocynece containing Alkaloids occurring in the DutchIndies.-The leaves cort.ex and seeds of Melodinus hvigutus Bl.,all contain a poisonous alkaloid which is present in the largestquantity in the seeds (0.8-1.0 per cent.). It is decomposed bydilute hydrochloric acid but is not a glucoside and gives the ordinaryalkaloid reactions in very dilute solutions and with feeble oxidisingagents in sulphuric acid solutions gives a greenish coloration whichthen becomes deep blue and finally orange.Leucorcotis rwgenifolia Dec. yields a poisonous crystalline alkaloidwhich is readily soluble in ether and shows the general reactions ofthe alkaloids but gives no colour reactions. The cortex of Rauwolfiuca?zescens W.yields an alkaloid which gives a beautiful blood-redcoloration with nitric acid. Rauwolfia (Ophioxylon) serpentirm andtrifolinta which is highly prized in Java RS it drug also contains acrystalline alkaloid which gives the same reaction with nitric acid,and its presence may be easilg recognised microscopically in thevarious parts of the plant by this reaction. The substance recentlydes aribed as ophioxylin is identical with Duloug’s plumbagin theerror being caused by a confusion between Ophioxylon se~pentinu~rz L.,and PEunzhago Tosea L. which though very different plants are bothtermed “‘ Poeleh Pasdak ” in Java.The above alkaloid also occursin Rauwol$a (Cyrtosiphonia) spectabilis and madurensis. All thesespecies of Rauwo@u contain a brown substance also ; this likewiseappears to be an alkaloid and yields a beautiful blue fluorescentsolution in ether.The cortex of H u i i t e k corymbosa Roxh. contains 0.3 per cent. ofa crystalline alkalo’id whicb a l ~ o forms crystalline salts and gires abeautiful violet coloration with Erdmann’s and Frohde’s reagents. Itis a strong poison and has a sharp burning taste even when dilut,edto 1 10,000. The cortex of Pseudochrosia glomerata Bl. also containsa poisonous crystalline alkaloid and the above fluorescent compound.The cortices of Ochrosia (Lnctaria) acuminata Acksringae andCoccinea are rich in alkaloYd constituents.Three products have heenisolated namely a colourless crystalline alkaloid soluble in ether,which is moderately poisonous an alkaloid insoluble in etter butIt is constitueiit o€ many Apocyn,eceORQANIO CHEMCSTRT. 337soluble in amyl alcohol which is bestl isolated as the rnerourochloride,and also the above-mentioned fluorescent compound. These substancesalso o c c x in the seeds and the sap. The cortex of the stem ofOchrosin (Bleekaria) kalocarpa contains 1.2 per cent!. of alkaloids.Tlre seeds of KopsiaJflrrzida BI. contain no less tJhan 1.83 per cent.of a homogeneous alkaloid which is soluble in ether and readily pre-pared pure and crystalline ; it likewise occurs in Kopsia arbo?-ea Bl.,the leaves of which contain in addition a fluorescent substance.Kopsia (Calpicccrpum) Rozburgliii yields quite a different alkaloid,which causes tetanus.The seeds and leaves of Kopsia (Culpicarp2cm)alb&run? contain RU alkalo'id as also do Vinca rosea L. and dZsto?ieu(Blaberopus) aillosn.Voacanga (Orchipedn) .fetida jields a bitter alkaloid readily solublein ether and the flnorescent compound already frequently mentioned.Tabernemontana spZmrocarpa BI. also contains an dkaloid and a,wax-like compound which is free from nitrogen and melts a t 18.5".Alkaloids are also present in Rhyncodia (C'ercocoma) macruntha andin Clmnemwpha mncrophylla Don which is of interest inasmuch asthese species both belong to the Echifidie the other members ofwhich are free from alkaloids.IV.Cerbera odollaw Hamilt.-The Rap leaves and cortex of thisplant have no toxicological action but the seed kernel contains ind d i tion to a non-poisonous fatty oil the compound cerbei in whichhas a poisonous action on the heart. It resemhles thevetin thevetosin,and tanghinin but is identical with none of them. It most nearlyrexm bles the last-named substance which is obtained from Tunyliirkzvenenifera Poir. the " test-plant " of Madagascar. Ceyberin is fre,ef rorn nitrogen and crystallises well and although decomposed byacids. is not a glucoside. It is insoluble in water but dissolves readilyin alcohol chloroform acetic acid and 80 per cent. ether and melts at165". It gives n violet coloration with sulpliui.ic acid bas a sharp,burning but not bitter taste and is very poisonous.The seeds containanother very poisonous substance which is readily soluble in water,alcohol and xmyl alcohol but i~soluhlc in chloroform for which thename odollin is proposed. It is not pvecipitated by lead acetate andgives the same colour reaction with sulphuric acid as ccrberin.V. Laurotetanine the Active Cnnstituw t of certain Lawacem.-Many of the Javan varieties of Lauraceae contain in addition to othernot yet clearly defined bases a crystalline alkaloid termed luurotet-anine which has a strong tetanic action on animals. It is coiitainedin quantity in the cortex of the stem of Litscen chrysocoma Bl. andis sparingly soluble in ether more readily i n chloroform. It is pre-cipitaled by sodium carbonate from solutions of its salts but readilyredissolves in an excess of potash or soda and is precipitated by theumal alkaloid reagents. The freshly prepared alkaloid cominenccstoo crystallise after some days in stellate groups of ncedles ; it gives adark indigo-blue coloration with Erdmann's reagent a pale rose-redwith pure sulphuric acid and a reddish-brown witth nitric acid.Abase which seenm t o be identical with laurotetanine is also found inthe varieties of TetrantheTa in Notaphmbe Bl. Aperuh Bl. andActinoduphne Nees. It is possible also that laurotetanine is identica338 ABSTRACTS OF OHEMICAL PAPERS.with the alkaloid discovered in 1886 by Eykmann in Huasia squarrosa,2. et M. as the author has also found it in 11. firma Bl.Hernandia sonma L.and H. ovigera L. both yield an alkaloidclosely resembling the bebeeriue obtained from Nectundru whilstIllipra pulchra Bl. contains laurotetauine.VI. l'he Distribution of Hydrocyauic Acid i n the Vegetable Kingdom.-The leaves of Gymlzema latt$oliurn Wall an Indian Asclepiadea,contain large quantities of amygdalin which can however only beobtained in the amorphous condition. The leaves do not contain anyenzyme and may therefore be distilled with water or dilute sulphuricacid without any hydrocyanic acid or benzaldehyde passing over. Onthe addition of emulsin hydrolysis readily takes place.'l'he fresh bark of many Javan forest trees gives off an odonr ofbitter almond oil. It was found that f'yqium parviJiorum T. et B.,and P. Zatifoliuna Miq.both contaiu amjgdalin which on botanicalgraunds was not improbable as the species Pygium is closely relatedto Ampgclalus.When the fruit of certain Javan Aro'ides (the genera Lasin and Cyrto-sperma) is cut a strong odour of hydrocyanic acid is observed and itwas found on investigation that it is present in the free state. italso occurs in the leaves of these plants. It is found however inmuch larger quantity in a Javan tree known as Pangium e d d e Reinw.,the seeds of which after cooking in a certain manner are looked on bythe Malays as a valuable food. It' this cooking is insuificient theseeds are a frigbtful poison and are used in Java for killing fisq andinsects. I t was found on investigation that all parts of the treecontain free hydrocjanic acid.Thus the leaves on distillation yielded0.34 per cent. which is equal to 1 per cent. on the dried leaves;in the other parts the proportion although less is still considerable.The amount of bydrocyaiiic acid is not constant old Pangium leaveshaving been examined which only contained 0.045 per cent.The leaves and seeds of the Pangium contain a substance whichreduces ammoniacal silver solution and E'eh ling's solution in the cold,arld whose solutions become dark-coloured in the air. Although nocrystalline componnd could be obtained with phenylhydrazine it isprobably a sugar with which the hydrocyanic acid forms an unstablecompound. 'l'he seeds which are originally white gradually becomedark the hydrocynnic acid disappearing at the same time.The only poisonous constituent of the genus Hydnocarpus is alsohydrocyauic acid.The fatty oils of certain species of Hydnocarpus areused externally in skin diseases their value being possibly due to theantiseptic action of hydrocyanic acid. H. G. C.Coagulation. Preparation of Soluble Casein. By A. BECHAMP(Rull. Soc. Ghim. [ 3 ] 4 181-186).-The author takes exception tothe undefined meaning of the word coagulation as applied to theseparation oE the proteids from milk under varying conditions anddescribes the following method for preparing a soluble casein whichis not coagulable by heat. Pure acetic acid is dropped into milkjust drawn from the cow or goat until the milk turns litmus-paper a pale pink and the coagulum which soon separates out iORGANIC CHEMISTRY.339collected and after drying by a filter pump is treated with ether toremove fat; it is then suspended in a volume of' water equal to that ofthe original milk and containing ammonium carbonate and themixture is filtered. To the limpid solution thus obtained acetic acidis added exactly sufficient to precipitate the casein which by a re-petition of the above treatment is obtained pure.The rotatory power of this substance in ammoniacal solution is[a] = -130". It is soluble in water 1 litre dissolving on agitatior,for 56 hours 1.005 grams and the rotatory power of this solution is[a]j = -117". A paste of casein and water softens at 70-80" andappears to be quite soft at go" tbe water separated from this productcontains 2.37 grams casein per litre ; and although the paste hardenson cooling it is soluble in ammonium carbonate solution and on pre-cipitation by acetic acid manifests its original properties.Caseinbebaves like a feeble acid its solutions redden litmus and it formsconipounds with the alkali metals and with ammonia which alsoredden litmns and are neither precipitated by carbonic anlrydride,nor by alcohol nor by heating. Calcium caseinate behaves likecalcium saccharate in becoming tnrbid on ebullition and in tbe dis-nppeararice of the turbidity on cooling. The author ascribes theincorrect results hitherto obtained to the practice of boiling the milkbefore adding the acid by which lactalbumin and galactozymaseare precipitated as well.These substances are separated from thewhey left after removal of the casein by adding to it alcohol of 95"as long as a precipitate falls ; the latter is collected and washed withalcohol of 80° to remove lactose and is then air-dried and suspendedin water ; after some time it is filtered and the precipitate is washedwith water as long as the washings give a precipitate with alcohol.Lactozymase is separated from the filtrate by the addition of alcoholand a trace of sodium acetate; i t is soluble in water and has thepower of determining the dissolution of starch without subsequenthydrolysis ; it is coagulable by heat and then loses this property.Lactalbumin is obtained by dissolving the residue in diluteammonium carhnate solution and precipitating by acetic acid ; whenit is suspended in water and heated to loo" it contracts in volumeand is no longer soluble in ammonium carbonate solution.Protei'ds of Milk.By W. D. HALLIBURTON (J. Physiol. 11,448-463).-Attention is drawn in this paper to the followingpoints :-(1.) The principal proteid in milk precipitable by saturation withcertain neutral salts or by acetic acid should be called caseinjogen.It may be most satisfactorily prepared free from impurities by acombination of the two methods just mentioned. The term caseinshould be restrid,ed to the curd formed from caseinogen by the actionof rennet.