57 Organic Chemistry. Californian Petroleum. By CHARLES F. MABERY (Anzer. Chena. J., 1897, 19, 796-804).-This paper contains a preliminary account of experiments on the composition of Californian petroleum. The samples examined diff ermarkedly ; one fromVentura County, which is very thick and nearly black, is a highly sulphurised oil (0.84 per cent.), and con- tains a large amount of nitrogen (0.53 per cent.). It unites with more bromine (17.72 per cent.) than Pennsylvanian or Ohio oils, but approxi- mately the same as Canadian oil ; pTobably a considerable portion of the bromine disappears by substitution, since the crude oil contains a large amount of aromatic hydrocarbons. In the lower fractions, the hydrocarbons belong to the series C,H,,. Fresno County petroleum is lighter in colour than the foregoing, and has more of a greenish hue.It contains 0.21 per cent.. of sulphur, and gave a bromine absorption of 9.07 per cent. A. W. C. Constitution of Inorganic Compounds, X. Ammoniacal Chromiumthiocyanogen Compounds, By ALFRED WERNER and GEORG RICHTER (Zeit. anorg. Chem., 189 7,15,243--277).-The authors have examined the two salts known as Reinecke’s and Morland’s salts which are formed by the action of potassium dichromate on fused ammonium thiocyanate, a mixture of the two salts being obtained by gradually adding the powdered dichromate (40 grams) to fused ammonium thiocyanate (200 grams) ; the powdered melt is treated with a small quantity of cold water, and the residue, which contains the two salts together with sulphur, is extracted with successive quantities of water a t 50’ with the addition of a few drops of acetic acid as long as considerable quantities of Reinecke’s salt are removed, Morland’s salt remaining undissolved.Reinecke’s salt, or, according to Werner’s nomenclature, potassium tetrathiocyanodiamminec?womiuna, KCr(NK,!,(SCN),,H,O, is prepared from the above aqueous extract, in which i t IS mixed with the ammo- nium salt, by precipitating it as cadmium salt and decomposing the latter by an aqueous solution of potassium hydrogen sulphide. It crystallises in ruby-red, lustrous plates, or, without water of crystal- lisation, in scarlet nodules or rhombododecahedra. A determination of the number of ions in the aqueous solutions shows that the salt is easily split into the two ions Cr(WH,),(SCN), and K.From the residue, obtained as mentioned above, Morland’s salt is ex- tracted by hot water containing a few drops of acetic acid; it cannot, however, be completely separated from the preceding salt, either by crystallisation from water or from alcohol. When it is converted into the cadmium salt, and the latter is decomposed by a soIution of potas- sium hydrogen sulphate, it yields Reinecke’s salt, and the filtrate from the cadmium salt contains guanidine. It is therefore guar~idine tetra- thioc yanodiamminechromium. Nitrosyl tet.r~ccthiocyanodiamminechromi~m., Cr(NH3),(SCN),N0, may VOL. LXXIV. i. f58 ABSTRACTS OF CHEMICAL PAPERS. be prepared by adding to a saturated solution of Reinecke's salt, 10 per cent. of its volume of dilute nitric acid (1 acid to 1 water).It is also obtained by treating an acidified solution of Reinecke's salt with nitric peroxide, or, better, with a mixture of nitric oxide and nitrous oxide, or with a nitrite; in the last two cases, a quantitative precipitation is obtained. The crystalline precipitate is washed with water containing a few drops of nitric acid and dried on a porous plate. It crystallises in right-angled, four-sided prisms which are dark reddish-brown by transmitted light ; the small crystals are dark brown in reflected light, the larger ones black. It is decomposed by water with partial oxida- tion into Reinecke's acid. With alkalis, it yields Reinecke's salt and a nitrite ; with ammonia, Reinecke's ammonium salt with violent evolu- tion of nitrogen.By careful oxidation with nitric acid, it yields the compound Cr(NH3)2(SCN)3(H,0),. a-Trithiocyanodiaquodium-nzinecl~romium, Cr(NH,)& SCN),(H,O),, has already been obtained by Nordenskjold (Zeit. unorg. Chern., 1, 137) by oxidising Reinecke's salt with hydrogen peroxide. It is also obtained by the electrolysis of a solution of Reinecke's salt, by oxidisingit with potassium chlorate and hydrochloric acid, and by cautious oxidation with warm dilute nitric acid. It is most easily obtained by acting on Reinecke'd salt (10 grams) with a concentrated solution of hydrogen peroxide prepared by treating sodium peroxide (10 grams) with a slight excess of concentrated hydrochloric acid and twice its volume of ice ; as soon as the violent evolution of hydrogen cyanide commences, the mixture is cooled sufficiently to maintain the temperature below 70-80".The mixture is then filtered and the filtrate evaporated a t the ordinary temperature until salt commences to separate, when the whole of the trithiocyanodiaquodiamminechromium will have crystal- lised out ; finally, the product is purified by crystallisation from alcohol. When dissolved in water, no ionisation takes place. When treated with ammonia, a mixture of compounds containing more ammonia is obtained, but these have not yet been separated. P-trithiocyunodiuquodiamminec~~~ionaium, isomeric with the preceding compound, is obtained along with the preceding salt by the oxidation of Reinecke's salt o r the compound Cr(NH,),(SCN),NO with nitric acid a t 100". It can be separated from its isomeride by crystallisation frpm warm water, in which it is less soluble.The a-trithiocyanide crystal- lises in six-sided tablets with an angle of 120" belonging to the hexa- gonal system ; the P