(2.) I n the classification of proteids casein should be grouped withother insoluble proteids like fibrin and gluten formed by fermentactivity from pre -existing more soluble proteids.Case'inogen shouldbe classified in a new gronp made t o include it and whey-proteid.These are very similar to the globulins ; the chief difference beingT. G. N3 10 ABSTRAOTS OF CHEMICAL PAPERS.that their solutions are not coagulated by heat like the globulins butonly rendered opalescent. This opalescence i f the heating has notbeen continued too long disappears on cooling.(3.) Lactalbumin id very similar in its properties to serum-albumin.Not only does it differ however from serum-albumin in its specificrotatory power as has previously been shown but in its behitviour onheat-coagulation and in precipitahility by certain neutral salts.(4.) Caseinogen and lactdbumin are the only proteids containedin milk.The proteid described as lactoglobulin does uot exist; i t isowing to tbe error of not recognising t h d the two salts sodiumchloride and magnesium sulphat? when both present to saturation,precipitate albumin that this proteid has been supposed to exist.The prote'ids variously called lactoprotein peptone and herni-albumose do not exist in milk. This mistake has also arisen fromfaulty methods of analysis.( 5 . ) The proteid called whey-proteid which passes into solutionsimultarieouslj with the forination of the rennet curd is not of thepeptone or proteose class b u t should bc included with caseinogen i i ia new class of proteids allied to the glokulins. It differs fromcasehopen in not being convertible into casein.(6.) When milk turns sour owing to the lactic acid fermentation,primary proteoses chiefly proto-proteose art! developed.W.D. H.Note.-Hammarsten in his text-book of Physiological Chemistryrecently published also recognises that caseinogen should not begrouped with nlkalii. albuminates as has hitherto been the case. Heclassifies it with the nucleo-albumins. W. D. H.Action of Lime Salts on Casein and on Milk. By S.RINGER (J. Physiol. 11 464-47i).-Casein preparcd by addingcommercial rennet to milk was found to be freely soluble in lime-water ; on the addition of calcium chloride to this solution a com-pound of casein is formed which is more soluble in cold than in hotsolutions. A few drops of calcium chloride solution does not causeprecipitation at all in the cold but on warming a precipitate formsclosely resembling a rennet curd and like it i t contracts squeezingout a whey.On cooling this however it completely redissolves.Larger quantities of calcium chloride cause a precipitate in the cold,which increases when the mixture is heated. Sodium chloride in 0.5,1 and 2 per cent. solutions does not modify this action ; whilst lactosegreatly aids the action of the calcium salt.Calcium chloridecauses no curdling of milk at the atmospheric temperature (loo tolSO) i n this respect differing strikingly from solutions cf casein inlime-water from which 1 to 3 drops of a 10 per cent. solution ofcalcium chloride precipitates abundance of curd or sets the fluid toa jelly. Calcium chloride however abundantly precipitates curdfrom milk with the assistance of heat the smaller the quantity ofcalcium chloride the higher the tcmperature required.Slight acidityfavours sodium chloride and to a less extent potassium chloride andmagnesium sulphate hi rider this action of calcium chloride. HenceSimilar experiments were then tried with milkORGANIC CHEMISTRY. 341milk differs from casein dissolved in lime-water in respect to theaction of sodium chloride. Lactose which greatly favours tbe clot-ting of a lime-water solution of casein by calcium chloride does notinfluence the clotting of cass'iaogen as contained in milk.Calcium chloride solution does not clot milk whicb ha8 been pre-viously boiled and then cooled. Hence it is evident that the biphtemperature necessary in the experiments does not alter the casehogen,and thus enable calcium chloride to precipitate it but that the hightemperature is necessary to enable cakium chloride to precipitate(combine with) casefnogen.Casebogen can be prepared as follows :-lo pel.cent. acetic acid isadded to milk; the resulting precipitate is washed with distilledwater until the washings are neutral and free from calcium salts.The curd is rubbed in a mortar with cnlcinm carbonate and distilledwater added ; the casehogen rapidly dissolves and the butter sepa-rates and floats on the top. After some hours the milky fluid below iseiphoried off. Rennet clots tbis solution if a small quantity of calciumcliloride is added but not without. The rennet used (Crosee andBlackwell's) contains a good deal of calcium but tbis is either insuffi-cient or in inappropriate form. But although the Anid does not clot,the case'inogen is courerted into casein which reninins in tohition andthis is at once deposited on adding calcium chloride eclch drop pro-ducing an abundant deposit insoluble in solut,ion of sodium chloride.Sodium and potassium salts antagonise the clotting of casehogensolutions a s iri the case of milk ; i n the former case they lessen too,the subsequent contraction of the clot. If phosphoric acid is essential,as Hammarsten etated the minute quantity present in the prepara-tion of rennet must have sufficed as none was added in the experi-ments.Calcium chloride solution precipitated casehogen from its solutionwithout the assistance of rennet; only larger quantities are necessarythan i s the case with solutions of casein. Lactose has no eBect OQthe precipitation of casei'nogcn by calcium chloride. Corroborativeresnlts were obi ained with case'inogen precipitated by saturating milkwith sodium chloride.Among further differences between casehogen and casein the twofollowing may be noted :-(1.) Casein is insoluble in a fairly strong solution of sodiumchloride ; casei'nogen is so!uble.( 2 ) Caseinogen precipitated by acetic acid and mixed in a mortarwith calcium carbonate is freely soluble in distilled water. Caseinsimilarly treated is insoluble.The process of ordinary curdling in milk by rennet is believed toconsist of two parts :-(1.) The change from casehogen to caseh produced by thef ermen t .(2.) The combination of the casein so formed with a lime salt theprecipitation of ihis compound being assisted by the lactose butopposed by the sodium and potassium salts of the milk. These saltsalso lessen the degree CJf contraction of the clot and hence a bulkyclot instead of a compact one is obtained. W. D. H34'2 ABSTRACTS OF CHEMICAL PAPERS.ChittendenPainter.Digestion Products of Gluten-caaeh. By R. H. CHITTENDENand E. E. SMITH (J. Physiol. 11,420-434).-The methods of investiga-tion are essentially the same as those adopted in the similar researchesof Kiihne Chittenden and others. Although it i s questionable whethergluten exists in fresh wheat grains i t is nevertheless true that glutenis formed whenever wheat flour is mixed with water and of thisgluten the insoluhle portion characterised by Ritthausen as gluten-case'in is the most important constituent. The percentage composi-tion of this material (the average of analyses of seven preparations)may be contrasted with the numbers obtained by Ritkhausen and withthe percentage composition of the case'in of milk as in the followingtable :-Halnmtlrsten.~Gluten- case'in.53 -307.0715 '910 -82Caseln of milk. I52 -967 -051.5 -650 72Chittenden and Ritthausen. I Smith. I52 -876 *W15 *861 *17c ........H ........ N .........8 .........52 947 *Q417 *140 -19On subjecting gluten-case'in to artificial gastric digestion,it was foundthat solution occurs very slowly probably the result of the prolongedwashing with alcohol in its preparation. Artificial pancreatic diges-tion also proceeds slowly but there is a more abundant formation oftrue peptone as compared with primary cleavage products (proteoses),than is the case with gastric digestion. The soluble products formedin each case bear essentially the aame relation to the parent substanceas the albumoses of albumin or fibrin do to the parent protei'd.There are slight differences in minor reactions but no essentialdifference in the general chamcter of the products formed in this case,at least between theanimal and vegetable prote'id. Both yield by theaction of peprjin acid 8 proportionately large amount of proteoses anda small amount of true peptone. The gluten-caseosee both in com-position and reactions show the ordinary proteose characteristics andthe composition of the individual products (proto- hetero- anddeutero-gluten-caseose) aa indicated by the gradually diminishedpercentage of carbon snggests that they are formed by a gradualprocess of hydration.Crystalline ViteUin and Vitelloses. By R. H. CHITTENDEN andJ. A. HARTWELL ( J . Physiol. 11 435-447) .-This research carriedout on the same lines asthe preceding confirms i n the main the workof Neumeister (Abstr. 1887,286) ; i t was judged advisable to repeatthe experiments 88 d d i n (crystallised in this research from extractsof squash or pumpkin eeeds by Drechsel and Grnbler's method) isthe purest proteid obtainable. Scarcity of material prevented theW. D. HORGANIC OHEMISTRY. 343Vitellin ......................Proto-vitellose ................Deutero-vitellose (1) ..........> 9 .. (2) ..........investigation of many points but the general conclusion is that ingastric digestion the changes as in the case of other prote'ids arehydrolytic in nature ; proto-proteose deutero-proteose and peptoneresulting from a series of gradual hydrations as indicated by thegradually diminished percentage of carbon. The amount of hetero-vitellose formed was small.Att.ention was particularly directed to the percentage cornpositionof the products and the following table collects a few of the averagesobtained :- -51 -60 6.97 18 -8051 *52 6 '98 18 -6750 42 6 9 4 18.4349 27 6.70 18 *78The results agree very closely with those previously obtained withthe globulin body myosin the composition of the myosinoses bearingalmost exactly the same relationship to myosin as the vitelloves do to tbecrystallised globulin. A single experiment on tryptic digestionsbowed nothing noteworthy.Crystallisation of Hemoglobin. By S. M. COPE~JAN ( J . Physiob.,11 401-40S).-This i s a full account of experiments a preliminarynotice of which has already appeared (Abstr. 1889 1092). Amongnew points noticed is the factt t h a t some crystals of human hsemo-globin were after the lapse of some months changed into crystals ofhsemochrotnogen. Hoppe-Sepler has previously prepared crystallinehmmochromogen (Abstr. 1889 788).T t was found that using the method of adding putrid serum to theblood the hsemoelobin crystals of the squirrel obtained were not theusual hexagons but rhombic prisms. (Compare Halliburton Abstr.,1886 637). W. D. H.Compounds of Hemoglobin with Carbonic Anhydride. ByC. BOHR (Chenz. Centr. 1890 ii 521 ; from Centr. PhysioZ. 4 253-254) .-As already communicated (Abstr. 1890 1450) there areseveral compounds of hsemoglobin and carhauic anhydride containingvarying proportions of the latter b u t showing dissociation curveswhich are approximately similar. The author now describes the threefollowing :-*,-carbohoeemogZobin wbioh contains about 3.0e.c. of carbonicanhydride per gram at 18" under a pressure o€ 60 mm. of carbonicanhydride ; 6-carhohoemogZobin which contaius about 6.0 C.C. of carb-onic anhydride under the same conditions of temperature and pres-sure ; P-carbohaemoglobin which contains about 1.5 C.C. of carbonicanhydride per gram. It' hsemoglobin is shaken with a mixture ofcarbonic anhydride and oxygen both the gases are absorbed in thesame manner as though each of the gases was present alone. Thespectrum of these hemoglobin compounds appear to be t h e same a8 thatof oxybemoglobin. The author concludes that the carbonic anhydrideW. D. H344 ABSTRACTS OF CHEMICAL PAPERS.and the oxygen combine differently and independently with the heemo-globin and the possibility exists that arterial blood fully charged withoxygen may nevertheless absorb carbonic anhydride. J. W. L

ISSN:0368-1769    

DOI:10.1039/CA8916000281

出版商:RSC    

年代:1891

数据来源: RSC

摘要:

344 ABSTRACTS OF CHEMICAL PAPERS. P hy s i o l o g i c a1 C h e m i s t ry. Effect of Acetic Acid on Respiratory Changes. Bg A. MALLEVRE (Cornpi. rend., 111, 826--828).-Rnbbits which had been subjected to tracheotomy were placed under artificial respiration, voluntary movements being prevented by injection of curarine. The prodiicts of respiration under these conditions were collected and analysed. A 3 per cent. solution of sodium acetate was introduced into the blood drop by drop, and the products of respiration were again examined. Before injection, the extreme values of the rcspira- tory ratio CO,/O were 1.04 and 0.77, but during injection, they sank to 0.86 and 0.69 respectively, a result due to oxidation of the sodium acetate. During injection, the blood becomes alkaline, bnt afterwards again becomes acid.Part, and part only, of the energy of the acetate is used with ,pro&, to the organism, and in this respect acetic acid diffbrs from the majority of food stuffs. C. H. B. By C . BOHR (Chemn. Centr., 1890, ii, 521-523 ; from Centr. Physiol., 4, 254-257). -As already intimated (Abstr., 1890, 1450). h~~moglobin does nc t always absorb the same quantity of oxygen. Pursuing tbis investi- gation, the author has estimated the amounts of hcemoglobin and of oxygen in blood taken systematically from dogs, the latter estimation being made after first shaking the blood with oxjgen of constant tern- peratlire and pressure. The ratio between these two quantities has been nanied the spec$% quantity qf‘ oxygen o j the blood. This ratio varies not only with different animals, but depends also on the exterior conditions under the will of the operator, and i t varies further.in the different parts ofone and the same animal at the same time. From these facts, it ma3 be deduced that the oxygen present in the Idood exerts a varying pres- sure, and that this pressure has a material regulating Influence on the respiratory organs, Moreover, the variations in the pressure thus exerted occur within yery small limits of time, and depend on the number of blood corpusclts which are influenced. In the author’s experiments, strong nncemia was brought about when the arterial blood shdwed a cordant and lower specific quantity of oxygen than before. A similar effect was produced by inhaling air poor in oxFgen.On the other hand, suffocation produced a n increase in the specific quantity of oxygen, and morphine exerted a like influence (compare preceding page). J. W. L. Influence of Protei’d on the Digestion of Foods free from Nitrogen. By T. ROSENHETM (P’iiger’s Archi?,, 46, 422-4331.- In receut researches by Eumagawa (Virchozu’s Archiv, 116), and The Specific Quantities of Oxygen in Blood.PHTSIOLOGICAL CHEMISTRY. 345 Oxygen used. Hirschfeld (Abstr., 1889. 174; on metabolism, these observers stated that equilibrium is possible on smaller quantities of proteid food tharl has hitherto been considered possible. Their experimeubs, however, lasted for too short a time for such a sweeping conclusion to be drawn ; and in the present research i t is shown that in a dog, proteid food is not only valuable in itself, but that i t aids the digestion of other foods which contain no nitrogen, such as carbohydrates and fats.The fmes were examined for undigested residues of carbo- hydrates and fats, and i t was found that these were alwa.ys smaller when there was adrnixthxe of protejid in the food; also that these residues were smaller in direct proportion to the amount of albn- ininons makerial administered. Tbese general results are supported by six series of analyses in which full details are given. W. D. H. Curb, lnic anhydride given out. The Influence of Glycerol and Fatty Acids on Gaseous Metabolism. By I. MUNK (P'liiyer's Arciiiv, 46, 303-334),- Niimerous observations have been made on the question whether glycerol and fatty acids aff'ict gaseous metabolism in any way, and particularly if they act as proteid- sparing or fat-spming foods.Scheremet6effaky (Arbeit. physiol. Alzstalt, L e i p i g , 1869, 194) st aied that in rabbits the intake of oxygen arid output of carbonic anhydride were correspondingly increased after two-grain doses of gljcerol. Zuutz arid v. Mering (P'iiger's Awhio, 32, 174) pointed out errors in Sclreremetkeffsky's niethods ard conclusions. They fonnd the i n - take of oxygen practically unaltered by the intravenous injection of glycerol. 'l'heir experimeri ts were, however, not performed 011 cura- rised animals, and it is possible t h a t the increased discharge of carbonic anhydride observed might! have been due to the musculw niovetnents of the animals. Under these circumstances, it w a s judged advisable to repeat these experiments, precluding the source of error 182 -6 176 '1.267 *9 863.3 237.8 283.5 277 -5 288 -2 268 - 4 281 -0 256 *S l i 8 '6 138.3 134 -1 186 7 193 -1 207 *O 188 7 191 '2 200 *8 2w2 -9 194.3 201 *3 1 178'6 RespirAtory quutient. ---. 0 -72 0.76 0.71 0 '73 0 79 0 '79 0 -67 0 -72 0 - i O 0 *67 0.72 0 'ti9 Period of observation. Before injection During ,, After ,, Before ,, During ,, After ,, Refom ,, During ,, After ,, Before ,, During ,, After ,, Dose of glycerol. 0.5 gr. per kilo. VOL. LX. 2 a346 ABSTRACTS OF CHEMICAL PAPERS. just alluded to, by curai-isation, and to extend the resemch to include ;*ertain fatty acids. The apparatns used was a modification of the Zuntz-Rohrig respiration apparatus, which is fully described.The experiments were made on rabbits ; and the accompanying tables of analyses are averages obtained in each case from a number o f obser- vations, each of which was for a period of 15 minutes. The glycerol was inject.ed slowly into the jugnlar vein. These experiments show that dnring the injection, the intake of oxygen falls slightly, and the output of carbonic anhydride increases to a small extent, thus raising the respiratory quotient ; and the con- clusion is drawn t h a t glycerol when burnt in the body protects from oxidation a fraction of the hody fat. A similar series of experiments were then madc, injecting sodium butyrate instead of glycerol, and again the results may be given in tabular form :- Oxygen used. 260.9 880 '0 253-3 290 -9 328 -2 299 '4 305 *3 330 *9 306 -6 278 -9 297.6 278.1 Carbonic anhydride given out.196 -1 190 -5 181.2 228 *3 214 *6 230 *9 243 *4 238 *O 235 '3 201 -0 197.9 205 -2 Respiratory quotient. 0.75 0 -68 0.71 0 '78 0 .R6 0 '78 0 *79 0 -72 0.77 0 '72 0 6s 0 -73 Period of observation. Before injection During ,, After ,, Before ,, During ,, After ,, Before ,, During ,, After ,, Before ,, During ,, After ,) Dose of butvric acid. 0.4 gr. per kilo. 1 0'56 9 , ?, \ These experiments show that during the injection, the intake o€ oxygen increases, snd the output of carbonic anhydride falls slight81y ; the respiratory quotient therefore falls. Just as in the previous experi- ments with glycerol, none of the substance injected appeared in the urine; it was, taerefore, burnt in the body, and thus must pro- tect it small fraction of the body fat from oxidation.The increased iutake of oxygen appears to be chiefly due to the iricreased frequency of the heart that the soap produces. The increased necessity for oxygen is seen when one notes that, whereas each molecule of glycerol requires 39 mols. of oxygen for complete oxidation, a molecule oE sodium butyrate requires 5 mols. of oxygen for the same purpose. A few experiments were then made with sodium oleate ; the effect of doses similar to those given of the other substances just described produced a rapid decrease of tbe gaseous exchanges, a weakening of tho heart, then syncope and death. A dose of 0.04 gram of ole'icPBY SIOLOGICATI CHEMISTRY. 347 acid per kilo. of body weight produced no a1terat.ion ; a repetition of this dose caused a diminution of the gaseous exchanges by 75 per cent.W. D. H. Transfusion of Mixtures of Blood and Salt Solution. By J. MAKSHACL (Zeit. physiol. Cham., 15, 62-7O).-T1*ansfusion of salt solu- tion is now so often iised i n niedical practice, that i t is important we shoiild have an accurate knowledge of the process of blood regeneration that follows this procedure. Rabbits were bled until convulsions were imminent, and then a solut.ion of one parhof de6brinated blood to nine parts of 0.6 sodium chloride solution was injected; tables are given with enumer3,tion of blood corpuscles, and percentages of hemoglobin before and at. intervals after the operation. When re- generation was complete, the animals were killed, brit in no case was anything abnormal found nt the autopsy. The blood corpuscles reach the normal number in a few dajs, but the percentage of hserno- globin is not normal for some days, in one experiment not until 15 days later.These results coincide closely with those of J . G. Otto (PJliiger's Archim, 36, 67), who used no injection, but simply watchid the course of regeneration after haemorrhage in rabbits. W. D. €1. Amount of Dry Residue and Fat in Arterial and Venous Blood. By F. RCHMANN and J. MUHSAM (Pjuger's Archl'v, 46, 383--397).--Tho statement was made by Bornstein (Zeit. Bid., 13, 133) that the dry residue and fat in veDous, espechlly portal, blood is greater than i n arterial blood. I n the present research, the blood was taken direct from the circulation oE t.he living animal (dog), and no difference in the amount of dry residue could be made out-in the two varieties of blood taken from the femoral vein and carotid artery respectively.Such small diaerences as were ohservable fell within the limits of experimental error. If, however, stasis of the blood within the vessels is allowed to occur, the solid residue of venous blood rises. After bmmorrhage, the specific gravity of the blood falls, but eqndly so in both arterial and veuous blood. Comparative estimations of the amount of fat showed that there was no appreciable difference between the two varieties of blood. Fortal blood was, however, not investigated. W, D. H. Alkalinity of the Blood after Large Doses of Sodium Sulphate. By J. SWIATECKT (Zeit.physiol. Chem., 15, 49--61).-C. Schmidt (Charakt. epid. Cholera, 1850) stated that in thc algide stage of cholera the nlkttlinitay of the hlood is diminished, or i t may become acid, and this observaiion has been, since his time, often confirmed. In order to ascertain whether this is merely dependent on excessive diarrhma, various laxative drugs were a.dministei.ed by Myia and Tassinari (Virchow's u. Hirsah Jahresh., 1887, i, 232), but their exa- mination of the blood gave no positive results. 111 the present research, doses of sodium sulphate, sufficiently large to make the blood very concentrated owing to excessive loss of water per rect.ztnz, 2 a 3348 ABSTRACTS OF CHEMICAL PAPERS. wt’re given t o dogs with the same object in view. The results ob- tained were- (1.) The alkalinity of the blood increases with its density as a con- bcquence of the drug treatment.(2.) This occurrence can be exphined by the greater transudxtion of acids than alkalis from the blood into the alimentarj- tract’, in accordance with laws of osmosis. ( 3 . ) The increase of alkalinity nf the blood which follows the use of nbineral waters cannot therefore he explained by it passing of hmic mlts into the blood froin the alimentary canal. New Method of Hemato-alkalimetry. Relative Alkalinity of the Blood of Vertebrates. By R. CROUIN (Compt. ?-end., 111, &%3-S30).-0*5 C.C. of serum is heated with water and a, drop of :ti1 alcoholic solution of phenolphthaleYn, and the alkalinity is deCer- tnined by means of very dilute sulphuric acid (1 : 1000). The alkalinity is due to salts, such as sodium hydrogen phosphate, sodium hydrogen nrate, &c.0.5 C.C. of serum is treated in a closed Cube with more than sufficient sodium hydroxide to neuti-alise all the acids, and barium chloride is added in quantity more than sufficient to precipitate all carbonates, phosphates, and nrates. The liquid is rnpirlly filtered, ant1 the filtrate is titrated, the sodium hydroxide that has disappeared giving the rtd acidity of the serum. The estiiiiation of water is likewise made with 0.5 C.C. of serum. The alkalinity of tlhe blood of the vertebrates is practically the same in the same groups, but different in different groups. I t is too hmall to be estimated in fishes, is high in manimals, and highest in birds, iiicieasing, in fact, with the rapidity of respiration.The tortoise and the rabbit occupy abnormal positions ; the former show- i n g even a higher alkalinity than birds, whilst the lather has less alkalinity than the frog. Formation of Lactic Acid in Muscles. By 31. WERTHER (P’iiger’s Arcltiv, 46, 63-92).--Snrcolactic acid is the variety of lactic acid formed both during the activity of living muscle and during the rigor which accompanies the death of muscle. In cold- hlooded nnimals, this acid passes, under certain conditions, into the urine (Marcuse, Nebelthan). During r i g o ~ wortis, the percentage of glyc.ogen i n the muscle diminishes, the possibility that this is due to putrefaction being excluded. This last conclusion is oppohed to that of R. Bohm, who states that the glycogen remains unaltered in amount during rigor (Pjliiger’s Archiv, 23).Formation of Lactic Acid in Muscles. Rg R. BOHM ( P f l i i g ~ . ~ ’ ~ A~chiw, 46, 265--266) -In aiiswer to the preceding paper, t I , e author renfirms his previous statements. The Influence of drinking large quantities of Water on the Excretion of Uric Acid. BF B. SCHONDORFF (P’liiger’s AY&Z, 46, 329--1551).-After a very complc>te summary of the literature re1:tt- ing to the influence of various drugs and other agents on the excre- W. D. H. C. H. B. W. D. H. W. D. H.PHYSIOLOGICAL CHEMISTRY. 349 tion of uric acid, the paper is more particularly concerned with tile influence of taking large quantities of water on the exc*retion of tlle aceid. Several investigators, especially Genth ( 17nter.9. ii.d. E’in&ss d. IfTasse4rinkens a. d. Stofwechsel, Wieshaden, i856), have stated that such a procedure, whilst iucreasing the total output of nitrogen (a st ntement since confirmed by many physiologists), diminishes that of iiric acid. Geiit’i, and those who agree with him on this latter point, used for the estimation of uric acid the very imperfect method of Heiutz; in the present research, which wits carried out on tile author’s own person, uric acid was estimated by the Foltker-Sal- kowski process. The total nitrogen was estimated by titration with mei*curic nitrate. The outcome of the experiments is that whilst the total nitrogen is increased, the drinking of large quantities of water has practically no influence on the uric acid.Observations were made daily, and the following table gives the average amounts of water taken atid of uric acid excreted per diem. Ordinary diet.. ................ 18.5 grams. 1.18 grams. Ordinary diet t 1000 C.C. water.. 23.1 ,, 1.14 Sweat of the Horse. By F. SMITH ( J . Phpiot., 11, 497-503). - The composition of the seci-etion of horse’s sweat was investigated because debility follows excessive sweating in these animals. Thc explanation probably is that proteids leave the system in the sweat of liorses (see also Leclerc, Abstr., 1888, 1320). The excreiion can be kept under control by the process of clipping horses in the winter. 500 C.C. of the secretioii was col!ected ; it was alkaline, and was found to have the following percentage composition :- Condition of experiment.Total nitrogen. Uric acid. Oi*dinary diet + 2000 C.C. water.. . 20.4 ,, 0.93 ,, Ordinary diet + 4000 C.C. water.. 20.6 ,, 1.01 ,, W. D:’H. Water.. ........ 94.3776 Serum albumin .... 0.1049 Fat ............... 0.0020 YC hlorine .......... 0.3300 Lime .............. 0-0940 Magnesia 0.2195 traces Soda, .............. 0.8265 [Potash ............ 1.2135 O1ganic matter.. 0.5288 Serum globulin .... 0.3273 { .......... ............ .... .... Sulphuric acid.. 1 I Ash 5*0936{ Phosphoric acid Peptoncs and albumoses are absent, so also is sugar. The amount of prote’id is ninch increased when the horse is in “ bad condition.” The small amount of fat formed probably indicates that the material in\estigat,ed wancl really S W C ~ , ~ , and not sebum.Ether extracts froin tbe sweat an organic, crystalline substance, which is not henzoic acitl, bat the exact nature of which was riot definitely determined. Tbc, mineral SKI bstnnces are nearly ten times larger than the organic, the two most prominent metals beitig potassium and sodium. There350 ABSTRAOTS OF OHEYIOAL PAPERS. would appear to be a close connection between the amount of these salts excreted by the skin and by the kidneys, for during work, when the skin is active, less potash and soda, are eliminaked in the urine than during rest. Excretion of Nitrogen in Sweat. By P. ARGUTINSKP ( P - i i g e r ’ s Archiv, 46, 59&600).-1t is shown that there is au increase of t4he output of nitrogen during excessive muscular work ; and that, more- over, the sweat poured out during such work contains more nitrogen than it normally does.No reference is made to the experiments of North (Abstr., 18d6, 5691, of’ which these are merely confirmatory. W. D. H. W. D. H. Influence of Muscular Work on the Output of Urea. By L. BLE~BTREU (P’iiger’s Archiv, 46, 601-6G7).--Y1he urea in the urine obtained in one of Argutinsky’s series of experiments (preceding abstract) was estimated by the method introduced by the author rtnd E. Pfluger (Abstr., 1890, 308). Represented by curve$, the output of total nitrogen and of urea are shown to be closely parallel ; the increase of both is most marked during the day of the work (walk- ing), and it was not uiitil three days afterwards that they reached the iiormal level. W. D. H. The Relation of Dextrose to the Proteids of the Blood.By I?. SCHENK (Yfliiger’s Archiv, 46,607--615).-1f dextrose is added to blood, serum, or solutions of yroteids, and the fluid is boiled and tiltcred to sepa.i*ate the proteids, a portion only (often less than half) of the sugar is discoverable in the filtrate and washings of the coagu- lum. If the clot is washed with water and with alcohol until no reducing substance passes into solution, and the clot is then boiled with dilute hydrochloric acid, a reducing substance passes into solution in quantities corresponding with the a.mount of sugar formerly lost. It is, therefore, probable that, during coagulation, some of the dextrose combines with the proteids. Diamaines and Cystinuria. By L. v. UDR~NSZKY and E. BAUMANN (Zeit. physiol.Chem., 15, 77--92).--In a previous communication (Abstr., 1889,1024), it mas shown that the urine and feces of patients suffering €rom cjstinuria contain diamines (ptomaines), and t h a t their formation is the result of bacterial activity in the intestinal canal. The cystin, on the other hand, is the result of disordered metabolism. In dogs, it is possible to produce a sort of art.ificial cystinuria; on administering halogen substitution products of benzene to these animals, mercapturic acid (from cystin) is passed in the urine in combination with glycuronic acid ; this, however, does not occur in the human subject. A possible explanation of the association of cgstinuria with diaminuria is that the dirtmines produced in the intestine unite with cystin in the tissues (which under normal cir- cumstances is further metabolised) ; and that this compound is dis- bociated during the act of secretion in the kidnep. I n order to see whether this will hold, dogs were fed on diamines, and their urine esamiued.The first diamine used was ethjlenediamine ; 1.5 grams W. D. H.PHY SIOLOOICSL CHEMISTRY. 351 of this was given to a dog, but the search for it i n the urine passed fiubsequently gave a negative result. The method employed in the isolation of diamines from the urine was that of forming benzoyl compound9 of these substances (Abstr., 1888, 1296). A larger dose was then given, namely, 3.6 grams, and 0.4 gram of dibenzoylethylene- diamine was separated from the urine. No trace of the base was found in the faeces.Cgstin was absent from the urine, or at least there was no more lead sulphide formed on boiling the urine with sodium hydroxide and lead acetate than normally is the case. With tetrarnethylenediamine (putrescine), the results were the same; with a large dose, 3 grams, a mere trace (0.05 gram) of the berizoyl compound was separated from the urine. With pentamethyleriediamiue (cadaverine), the results were also practically the same. The specimen of the base used was found to consist, of two isomerides ; the one with the higher melting point was the least abundant, but in the small amount of the benzoyl compound separated from the urine, i t was the more abundant, being seemingly less readily destroyed in the organism. Such experiments entirely negative the idea that the cause of cystinnria is the formation of diarnines in the alimentary canal.The possibility, however, remains that some other unknown substance accompanying the diauiiues may act i n this way. If this hypothesis is correct, and if this substance is produced by bacteria, anti-bacterial drugs should lessen the amount of cystin in the urine. lllester lirts already bhown (Abstr., 1890, 189) that salol and sulphur have no such effect. In the present researcb, the influence of washing out the large intestine of patients sufGring from cystinuria, with large quantities of water, was observed. The cystin in the uriue was estimated as benzoylcystin, and its amount, and also tbe amount of diamines in the urine, remained practically un- altered. The estimatioii of oxidised and non-oxidised sulphur, by Mester’s method (Abstr., 1890, LS9), con6rmed this conclusion.The question of the relation of cyatinuria to diaminuria is, there- fore, at present unanswered. Absorption of Mercury Salicylate. By L. € 3 6 ~ ~ (Zeit. physiol. Chern., 15’1--36).-Mucb of the present paper is a dissertatiou on the methods of detecticg and estimating mercury in organic mixtures like the urine and faeces. The method adopted in the research is a modi- fication of that of Winternitz (Arch. exper. Path. u. Pharm., 25, 225). Doses of mercury salicylate were given to a cow, but no mercury was found in ’,hc urine or milk. An experiment wag then made on a dog; the urine, bile, blood, faces, and tissues, were examined. 1.5 grams of mercury salicylate (containing 0.85 gram of mercury) was given. Of this tile faeces yielded Us4 ; the remainder was absorbed, and found either in the tissues or excretions.Comparing this with previous similar researches with non-poisonois doses of calomel, the conclusion i s drawn that much more mercury can be abaorbed into the systerri from the salicrlitte than from calomel. W. D. H. W. D. H.344 ABSTRACTS OF CHEMICAL PAPERS.P hy s i o l o g i c a1 C h e m i s t ry.Effect of Acetic Acid on Respiratory Changes. Bg A.MALLEVRE (Cornpi. rend., 111, 826--828).-Rnbbits which had beensubjected to tracheotomy were placed under artificial respiration,voluntary movements being prevented by injection of curarine. Theprodiicts of respiration under these conditions were collected andanalysed.A 3 per cent. solution of sodium acetate was introducedinto the blood drop by drop, and the products of respiration wereagain examined. Before injection, the extreme values of the rcspira-tory ratio CO,/O were 1.04 and 0.77, but during injection, they sankto 0.86 and 0.69 respectively, a result due to oxidation of the sodiumacetate. During injection, the blood becomes alkaline, bnt afterwardsagain becomes acid. Part, and part only, of the energy of the acetateis used with ,pro&, to the organism, and in this respect acetic aciddiffbrs from the majority of food stuffs. C. H. B.By C . BOHR(Chemn. Centr., 1890, ii, 521-523 ; from Centr. Physiol., 4, 254-257).-As already intimated (Abstr., 1890, 1450). h~~moglobin does nc talways absorb the same quantity of oxygen.Pursuing tbis investi-gation, the author has estimated the amounts of hcemoglobin and ofoxygen in blood taken systematically from dogs, the latter estimationbeing made after first shaking the blood with oxjgen of constant tern-peratlire and pressure. The ratio between these two quantities has beennanied the spec$% quantity qf‘ oxygen o j the blood. This ratio varies notonly with different animals, but depends also on the exterior conditionsunder the will of the operator, and i t varies further. in the different partsofone and the same animal at the same time. From these facts, it ma3be deduced that the oxygen present in the Idood exerts a varying pres-sure, and that this pressure has a material regulating Influence onthe respiratory organs, Moreover, the variations in the pressurethus exerted occur within yery small limits of time, and depend onthe number of blood corpusclts which are influenced.In the author’sexperiments, strong nncemia was brought about when the arterialblood shdwed a cordant and lower specific quantity of oxygen thanbefore. A similar effect was produced by inhaling air poor in oxFgen.On the other hand, suffocation produced a n increase in the specificquantity of oxygen, and morphine exerted a like influence (comparepreceding page). J. W. L.Influence of Protei’d on the Digestion of Foods free fromNitrogen. By T. ROSENHETM (P’iiger’s Archi?,, 46, 422-4331.-In receut researches by Eumagawa (Virchozu’s Archiv, 116), andThe Specific Quantities of Oxygen in BloodPHTSIOLOGICAL CHEMISTRY. 345Oxygen used.Hirschfeld (Abstr., 1889.174; on metabolism, these observers statedthat equilibrium is possible on smaller quantities of proteid food tharlhas hitherto been considered possible. Their experimeubs, however,lasted for too short a time for such a sweeping conclusion to bedrawn ; and in the present research i t is shown that in a dog, proteidfood is not only valuable in itself, but that i t aids the digestion ofother foods which contain no nitrogen, such as carbohydrates andfats. The fmes were examined for undigested residues of carbo-hydrates and fats, and i t was found that these were alwa.ys smallerwhen there was adrnixthxe of protejid in the food; also that theseresidues were smaller in direct proportion to the amount of albn-ininons makerial administered.Tbese general results are supported by six series of analyses inwhich full details are given.W. D. H.Curb, lnicanhydridegiven out.The Influence of Glycerol and Fatty Acids on GaseousMetabolism. By I. MUNK (P'liiyer's Arciiiv, 46, 303-334),-Niimerous observations have been made on the question whetherglycerol and fatty acids aff'ict gaseous metabolism in any way, andparticularly if they act as proteid- sparing or fat-spming foods.Scheremet6effaky (Arbeit. physiol. Alzstalt, L e i p i g , 1869, 194) st aiedthat in rabbits the intake of oxygen arid output of carbonic anhydridewere correspondingly increased after two-grain doses of gljcerol.Zuutz arid v.Mering (P'iiger's Awhio, 32, 174) pointed out errorsin Sclreremetkeffsky's niethods ard conclusions. They fonnd the i n -take of oxygen practically unaltered by the intravenous injection ofglycerol. 'l'heir experimeri ts were, however, not performed 011 cura-rised animals, and it is possible t h a t the increased discharge ofcarbonic anhydride observed might! have been due to the musculwniovetnents of the animals. Under these circumstances, it w a s judgedadvisable to repeat these experiments, precluding the source of error182 -6176 '1.267 *9863.3237.8283.5277 -5288 -2268 - 4281 -0256 *Sl i 8 '6138.3134 -1186 7193 -1207 *O188 7191 '2200 *82w2 -9194.3201 *3 1 178'6RespirAtoryquutient.---.0 -720.760.710 '730 790 '790 -670 -720 - i O0 *670.720 'ti9Period ofobservation.Before injectionDuring ,,After ,,Before ,,During ,,After ,,Refom ,,During ,,After ,,Before ,,During ,,After ,,Dose of glycerol.0.5 gr.per kilo.VOL. LX. 2 346 ABSTRACTS OF CHEMICAL PAPERS.just alluded to, by curai-isation, and to extend the resemch to include;*ertain fatty acids. The apparatns used was a modification of theZuntz-Rohrig respiration apparatus, which is fully described. Theexperiments were made on rabbits ; and the accompanying tables ofanalyses are averages obtained in each case from a number o f obser-vations, each of which was for a period of 15 minutes. The glycerolwas inject.ed slowly into the jugnlar vein.These experiments show that dnring the injection, the intake ofoxygen falls slightly, and the output of carbonic anhydride increasesto a small extent, thus raising the respiratory quotient ; and the con-clusion is drawn t h a t glycerol when burnt in the body protects fromoxidation a fraction of the hody fat.A similar series of experiments were then madc, injecting sodiumbutyrate instead of glycerol, and again the results may be given intabular form :-Oxygen used.260.9880 '0253-3290 -9328 -2299 '4305 *3330 *9306 -6278 -9297.6278.1Carbonicanhydridegiven out.196 -1190 -5181.2228 *3214 *6230 *9243 *4238 *O235 '3201 -0197.9205 -2Respiratoryquotient.0.750 -680.710 '780 .R60 '780 *790 -720.770 '720 6s0 -73Period ofobservation.Before injectionDuring ,,After ,,Before ,,During ,,After ,,Before ,,During ,,After ,,Before ,,During ,,After ,)Dose ofbutvric acid.0.4 gr.per kilo. 10'56 9 , ?, \These experiments show that during the injection, the intake o€oxygen increases, snd the output of carbonic anhydride falls slight81y ;the respiratory quotient therefore falls. Just as in the previous experi-ments with glycerol, none of the substance injected appeared in theurine; it was, taerefore, burnt in the body, and thus must pro-tect it small fraction of the body fat from oxidation. The increasediutake of oxygen appears to be chiefly due to the iricreased frequencyof the heart that the soap produces. The increased necessity foroxygen is seen when one notes that, whereas each molecule of glycerolrequires 39 mols.of oxygen for complete oxidation, a molecule oEsodium butyrate requires 5 mols. of oxygen for the same purpose.A few experiments were then made with sodium oleate ; the effectof doses similar to those given of the other substances just describedproduced a rapid decrease of tbe gaseous exchanges, a weakening oftho heart, then syncope and death. A dose of 0.04 gram of ole'iPBY SIOLOGICATI CHEMISTRY. 347acid per kilo. of body weight produced no a1terat.ion ; a repetition ofthis dose caused a diminution of the gaseous exchanges by 75 percent. W. D. H.Transfusion of Mixtures of Blood and Salt Solution.By J.MAKSHACL (Zeit. physiol. Cham., 15, 62-7O).-T1*ansfusion of salt solu-tion is now so often iised i n niedical practice, that i t is important weshoiild have an accurate knowledge of the process of blood regenerationthat follows this procedure. Rabbits were bled until convulsions wereimminent, and then a solut.ion of one parhof de6brinated blood to nineparts of 0.6 sodium chloride solution was injected; tables aregiven with enumer3,tion of blood corpuscles, and percentages ofhemoglobin before and at. intervals after the operation. When re-generation was complete, the animals were killed, brit in no case wasanything abnormal found nt the autopsy. The blood corpusclesreach the normal number in a few dajs, but the percentage of hserno-globin is not normal for some days, in one experiment not until 15 dayslater.These results coincide closely with those of J . G. Otto (PJliiger'sArchim, 36, 67), who used no injection, but simply watchid thecourse of regeneration after haemorrhage in rabbits. W. D. €1.Amount of Dry Residue and Fat in Arterial and VenousBlood. By F. RCHMANN and J. MUHSAM (Pjuger's Archl'v, 46,383--397).--Tho statement was made by Bornstein (Zeit. Bid., 13,133) that the dry residue and fat in veDous, espechlly portal, bloodis greater than i n arterial blood. I n the present research, the bloodwas taken direct from the circulation oE t.he living animal (dog), andno difference in the amount of dry residue could be made out-in thetwo varieties of blood taken from the femoral vein and carotidartery respectively. Such small diaerences as were ohservable fellwithin the limits of experimental error.If, however, stasis of theblood within the vessels is allowed to occur, the solid residue ofvenous blood rises.After bmmorrhage, the specific gravity of the blood falls, buteqndly so in both arterial and veuous blood.Comparative estimations of the amount of fat showed that therewas no appreciable difference between the two varieties of blood.Fortal blood was, however, not investigated. W, D. H.Alkalinity of the Blood after Large Doses of SodiumSulphate. By J. SWIATECKT (Zeit. physiol. Chem., 15, 49--61).-C.Schmidt (Charakt. epid. Cholera, 1850) stated that in thc algide stageof cholera the nlkttlinitay of the hlood is diminished, or i t may becomeacid, and this observaiion has been, since his time, often confirmed.In order to ascertain whether this is merely dependent on excessivediarrhma, various laxative drugs were a.dministei.ed by Myia andTassinari (Virchow's u.Hirsah Jahresh., 1887, i, 232), but their exa-mination of the blood gave no positive results. 111 the presentresearch, doses of sodium sulphate, sufficiently large to make theblood very concentrated owing to excessive loss of water per rect.ztnz,2 a 348 ABSTRACTS OF CHEMICAL PAPERS.wt’re given t o dogs with the same object in view. The results ob-tained were-(1.) The alkalinity of the blood increases with its density as a con-bcquence of the drug treatment.(2.) This occurrence can be exphined by the greater transudxtionof acids than alkalis from the blood into the alimentarj- tract’, inaccordance with laws of osmosis.( 3 .) The increase of alkalinity nf the blood which follows the useof nbineral waters cannot therefore he explained by it passing of hmicmlts into the blood froin the alimentary canal.New Method of Hemato-alkalimetry. Relative Alkalinityof the Blood of Vertebrates. By R. CROUIN (Compt. ?-end., 111,&%3-S30).-0*5 C.C. of serum is heated with water and a, drop of:ti1 alcoholic solution of phenolphthaleYn, and the alkalinity is deCer-tnined by means of very dilute sulphuric acid (1 : 1000). Thealkalinity is due to salts, such as sodium hydrogen phosphate, sodiumhydrogen nrate, &c. 0.5 C.C.of serum is treated in a closed Cubewith more than sufficient sodium hydroxide to neuti-alise all theacids, and barium chloride is added in quantity more than sufficientto precipitate all carbonates, phosphates, and nrates. The liquid isrnpirlly filtered, ant1 the filtrate is titrated, the sodium hydroxide thathas disappeared giving the rtd acidity of the serum.The estiiiiation of water is likewise made with 0.5 C.C. of serum.The alkalinity of tlhe blood of the vertebrates is practically thesame in the same groups, but different in different groups. I t is toohmall to be estimated in fishes, is high in manimals, and highest inbirds, iiicieasing, in fact, with the rapidity of respiration. Thetortoise and the rabbit occupy abnormal positions ; the former show-i n g even a higher alkalinity than birds, whilst the lather has lessalkalinity than the frog.Formation of Lactic Acid in Muscles. By 31.WERTHER(P’iiger’s Arcltiv, 46, 63-92).--Snrcolactic acid is the variety oflactic acid formed both during the activity of living muscle andduring the rigor which accompanies the death of muscle. In cold-hlooded nnimals, this acid passes, under certain conditions, into theurine (Marcuse, Nebelthan). During r i g o ~ wortis, the percentage ofglyc.ogen i n the muscle diminishes, the possibility that this is due toputrefaction being excluded. This last conclusion is oppohed to that ofR. Bohm, who states that the glycogen remains unaltered in amountduring rigor (Pjliiger’s Archiv, 23).Formation of Lactic Acid in Muscles.Rg R. BOHM ( P f l i i g ~ . ~ ’ ~A~chiw, 46, 265--266) -In aiiswer to the preceding paper, t I , eauthor renfirms his previous statements.The Influence of drinking large quantities of Water on theExcretion of Uric Acid. BF B. SCHONDORFF (P’liiger’s AY&Z, 46,329--1551).-After a very complc>te summary of the literature re1:tt-ing to the influence of various drugs and other agents on the excre-W. D. H.C. H. B.W. D. H.W. D. HPHYSIOLOGICAL CHEMISTRY. 349tion of uric acid, the paper is more particularly concerned with tileinfluence of taking large quantities of water on the exc*retion of tlleaceid. Several investigators, especially Genth ( 17nter.9. ii. d. E’in&ss d.IfTasse4rinkens a. d. Stofwechsel, Wieshaden, i856), have stated thatsuch a procedure, whilst iucreasing the total output of nitrogen (ast ntement since confirmed by many physiologists), diminishes that ofiiric acid.Geiit’i, and those who agree with him on this latter point,used for the estimation of uric acid the very imperfect method ofHeiutz; in the present research, which wits carried out on tileauthor’s own person, uric acid was estimated by the Foltker-Sal-kowski process. The total nitrogen was estimated by titration withmei*curic nitrate. The outcome of the experiments is that whilstthe total nitrogen is increased, the drinking of large quantities ofwater has practically no influence on the uric acid.Observations were made daily, and the following table gives theaverage amounts of water taken atid of uric acid excreted per diem.Ordinary diet.................. 18.5 grams. 1.18 grams.Ordinary diet t 1000 C.C. water.. 23.1 ,, 1.14Sweat of the Horse. By F. SMITH ( J . Phpiot., 11, 497-503). -The composition of the seci-etion of horse’s sweat was investigatedbecause debility follows excessive sweating in these animals. Thcexplanation probably is that proteids leave the system in the sweat ofliorses (see also Leclerc, Abstr., 1888, 1320). The excreiion can bekept under control by the process of clipping horses in the winter.500 C.C. of the secretioii was col!ected ; it was alkaline, and wasfound to have the following percentage composition :-Condition of experiment. Total nitrogen. Uric acid.Oi*dinary diet + 2000 C.C.water.. . 20.4 ,, 0.93 ,,Ordinary diet + 4000 C.C. water.. 20.6 ,, 1.01 ,,W. D:’H.Water.. ........ 94.3776Serum albumin .... 0.1049Fat ............... 0.0020YC hlorine .......... 0.3300Lime .............. 0-0940Magnesia 0.2195tracesSoda, .............. 0.8265[Potash ............ 1.2135O1ganic matter.. 0.5288 Serum globulin .... 0.3273 {.......... ............ .... .... Sulphuric acid.. 1I Ash 5*0936{ Phosphoric acidPeptoncs and albumoses are absent, so also is sugar. The amountof prote’id is ninch increased when the horse is in “ bad condition.”The small amount of fat formed probably indicates that the materialin\estigat,ed wancl really S W C ~ , ~ , and not sebum. Ether extracts frointbe sweat an organic, crystalline substance, which is not henzoic acitl,bat the exact nature of which was riot definitely determined. Tbc,mineral SKI bstnnces are nearly ten times larger than the organic, thetwo most prominent metals beitig potassium and sodium.Ther350 ABSTRAOTS OF OHEYIOAL PAPERS.would appear to be a close connection between the amount of thesesalts excreted by the skin and by the kidneys, for during work, whenthe skin is active, less potash and soda, are eliminaked in the urinethan during rest.Excretion of Nitrogen in Sweat. By P. ARGUTINSKP ( P - i i g e r ’ sArchiv, 46, 59&600).-1t is shown that there is au increase of t4heoutput of nitrogen during excessive muscular work ; and that, more-over, the sweat poured out during such work contains more nitrogenthan it normally does.No reference is made to the experiments of North (Abstr., 18d6,5691, of’ which these are merely confirmatory.W.D. H.W. D. H.Influence of Muscular Work on the Output of Urea. By L.BLE~BTREU (P’iiger’s Archiv, 46, 601-6G7).--Y1he urea in the urineobtained in one of Argutinsky’s series of experiments (precedingabstract) was estimated by the method introduced by the author rtndE. Pfluger (Abstr., 1890, 308). Represented by curve$, the outputof total nitrogen and of urea are shown to be closely parallel ; theincrease of both is most marked during the day of the work (walk-ing), and it was not uiitil three days afterwards that they reached theiiormal level. W. D. H.The Relation of Dextrose to the Proteids of the Blood.ByI?. SCHENK (Yfliiger’s Archiv, 46,607--615).-1f dextrose is added toblood, serum, or solutions of yroteids, and the fluid is boiled andtiltcred to sepa.i*ate the proteids, a portion only (often less than half)of the sugar is discoverable in the filtrate and washings of the coagu-lum. If the clot is washed with water and with alcohol until noreducing substance passes into solution, and the clot is then boiledwith dilute hydrochloric acid, a reducing substance passes into solutionin quantities corresponding with the a.mount of sugar formerly lost.It is, therefore, probable that, during coagulation, some of thedextrose combines with the proteids.Diamaines and Cystinuria. By L. v. UDR~NSZKY and E. BAUMANN(Zeit. physiol.Chem., 15, 77--92).--In a previous communication(Abstr., 1889,1024), it mas shown that the urine and feces of patientssuffering €rom cjstinuria contain diamines (ptomaines), and t h a t theirformation is the result of bacterial activity in the intestinal canal.The cystin, on the other hand, is the result of disordered metabolism.In dogs, it is possible to produce a sort of art.ificial cystinuria; onadministering halogen substitution products of benzene to theseanimals, mercapturic acid (from cystin) is passed in the urine incombination with glycuronic acid ; this, however, does not occur inthe human subject. A possible explanation of the association ofcgstinuria with diaminuria is that the dirtmines produced in theintestine unite with cystin in the tissues (which under normal cir-cumstances is further metabolised) ; and that this compound is dis-bociated during the act of secretion in the kidnep.I n order to seewhether this will hold, dogs were fed on diamines, and their urineesamiued. The first diamine used was ethjlenediamine ; 1.5 gramsW. D. HPHY SIOLOOICSL CHEMISTRY. 351of this was given to a dog, but the search for it i n the urine passedfiubsequently gave a negative result. The method employed in theisolation of diamines from the urine was that of forming benzoylcompound9 of these substances (Abstr., 1888, 1296). A larger dosewas then given, namely, 3.6 grams, and 0.4 gram of dibenzoylethylene-diamine was separated from the urine. No trace of the base wasfound in the faeces.Cgstin was absent from the urine, or at leastthere was no more lead sulphide formed on boiling the urine withsodium hydroxide and lead acetate than normally is the case.With tetrarnethylenediamine (putrescine), the results were thesame; with a large dose, 3 grams, a mere trace (0.05 gram) of theberizoyl compound was separated from the urine.With pentamethyleriediamiue (cadaverine), the results were alsopractically the same. The specimen of the base used was found toconsist, of two isomerides ; the one with the higher melting point wasthe least abundant, but in the small amount of the benzoyl compoundseparated from the urine, i t was the more abundant, being seeminglyless readily destroyed in the organism. Such experiments entirelynegative the idea that the cause of cystinnria is the formation ofdiarnines in the alimentary canal. The possibility, however, remainsthat some other unknown substance accompanying the diauiiues mayact i n this way. If this hypothesis is correct, and if this substanceis produced by bacteria, anti-bacterial drugs should lessen the amountof cystin in the urine. lllester lirts already bhown (Abstr., 1890, 189)that salol and sulphur have no such effect. In the present researcb,the influence of washing out the large intestine of patients sufGringfrom cystinuria, with large quantities of water, was observed. Thecystin in the uriue was estimated as benzoylcystin, and its amount,and also tbe amount of diamines in the urine, remained practically un-altered. The estimatioii of oxidised and non-oxidised sulphur,by Mester’s method (Abstr., 1890, LS9), con6rmed this conclusion.The question of the relation of cyatinuria to diaminuria is, there-fore, at present unanswered.Absorption of Mercury Salicylate. By L. € 3 6 ~ ~ (Zeit. physiol.Chern., 15’1--36).-Mucb of the present paper is a dissertatiou on themethods of detecticg and estimating mercury in organic mixtures likethe urine and faeces. The method adopted in the research is a modi-fication of that of Winternitz (Arch. exper. Path. u. Pharm., 25, 225).Doses of mercury salicylate were given to a cow, but no mercury wasfound in ’,hc urine or milk. An experiment wag then made on a dog;the urine, bile, blood, faces, and tissues, were examined. 1.5 grams ofmercury salicylate (containing 0.85 gram of mercury) was given. Ofthis tile faeces yielded Us4 ; the remainder was absorbed, and foundeither in the tissues or excretions. Comparing this with previoussimilar researches with non-poisonois doses of calomel, the conclusioni s drawn that much more mercury can be abaorbed into the systerrifrom the salicrlitte than from calomel.W. D. H.W. D. H

ISSN:0368-1769    

DOI:10.1039/CA8916000344

出版商:RSC    

年代:1891

数据来源: RSC

摘要:

352 ABSTRACTS OF CEEBLICAL PAPE;EtS. Chemistry of Vegetable Physiology and Agriculture. Apparatus for the Manufacture of Pure Yeast. By A. FERX- EACH (Bull. SOC. Chim. [3], 4, 11;3-116).-The apparatus consists of a tinned-copper cylinder provided with a movable head, which can be adapted hermetically to the body by means of screw clamps and a caoutchouc washer ; through oritices in the head, tubes paqs by which steam can be passed into the vessel, as also filtered air, which makes its escape into the liquid from small orifices in a. flat coil at the base of the cylinder. The clcar wort is boiled in the vessel, and steam is passed through to completely sterilise i t ; all the orifices are then closed by tubes containing colton-wool ; on cooling, the yeast is sowu, and while growing a curreut of filtered air is driven through the spiral, so that the fungus is grown under aikobiotic conditions.The yield obtained is ver.y good ; a wort derived from 3 kilos. of malt at 63-65" furnishing a crop of 300 grams of pressed yeast i n eight dsyu. T. G. N. The Nitrifying Process and its Specific Ferment. By P. l?. FRANKLAND and G. C. FHANKLANL) (Proc. tzoy. Soc., 47, 296-298).- Nitrification was induced i n an atnmoniacal solution by means of a small quantity of garden soil, and then carried thi-ough 24 genera- tions. Gelatin plates were prepared from several of the generations, and the resulting colonies inoculated into ammoniacal solutious, but in no case did nitrification ensne. Experiments wGre then made to isolate the nitrifying organism by dilution with sterilised distilled water.When an attenuation of 1 part of original solution in 1,000,000 had been reached in three diffarent cases, the liquids thus produced behaved as tollows: One nitrified but refused to grow in gelatin-peptone ; another protliiced a growth but would not nitrify ; whilst the third did both. I t was thus shown that the organisms were reduced to two, one of which caused nitrification. Uncler the miciwscope, this appeared to be a bacillus scarcely longer than broad. Although i t will not gmw in gelatin when inoculated from dilute media, it produces a characteristic slow growth in broth, which nitrifies amnioniacal solutions, and also grows in gelatin. The form of the organism from the broth is slightly ciilkrent from the original organism, but the identity of the two is established by the former returning to the original form when grown again in arnmouiacal solution.A Bacteria-killing Globulin. By E. H. HANKIN (PTOC. BUY. SOC., 48, 93--101).-l'he results described in this paper were arrived at by the author while trying t o discover the nature c;f the substance to which the bacteria-killing powers of the blcod serum is due. Halli- burton's cell-globulin-p wa8 extracted from the lymphatic glands of an animal by sodium sulphate solution. It was found to have the 1)ower of killing anthrax bacilli, which property seems to dis- tinguibh it fwm fibrin ferment. This b,zcteris-killing power is of J. W.VEQETABLE PHYSIOLOGY AND AQRICULTURE. 853 the trame nature as that possessed by blood serum, which, therefore, probably acts in virtue of the same or of some allied substance.From his experiments, the author further concludes that, inasmuch as it is possible to obtain from the cells that are, or can become, phago- cytes, a substance having bacteria-killing powers, itl may be supposed that phagocytes can not only kill microbes that they have ingested, but also do this by breaking down, and liberating their contents. Antiseptic Action of Methylene Fluoride. By C. CHAVRTE (Cowipt. r e i d , 111, 748 -750).-Methylene fluoride prevents the development of the pyogenic bacterium of urine and kills the bacteria already developed. It has no irritating action on the digit’al membrane or meseutery of a frog. J. W. C. H. R. Acquisition of Atmospheric Nitrogen by Plants.By W. 0. AT\vA*rw and C. D. WOODS (Amer. Chern. J., 12, 526--54.j).-The authors describe a very 1;lrge number of experiments with peas, oats, and corn, which confirm the view that nitrogen is readily absorbed from the atmosphere by these plants, when treated with “soil- infusion,” and that the gain of nitmgen is dependent on the number of root-tubercles which the application of “ soil-infusion ” induces. (Compare Lawes and Gilbert, Abstr., 3889, 814, and Phil. Truus., 1889, 1-107.) G. T. M. Fixation of Gaseous Nitrogen by Leguminosae. By T. ~ C H L O E S ~ N G , JuN., and E. LAUKENT ( C o r q t . rend., 111, 750 -753).- Legurninom were grown in closed vessels, so arranged that the gases introduced and withdrawn (air, carbonic anhydride, nitrogen, and oxygen) could be accurately measured and analysed.When the legumes had been watered with an infusion of nodosities from other plants of tbe same order, there was an absorption of nitrogen much greater than could be attributed to errors of experiment. Where the legumes had not beeu inoculated in this way, and, consequently, were free from nodosi ties, no such absorption of nitrogen was observed. The results obtained by direct measurement, therefore, agree with the result obtained indirectly from gravirnetric analyses. Berthelot (ibid., 753) regards these results as a final proof that, under the influence of microbes, legumes can utilise and fix the gaseous nitrogen of the atmosphere. C. H. B. The Fungus-symbiosis of the Leguminosae. By B. FRAKK (Lundw. Juhrb., 19, 523--64O).-A large part of the paper is devoted to the description and discussion of experiments and microscopic observations relating to the mode of acquisition of organisms by legu- minous plants ; the cultivation of the organisms, their relations to the plants, and the r62e of the infected plant, &c.In order to ascertain the influence exerted by the organism (which be terms Rhizobium leguminosawm), quantitative experiments w e ~ c made with beans, penns, and lupins, grown in ignited sand, in sandy soil, atid in hnmous soil. It1 some experiments, the soil was aterilised, in others it mas seeded with soil organisms, and to some nitrate was354 ABSTRACTS OF CHEMICAL PAPERS. Dry plvduce (grams). applied. Tbe results of the experiments, as well as those obtained with oats and rape, are given in the following table.Three or four, or more, pots were used for each experimerit ; at the conclusion the soil of all the siinilar pots was mixed; and the produce was also united and mixed for analysis. The soils used for microbe seeding were:-Sandy soil (3 and 16), bean soil (4), pea soil (9), meadow soil (17), and lupiii soil (18). 4 g r a m s of soil was given to each pot, for tbe purpose of seeding. The ainount of soil used for each experi- ment (not pot) is given at the headings of each series. Nitrogen (grams). At coa.mencernent. At conclusion. - - - Soil. 1 sz:::&pr 1 Seeds. I Total. Soil. 14.767 1'450 - 0'035 1.435 2.371 0'361 - 0.042 1-782 3"&0 0.134 - O"42 1'7J'& 2'446 0'300 :$ 11'455 1.740 16t 17%5 1.740 l i t 16.09)Y 1'740 0.730 0'04t 2.512 3.438 0'304 lat 38.754 1-740 0'00ri 0.042 1,766 4'404 0.777 Beans i n Sandy Soil (12 kilos.).2'732 1-247 3'424 I%#L 2'i46 0'964 3 . 7 ~ 7 1 'LL5 5'181 3.893 Kitrate. Sterilised. t Sterilised and seeded. 5 One pot less LII~II 15-16; 13 kilos. of soil.VEQETABLE PHYSIOLOGY AND AQRICULTURE. 355 Lupins (21) and Bare Soil (22) (Sandy Sod 12 kilos.). O1 8.480 1.154 - 0-070 1-224 2-172 0.184 2'356 1-131 'k I - I 1'154 1 - 1 - 1 1'154 I 2,062 1 - 1 2'062 1 0'908 With regard to beans, the growth was always only slight in poor soil, whether microbe-seeded or not ; beans therefore resemble non-leguminous plants. The fungus in symbiosis with beans has the cliaracter of a parasite, and is fed by the plant without asskting it in return.Lupins assiniilatc a small amount of nitrogen when free from organisms, but much more when seeded. Peas are only able to fix nitmgen when microbe-seeded, or when grown in soil, or in sand containing organic matter (compare Ahstr., 1890, 1000). In every case (except those of peas grown in sandy soil) there was a gain of nitrogen in the soil. The gain which takes place in bare soil (Experiment 2 ~ ) is attributed to the presence of algaa under the influence of light and moisture. The results obtained with oats and rape are given in support of the author's view that the power of assimilating free nitrogen by plants is not con6ned to the Legumi- ~nosce, but is as general as the assimilation of carbonic anhydride. The nodule-organisms could not be cultivated except in nilsogenous menstrua, and are, tberefore, assumed to be incapable of assimilating nitrogen.The high percentage of nitrogen in the nodules, and the presence of starch in them, indicate that the building up of proteids takes place in them. At the same time, i t is hardly con- ceivable thst the fixation of free nitrogen takes place in the under- ground organs of the plant. It might be suggested that nitric nitrogen is formed, which yields proteids with starch; but the fact that no nitrates or nitrites could be detected (by diphenylamine) in the nodules, although nitric acid was found in the roots of peas (but not lupins), is opposed to this view. On the other hand, amides OCCIII* in all pnrts of the plants, and also in the nodules ; and it is probable that in the first instance, the frco nitrogen of the air combines with the elements of a uon-nitrogenous carbon com- pound present in the leaves, where i t is first produced, to form an ainide, and that tbis finds its way into the nodules, where it reacts with starch and yields proteids.The fixation therefore, takes place in the leaves.3.56 ABSTRACTS OF CHEMICAL PAPERS. The author considers tliat there is only one nodule organism, common to all leguminous plants, and that it is present in all natural ~nils, although in varying amounts (compare Hellriegel and W ilfAi-th, Ber. deut. bot. Gss., 7 , 138). No‘rE.-Prairnowski’s experiments with pure cultivations of nodule-organisms from peas indicate that the organisms have the power of assimilating free iiitrogen, in absence of any other source, although the amount of nitrogen assimilated by the organisms apart from the plant is only small.I n view of the great change which the organisms undergo in symbiosis with plants, the diflerence is not remarkable (Landw. Versuchs-Stat., 38, 55). N. H. J. M. N. H. J. M. Nature of Reserve Cellulose and its Mode of Solution during Germination of Seed. By REISS (Ann. AgrOlt., 16, 478-4801.- The cellulose forming the thickened walls of the albumen (botanical) containing cells of many seeds dissolves during germination, and assists in the nutrition of the young seedling ; it is, therefoxe, called reserve cellulose. In date seeds, it is the portion of the cell-wall nearest the cell-centre which dissolves ; in asparagits seeds, the middle layer between neighbouring cells and the iiiner layer next the proto- plasm both dissolve; garlic seeds are similar, but, the thickened walls have innumerable fine branching canals, which the author calls canals of corrosion, and which facilitate the solution.Even in seeds whose cell-walls are not thickened, the cellulose dissolves, com- mencing a t the niiddle layers and proceeding towards the internal linings. In other seeds (balsam, monkshood, cyclamen, for example), this reserve cellulose is replaced by an amyloid substance, which also is traversed by canals of corrosion and dissolves. It is more soluble in 50 per cent. nitric acid thari reserve cellulose. Reserve cellulose cannot be separaked b j Hofmeister’s process for “ crude fibre,” since: a portion dissolves in ammonia. The product of its hydrolysis (studied in the “albumen” of Phytelcphas) with sulphuric acid is strnhin, a lsevogyratory substance or mixture ; the dextrins of ordinary cellulose foymed in the same way being dextrogyratorg.Submitted to further liydrolytic treatment, seminin gives a new mgitr, fermentable, reducing, and dextogyratory, which the author calls semiriose. Seminose gives with phenylhydrazine acetate, in the cold, a colour- less hydrazone sparingly soluble in water ; it gives also an isonitroso- compound in fi tie, colourless crystals, analogous to the compound Risclrbieth obtained with galactose, but not with dextrose, ltevulose, or arabinose. Seminose is precipitated by lead acetate in neutral nqueous solution, and this, according to the author, distinguishes it from Vischer and Hirschberger’s mctri,nose, the only other known sugar giving a slightly soluble phenylhydrazone ; mannose is pre- cipitable only by amrrioniacal lead acetate.The abstractor to tbe Am.. Agron., however, points out that Fischer and Hirschberger have recently found that mannose is rapidly precipitated from strong soliit.ions by lead acetate, and that these an thws consider seminose to be identical with rnaticose. Seminin exists ready formed in the seedVEGETABLE PHYSIOLOGY AND AGRICULTURE. 357 o f PhyteEephas ; it has been obkained by saccharifying the reserve cellu- lose of seeds of date, Chanzacrops, Lodokca, Elais guineensis, AlEi~m crpn, asparagus, Iris pseudoacorus, fennel, coffee, and nux vomicn. The seedzings contain only ordinary cellulose, the reserve cellulose having been perhaps transformed into seminose during germination.Seminose, howerer, was not discorered in germinating date seeds, but plenty of (probsblv) dextrose, Hydrolysis of the amyloid substance of balsam, monkshood, primrose, and peony seeds gave dextrose, not fie mi n ose. J. M. H. M. Conversion Products of Starch. Bp A . MARCACCI (Bied. Centr., 19, 792; from Sfaa. sper. agr. ital., 18, 618--619).-Potato starch, even in quite ripe potatoes, becomes converted into cme-sugar; and barley and wheat grains, in germinating. double the amount of cme- sugar at the expense of the starch they originally contained. Samples of potato meal and finely-cut potat,oes were dried, some in the sun, nnd some in a dryin? oven a t 45" ; an illcrease of cane-sugar was observed in the artificially dried potato ; in the cut.potatoes, the amount of sugar was more than doubled when dried at 43". I n ger- mination, potatoes gain saccharose ; the starch is probably converted, first into saccharose, and then into glucose. The formation of dextriri is not necessnry. Unripe wheat graius contain much glucose and sacchsrose ; when the same anloant o€ grains were examined after being dried in the sun, the sugar had disappeared, and was found to be replaced by starch. The Presence of Cholesterol and a Soluble Carbohydrate in Melon Seeds. By C. FORTI (Chwn. Cenfr., 1890, ii, 581-582; from Staz. sperirn. a g ~ i c . ital., 18, SSO--SSS) .-Determinations of the amount of phosphorus in the ether extract of the seeds of melons showed i t to be present in the proportion of O.Cl189 to 0.U3 per cent.I t exists as lecithin, and is equivalent to 0.494 to 0.526 per cent. of the latter. Adopting the views of Scliulze arid Steiger (Abstr., 1889, ti45), that the substance should be extracted witah alcohol in order to obtain all the lecilhin, the author found 0.024 per cent. of phosphorus, equivalent to 0.629 per cent. of lecithin. The seeds contain abont 49 per cent. of oi;, which is almost Free from free fatty acids; the distillate of 25 grams neutralised 3.2 C.C. of decinormal barium hydr- oxide solution. Having saponified the fat with sodium hydroxide, the dry sonp was treated wit,h ether, which extracttd a' substance, soluble ill alcohol ; this crjstallised in yellowish, fatty scales, and did not consist entirely of fat, and WAX.When treated with alcoholic potash, a nori-sn;oonitiable residue was leftt, which proved to be cholsterol. It melted at 160", contailled 1 mol. of water of crystallisation, and has the formula C2(,H140,€T20 ; the water separntes at 100". A minute portion of this cholesterol. wlien treated with a drop of iiitric acid aiid evaporated tc dryness, left a yellow residue, which became colonred bright red by ammonia; the coloration was intensified by the addition of sodium hydroxide. The cLlorofonu solution was coloured bromn by Starch is formed by the elimination of water. N. H. J. M.358 ABSTRAOTS OF CHEMICAL PAPERS. siilphiiric acid, the coloration changing to violet and finally Fellow Rfter a time, whilst the suiphnric acid layer became reddish-brown arid fluoresced.The chloroform solution, when shaken with a little ferric chloride and hydrochloric acid and evaporated to dryness, left a yellow residue, whicb, when again treated with chloroform in the cold and then gently warmed, became violet, and left a dirty-green residue on evaporating to dryness. The specific rotatory power of the substance in chloroform solution was [ a ] ~ = 14.17. The acetyl derivative, C,,H,,-OAc, crystallised from absolnte alcohol in lustrou~ plates melting at li0-173" to a lemon yellow fluid. When boiled with potash, potassium acetate and the original cholesterol are obtained. The acetyl derivative of cholesterol from bile crptdlises in needles and melts a t 111".The benzoyl dei-izutive is very slightly soluble in alcohol, and separates from the solution, on cooling, in small crystals which melt at 172-179'. These properties of this cholesterin differ from those of the better-known cholesterol, and require further investigation. The soluble carbohydrate of melon seeds is dextro-rotatory, even after treatment with acids, and appears to belong to the galactan ponp. It forms rtn amorphous, yellowish-white, very hrgroscopic powder. After boiling with hydrochloric acid, the phenylhydrazine derivative of the product was prepared ; this melts at 184-186". J. W. L. Amount of The'ine in Tea. By R . H. PAUL and A. J. COWNLEY (Yharm. J . Trans., [3 3, 21, 61).-Believing that the amount of thehe in t.en has commonly been understated, owing to defective methods of determination, the authors have made a f urhher series of analyses.Eight, samples, purchased at grocers' shops in the ordinary way, yielded from 2-93 t o 3.93, average 3-39, per cent. of theine calculated on the dried tea. Four samples of China tea gave 2.42, 3.50, 3-63, and 3.78 per cent. respectively. Four samples of cheap Japan Congou averaged 2-80 per cent. thebe, but as much as 4.10 per cent. was found in a Java tea. Japan and China teas appear, therefore, generallv inferior as regards content of the'ine to Indian or Ceylon teas, which, on the other hand, are approached by Java ten. In these analyses duplicate determinations of the the'itie were made with magnesia and with lime -the only methods that are trustwortliy. R. R. Acidity of Potato Starch.By SAARE ( A m . Agron., 16, 471).- Most samples of potato starch are slightly acid, and the acid is said to increase with age, but the author believes that perfectly neutral fitarch can be obtained, and that it will, if properly dried, keep with- out, developing the slightest acidify. Discussing the source of the acid, the author remarks that potato-juice is naturally acid, and that. the starch, if imperfectly washed, will retain some of this ; that lactic and butyric acids may be developed by bacterial fermentations during manufacture ; and that sulphuric and sulphurous acids are sometimes nsed in the pmcess of manufactme. The acid, whatever it is, canttot be perfectly removed bv washing with pure water, but, if hard water be used, the acid becomes neutralised by the lime.J. M. H. M.VEGETABLE PHYSIOLOGY AND AGRICULTURE. 359 Maize dried in the Field and as Silage. By H. P. ARUSBY and W. €3. CALDWELL (Bied. Centr., 19, 753- 756; from Agric. Science, 4, 119--146).-A maize field, manured with farm-yard manure, Carolina phosphrlte, and blood meal, was divided into three parts, the produce of Iwo divisions put into two silos, and that of the third division kept for a month on the field to dry. The one silo was filled quickly (one day) and contained 17,000 kilos. ; the second was filled slonflv (seven davs), and contained about 15,600 kilos. The weight of the hay was 4300 kilos. The maize put into the silos had the followinq composition; (1) refers to the quickly and (2) to the slowly filled silo :- Non- Crude Non-nit.rogenous Water.Ash. Proteld. protei'd. fibre. extract. Fat. 1. 7690 1-97 !.63 0.13 5.16 13.42 0.77 2. 76.26 1.43 1-46 0.30 5-65 14.26 0.66 The temperature rose qnickly at first, especially at the snrface, and more in t,he slowly-filied silo than in the other one. The following table shows the total amount of produce (in kilos.) in the two silos (1 and 2, as before) and of hay (3) :- Non- Crude Non-nit,rogenous extract. Fat. 1. 3920 333 277 27 876 2276 131 2. 3 i l 3 238 228 48 832 2284 104 3. 2677 195 176 26 617 1579 82 Experiments were made with two Ilevonshire bullocks to determine t,he digestibility of the different preparations, the food being given for seven days before the experiments began. Samples of food and feces were taken daily for analysis, and the animals were weighed each day befnre and after drinking.The amounts giren were: silage, (1) 20.412 kilos., (2) 15.899 kilos. of fresh, or 5.655 and 4.662 kilos. of dry substance ; hay, 7 265 or 5.263 kilos. of dry matter. The results show that the dry substance of the ma4ize hay is the most readily digested, and that that of the silage from thc slowly filled silo i-J the least digestible. The digestibility of the prote'id is nearly the game in each case, whilst the fat of the hay seems to be less digestible than that of the ensilage. The variation i n the digestibility of the dry substance is chiefly due to differences in the digestibility of the crude fibre rtnd tbe non-nitrogenous extract. The results are given in tables, together with those of Woll rtnd of Sturtevant. The results do not indicate any great difference of digestibility between maize ensilage and maize hay.The ensilage lost (in the silo) half as much dry matter and two- lifthe as much prote'id as the hay lost; but a quarter of the prote'id was converted into non-proteid. The hay lost 14 per cent. of crude fibre ; no snch loss was observed in the cme of the ensilage. Dry snbstttnce. Ash. ProteCd. protei'd. fibre. N. H. .T. M. Wine Analyses. By E. BOSSHARD (Zeit. anal. Chem., 1890, 551- 556).-The results are given of the analysis, by the usual methods,3 60 ABSTRACTS OF CHEMICAL PAPERS. of 24 specimens of wine from the Valtellina, 24 from the Coire Valley, 5 specimens of Medoc (1883-1887), and 4 Tuscan wines. The composition of the Valtellina wines does not differ notably from that of other red wines, the alcohol ranging from 7.83 (in a cheap bpecimen of Veltlincr) to 1443 vols.per cent. (in a fine Valgella), with an average of 10.97, and the solid residue from 17-24 to 26-45 (average 23.0) grams per litre The ash of several of the varieties contained much manganese. The wines of the Coire Valley are, on the average, less alcoholic: (max. 11 44, min. 8.01 ; average 9.73). but contain rather more ex- tractive matter (max. 25.61, min. 19.86 ; average 24.05). I n compo- sition they show coiisiderable resernblance to Burgundy, and, if more carefully fermented, they would take a much higher position than they do at present. rd. J. s.352 ABSTRACTS OF CEEBLICAL PAPE;EtS.Chemistry of Vegetable Physiology and Agriculture.Apparatus for the Manufacture of Pure Yeast.By A. FERX-EACH (Bull. SOC. Chim. [3], 4, 11;3-116).-The apparatus consists ofa tinned-copper cylinder provided with a movable head, which can beadapted hermetically to the body by means of screw clamps and acaoutchouc washer ; through oritices in the head, tubes paqs by whichsteam can be passed into the vessel, as also filtered air, which makesits escape into the liquid from small orifices in a. flat coil at the baseof the cylinder. The clcar wort is boiled in the vessel, and steam ispassed through to completely sterilise i t ; all the orifices are thenclosed by tubes containing colton-wool ; on cooling, the yeast is sowu,and while growing a curreut of filtered air is driven through thespiral, so that the fungus is grown under aikobiotic conditions.Theyield obtained is ver.y good ; a wort derived from 3 kilos. of malt at63-65" furnishing a crop of 300 grams of pressed yeast i n eightdsyu. T. G. N.The Nitrifying Process and its Specific Ferment. By P. l?.FRANKLAND and G. C. FHANKLANL) (Proc. tzoy. Soc., 47, 296-298).-Nitrification was induced i n an atnmoniacal solution by means of asmall quantity of garden soil, and then carried thi-ough 24 genera-tions. Gelatin plates were prepared from several of the generations,and the resulting colonies inoculated into ammoniacal solutious, butin no case did nitrification ensne.Experiments wGre then made to isolate the nitrifying organism bydilution with sterilised distilled water.When an attenuation of1 part of original solution in 1,000,000 had been reached in threediffarent cases, the liquids thus produced behaved as tollows: Onenitrified but refused to grow in gelatin-peptone ; another protliiced agrowth but would not nitrify ; whilst the third did both. I t was thusshown that the organisms were reduced to two, one of which causednitrification. Uncler the miciwscope, this appeared to be a bacillusscarcely longer than broad. Although i t will not gmw in gelatinwhen inoculated from dilute media, it produces a characteristic slowgrowth in broth, which nitrifies amnioniacal solutions, and also growsin gelatin. The form of the organism from the broth is slightlyciilkrent from the original organism, but the identity of the two isestablished by the former returning to the original form when grownagain in arnmouiacal solution.A Bacteria-killing Globulin.By E. H. HANKIN (PTOC. BUY. SOC.,48, 93--101).-l'he results described in this paper were arrived atby the author while trying t o discover the nature c;f the substance towhich the bacteria-killing powers of the blcod serum is due. Halli-burton's cell-globulin-p wa8 extracted from the lymphatic glands ofan animal by sodium sulphate solution. It was found to have the1)ower of killing anthrax bacilli, which property seems to dis-tinguibh it fwm fibrin ferment. This b,zcteris-killing power is ofJ. WVEQETABLE PHYSIOLOGY AND AQRICULTURE. 853the trame nature as that possessed by blood serum, which, therefore,probably acts in virtue of the same or of some allied substance.From his experiments, the author further concludes that, inasmuch asit is possible to obtain from the cells that are, or can become, phago-cytes, a substance having bacteria-killing powers, itl may be supposedthat phagocytes can not only kill microbes that they have ingested,but also do this by breaking down, and liberating their contents.Antiseptic Action of Methylene Fluoride.By C. CHAVRTE(Cowipt. r e i d , 111, 748 -750).-Methylene fluoride prevents thedevelopment of the pyogenic bacterium of urine and kills the bacteriaalready developed. It has no irritating action on the digit’al membraneor meseutery of a frog.J. W.C. H. R.Acquisition of Atmospheric Nitrogen by Plants.By W. 0.AT\vA*rw and C. D. WOODS (Amer. Chern. J., 12, 526--54.j).-Theauthors describe a very 1;lrge number of experiments with peas, oats,and corn, which confirm the view that nitrogen is readily absorbedfrom the atmosphere by these plants, when treated with “soil-infusion,” and that the gain of nitmgen is dependent on the numberof root-tubercles which the application of “ soil-infusion ” induces.(Compare Lawes and Gilbert, Abstr., 3889, 814, and Phil. Truus.,1889, 1-107.) G. T. M.Fixation of Gaseous Nitrogen by Leguminosae. By T.~ C H L O E S ~ N G , JuN., and E. LAUKENT ( C o r q t . rend., 111, 750 -753).-Legurninom were grown in closed vessels, so arranged that the gasesintroduced and withdrawn (air, carbonic anhydride, nitrogen, andoxygen) could be accurately measured and analysed. When the legumeshad been watered with an infusion of nodosities from other plants of tbesame order, there was an absorption of nitrogen much greater thancould be attributed to errors of experiment.Where the legumes hadnot beeu inoculated in this way, and, consequently, were free fromnodosi ties, no such absorption of nitrogen was observed. The resultsobtained by direct measurement, therefore, agree with the resultobtained indirectly from gravirnetric analyses.Berthelot (ibid., 753) regards these results as a final proof that,under the influence of microbes, legumes can utilise and fix thegaseous nitrogen of the atmosphere. C. H. B.The Fungus-symbiosis of the Leguminosae. By B.FRAKK(Lundw. Juhrb., 19, 523--64O).-A large part of the paper is devotedto the description and discussion of experiments and microscopicobservations relating to the mode of acquisition of organisms by legu-minous plants ; the cultivation of the organisms, their relations to theplants, and the r62e of the infected plant, &c.In order to ascertain the influence exerted by the organism (whichbe terms Rhizobium leguminosawm), quantitative experiments w e ~ cmade with beans, penns, and lupins, grown in ignited sand, in sandysoil, atid in hnmous soil. It1 some experiments, the soil was aterilised,in others it mas seeded with soil organisms, and to some nitrate wa354 ABSTRACTS OF CHEMICAL PAPERS.Dryplvduce(grams).applied.Tbe results of the experiments, as well as those obtainedwith oats and rape, are given in the following table. Three or four,or more, pots were used for each experimerit ; at the conclusion thesoil of all the siinilar pots was mixed; and the produce was alsounited and mixed for analysis. The soils used for microbe seedingwere:-Sandy soil (3 and 16), bean soil (4), pea soil (9), meadowsoil (17), and lupiii soil (18). 4 g r a m s of soil was given to each pot,for tbe purpose of seeding. The ainount of soil used for each experi-ment (not pot) is given at the headings of each series.Nitrogen (grams).At coa.mencernent. At conclusion.- --Soil. 1 sz:::&pr 1 Seeds. I Total. Soil.14.767 1'450 - 0'035 1.435 2.371 0'361 - 0.042 1-782 3"&0 0.134 - O"42 1'7J'& 2'446 0'300:$ 11'455 1.74016t 17%5 1.740l i t 16.09)Y 1'740 0.730 0'04t 2.512 3.438 0'304lat 38.754 1-740 0'00ri 0.042 1,766 4'404 0.777Beans i n Sandy Soil (12 kilos.).2'732 1-2473'424 I%#L2'i46 0'9643 .7 ~ 7 1 'LL55'181 3.893Kitrate. Sterilised. t Sterilised and seeded.5 One pot less LII~II 15-16; 13 kilos. of soilVEQETABLE PHYSIOLOGY AND AQRICULTURE. 355Lupins (21) and Bare Soil (22) (Sandy Sod 12 kilos.).O1 8.480 1.154 - 0-070 1-224 2-172 0.184 2'356 1-131 'k I - I 1'154 1 - 1 - 1 1'154 I 2,062 1 - 1 2'062 1 0'908With regard to beans, the growth was always only slight in poorsoil, whether microbe-seeded or not ; beans therefore resemblenon-leguminous plants. The fungus in symbiosis with beans has thecliaracter of a parasite, and is fed by the plant without asskting it inreturn.Lupins assiniilatc a small amount of nitrogen when freefrom organisms, but much more when seeded. Peas are only ableto fix nitmgen when microbe-seeded, or when grown in soil, or insand containing organic matter (compare Ahstr., 1890, 1000). Inevery case (except those of peas grown in sandy soil) there was again of nitrogen in the soil. The gain which takes place in bare soil(Experiment 2 ~ ) is attributed to the presence of algaa under theinfluence of light and moisture. The results obtained with oats andrape are given in support of the author's view that the power ofassimilating free nitrogen by plants is not con6ned to the Legumi-~nosce, but is as general as the assimilation of carbonic anhydride.The nodule-organisms could not be cultivated except in nilsogenousmenstrua, and are, tberefore, assumed to be incapable of assimilatingnitrogen. The high percentage of nitrogen in the nodules, and thepresence of starch in them, indicate that the building up of proteidstakes place in them.At the same time, i t is hardly con-ceivable thst the fixation of free nitrogen takes place in the under-ground organs of the plant. It might be suggested that nitricnitrogen is formed, which yields proteids with starch; but thefact that no nitrates or nitrites could be detected (by diphenylamine)in the nodules, although nitric acid was found in the roots of peas(but not lupins), is opposed to this view. On the other hand,amides OCCIII* in all pnrts of the plants, and also in the nodules ; andit is probable that in the first instance, the frco nitrogen of the aircombines with the elements of a uon-nitrogenous carbon com-pound present in the leaves, where i t is first produced, to form anainide, and that tbis finds its way into the nodules, where it reactswith starch and yields proteids.The fixation therefore, takesplace in the leaves3.56 ABSTRACTS OF CHEMICAL PAPERS.The author considers tliat there is only one nodule organism,common to all leguminous plants, and that it is present in all natural~nils, although in varying amounts (compare Hellriegel and W ilfAi-th,Ber. deut. bot. Gss., 7 , 138).No‘rE.-Prairnowski’s experiments with pure cultivations ofnodule-organisms from peas indicate that the organisms have thepower of assimilating free iiitrogen, in absence of any other source,although the amount of nitrogen assimilated by the organisms apartfrom the plant is only small.I n view of the great change which theorganisms undergo in symbiosis with plants, the diflerence is notremarkable (Landw. Versuchs-Stat., 38, 55).N. H. J. M.N. H. J. M.Nature of Reserve Cellulose and its Mode of Solution duringGermination of Seed. By REISS (Ann. AgrOlt., 16, 478-4801.-The cellulose forming the thickened walls of the albumen (botanical)containing cells of many seeds dissolves during germination, andassists in the nutrition of the young seedling ; it is, therefoxe, calledreserve cellulose.In date seeds, it is the portion of the cell-wallnearest the cell-centre which dissolves ; in asparagits seeds, the middlelayer between neighbouring cells and the iiiner layer next the proto-plasm both dissolve; garlic seeds are similar, but, the thickenedwalls have innumerable fine branching canals, which the author callscanals of corrosion, and which facilitate the solution. Even in seedswhose cell-walls are not thickened, the cellulose dissolves, com-mencing a t the niiddle layers and proceeding towards the internallinings. In other seeds (balsam, monkshood, cyclamen, for example),this reserve cellulose is replaced by an amyloid substance, which alsois traversed by canals of corrosion and dissolves. It is more solublein 50 per cent. nitric acid thari reserve cellulose.Reserve cellulosecannot be separaked b j Hofmeister’s process for “ crude fibre,” since:a portion dissolves in ammonia. The product of its hydrolysis(studied in the “albumen” of Phytelcphas) with sulphuric acid isstrnhin, a lsevogyratory substance or mixture ; the dextrins ofordinary cellulose foymed in the same way being dextrogyratorg.Submitted to further liydrolytic treatment, seminin gives a newmgitr, fermentable, reducing, and dextogyratory, which the authorcalls semiriose.Seminose gives with phenylhydrazine acetate, in the cold, a colour-less hydrazone sparingly soluble in water ; it gives also an isonitroso-compound in fi tie, colourless crystals, analogous to the compoundRisclrbieth obtained with galactose, but not with dextrose, ltevulose, orarabinose.Seminose is precipitated by lead acetate in neutralnqueous solution, and this, according to the author, distinguishes itfrom Vischer and Hirschberger’s mctri,nose, the only other knownsugar giving a slightly soluble phenylhydrazone ; mannose is pre-cipitable only by amrrioniacal lead acetate. The abstractor to tbeAm.. Agron., however, points out that Fischer and Hirschberger haverecently found that mannose is rapidly precipitated from strongsoliit.ions by lead acetate, and that these an thws consider seminoseto be identical with rnaticose. Seminin exists ready formed in the seeVEGETABLE PHYSIOLOGY AND AGRICULTURE. 357o f PhyteEephas ; it has been obkained by saccharifying the reserve cellu-lose of seeds of date, Chanzacrops, Lodokca, Elais guineensis, AlEi~m crpn,asparagus, Iris pseudoacorus, fennel, coffee, and nux vomicn.Theseedzings contain only ordinary cellulose, the reserve cellulose havingbeen perhaps transformed into seminose during germination.Seminose, howerer, was not discorered in germinating date seeds,but plenty of (probsblv) dextrose, Hydrolysis of the amyloid substanceof balsam, monkshood, primrose, and peony seeds gave dextrose, notfie mi n ose. J. M. H. M.Conversion Products of Starch. Bp A . MARCACCI (Bied. Centr.,19, 792; from Sfaa. sper. agr. ital., 18, 618--619).-Potato starch,even in quite ripe potatoes, becomes converted into cme-sugar; andbarley and wheat grains, in germinating. double the amount of cme-sugar at the expense of the starch they originally contained.Samplesof potato meal and finely-cut potat,oes were dried, some in the sun,nnd some in a dryin? oven a t 45" ; an illcrease of cane-sugar wasobserved in the artificially dried potato ; in the cut. potatoes, theamount of sugar was more than doubled when dried at 43". I n ger-mination, potatoes gain saccharose ; the starch is probably converted,first into saccharose, and then into glucose. The formation of dextririis not necessnry.Unripe wheatgraius contain much glucose and sacchsrose ; when the same anloanto€ grains were examined after being dried in the sun, the sugar haddisappeared, and was found to be replaced by starch.The Presence of Cholesterol and a Soluble Carbohydrate inMelon Seeds.By C. FORTI (Chwn. Cenfr., 1890, ii, 581-582; fromStaz. sperirn. a g ~ i c . ital., 18, SSO--SSS) .-Determinations of theamount of phosphorus in the ether extract of the seeds of melonsshowed i t to be present in the proportion of O.Cl189 to 0.U3 per cent.I t exists as lecithin, and is equivalent to 0.494 to 0.526 per cent. ofthe latter. Adopting the views of Scliulze arid Steiger (Abstr., 1889,ti45), that the substance should be extracted witah alcohol in order toobtain all the lecilhin, the author found 0.024 per cent. of phosphorus,equivalent to 0.629 per cent. of lecithin. The seeds contain abont49 per cent. of oi;, which is almost Free from free fatty acids; thedistillate of 25 grams neutralised 3.2 C.C. of decinormal barium hydr-oxide solution.Having saponified the fat with sodium hydroxide, the dry sonp wastreated wit,h ether, which extracttd a' substance, soluble ill alcohol ;this crjstallised in yellowish, fatty scales, and did not consistentirely of fat, and WAX.When treated with alcoholic potash,a nori-sn;oonitiable residue was leftt, which proved to be cholsterol.It melted at 160", contailled 1 mol. of water of crystallisation, andhas the formula C2(,H140,€T20 ; the water separntes at 100". A minuteportion of this cholesterol. wlien treated with a drop of iiitric acid aiidevaporated tc dryness, left a yellow residue, which became colonredbright red by ammonia; the coloration was intensified by the additionof sodium hydroxide. The cLlorofonu solution was coloured bromn byStarch is formed by the elimination of water.N.H. J. M358 ABSTRAOTS OF CHEMICAL PAPERS.siilphiiric acid, the coloration changing to violet and finally FellowRfter a time, whilst the suiphnric acid layer became reddish-brown aridfluoresced. The chloroform solution, when shaken with a little ferricchloride and hydrochloric acid and evaporated to dryness, left a yellowresidue, whicb, when again treated with chloroform in the cold andthen gently warmed, became violet, and left a dirty-green residue onevaporating to dryness. The specific rotatory power of the substancein chloroform solution was [ a ] ~ = 14.17.The acetyl derivative, C,,H,,-OAc, crystallised from absolnte alcohol inlustrou~ plates melting at li0-173" to a lemon yellow fluid.Whenboiled with potash, potassium acetate and the original cholesterol areobtained. The acetyl derivative of cholesterol from bile crptdlises inneedles and melts a t 111". The benzoyl dei-izutive is very slightlysoluble in alcohol, and separates from the solution, on cooling, in smallcrystals which melt at 172-179'. These properties of this cholesterindiffer from those of the better-known cholesterol, and require furtherinvestigation.The soluble carbohydrate of melon seeds is dextro-rotatory, evenafter treatment with acids, and appears to belong to the galactanponp. It forms rtn amorphous, yellowish-white, very hrgroscopicpowder. After boiling with hydrochloric acid, the phenylhydrazinederivative of the product was prepared ; this melts at 184-186".J. W.L.Amount of The'ine in Tea. By R . H. PAUL and A. J. COWNLEY(Yharm. J . Trans., [3 3, 21, 61).-Believing that the amount of thehein t.en has commonly been understated, owing to defective methods ofdetermination, the authors have made a f urhher series of analyses.Eight, samples, purchased at grocers' shops in the ordinary way, yieldedfrom 2-93 t o 3.93, average 3-39, per cent. of theine calculated on thedried tea. Four samples of China tea gave 2.42, 3.50, 3-63, and 3.78per cent. respectively. Four samples of cheap Japan Congou averaged2-80 per cent. thebe, but as much as 4.10 per cent. was found in aJava tea. Japan and China teas appear, therefore, generallv inferioras regards content of the'ine to Indian or Ceylon teas, which, on theother hand, are approached by Java ten.In these analyses duplicatedeterminations of the the'itie were made with magnesia and with lime-the only methods that are trustwortliy. R. R.Acidity of Potato Starch. By SAARE ( A m . Agron., 16, 471).-Most samples of potato starch are slightly acid, and the acid is saidto increase with age, but the author believes that perfectly neutralfitarch can be obtained, and that it will, if properly dried, keep with-out, developing the slightest acidify. Discussing the source of theacid, the author remarks that potato-juice is naturally acid, and that.the starch, if imperfectly washed, will retain some of this ; that lacticand butyric acids may be developed by bacterial fermentations duringmanufacture ; and that sulphuric and sulphurous acids are sometimesnsed in the pmcess of manufactme.The acid, whatever it is, canttotbe perfectly removed bv washing with pure water, but, if hard waterbe used, the acid becomes neutralised by the lime. J. M. H. MVEGETABLE PHYSIOLOGY AND AGRICULTURE. 359Maize dried in the Field and as Silage. By H. P. ARUSBY andW. €3. CALDWELL (Bied. Centr., 19, 753- 756; from Agric. Science, 4,119--146).-A maize field, manured with farm-yard manure, Carolinaphosphrlte, and blood meal, was divided into three parts, the produceof Iwo divisions put into two silos, and that of the third division keptfor a month on the field to dry. The one silo was filled quickly (oneday) and contained 17,000 kilos.; the second was filled slonflv (sevendavs), and contained about 15,600 kilos. The weight of the hay was4300 kilos.The maize put into the silos had the followinq composition; (1)refers to the quickly and (2) to the slowly filled silo :-Non- Crude Non-nit.rogenousWater. Ash. Proteld. protei'd. fibre. extract. Fat.1. 7690 1-97 !.63 0.13 5.16 13.42 0.772. 76.26 1.43 1-46 0.30 5-65 14.26 0.66The temperature rose qnickly at first, especially at the snrface, andmore in t,he slowly-filied silo than in the other one. The followingtable shows the total amount of produce (in kilos.) in the two silos(1 and 2, as before) and of hay (3) :-Non- Crude Non-nit,rogenousextract. Fat.1. 3920 333 277 27 876 2276 1312. 3 i l 3 238 228 48 832 2284 1043.2677 195 176 26 617 1579 82Experiments were made with two Ilevonshire bullocks to determinet,he digestibility of the different preparations, the food being given forseven days before the experiments began. Samples of food and feceswere taken daily for analysis, and the animals were weighed each daybefnre and after drinking. The amounts giren were: silage, (1)20.412 kilos., (2) 15.899 kilos. of fresh, or 5.655 and 4.662 kilos. ofdry substance ; hay, 7 265 or 5.263 kilos. of dry matter. The resultsshow that the dry substance of the ma4ize hay is the most readilydigested, and that that of the silage from thc slowly filled silo i-J theleast digestible. The digestibility of the prote'id is nearly the gamein each case, whilst the fat of the hay seems to be less digestiblethan that of the ensilage. The variation i n the digestibility of thedry substance is chiefly due to differences in the digestibility of thecrude fibre rtnd tbe non-nitrogenous extract. The results are given intables, together with those of Woll rtnd of Sturtevant. The resultsdo not indicate any great difference of digestibility between maizeensilage and maize hay.The ensilage lost (in the silo) half as much dry matter and two-lifthe as much prote'id as the hay lost; but a quarter of the prote'idwas converted into non-proteid. The hay lost 14 per cent. of crudefibre ; no snch loss was observed in the cme of the ensilage.Drysnbstttnce. Ash. ProteCd. protei'd. fibre.N. H. .T. M.Wine Analyses. By E. BOSSHARD (Zeit. anal. Chem., 1890, 551-556).-The results are given of the analysis, by the usual methods3 60 ABSTRACTS OF CHEMICAL PAPERS.of 24 specimens of wine from the Valtellina, 24 from the CoireValley, 5 specimens of Medoc (1883-1887), and 4 Tuscan wines.The composition of the Valtellina wines does not differ notably fromthat of other red wines, the alcohol ranging from 7.83 (in a cheapbpecimen of Veltlincr) to 1443 vols. per cent. (in a fine Valgella),with an average of 10.97, and the solid residue from 17-24 to 26-45(average 23.0) grams per litre The ash of several of the varietiescontained much manganese.The wines of the Coire Valley are, on the average, less alcoholic:(max. 11 44, min. 8.01 ; average 9.73). but contain rather more ex-tractive matter (max. 25.61, min. 19.86 ; average 24.05). I n compo-sition they show coiisiderable resernblance to Burgundy, and, if morecarefully fermented, they would take a much higher position thanthey do at present. rd. J. s

ISSN:0368-1769    

DOI:10.1039/CA8916000352

出版商:RSC    

年代:1891

数据来源: RSC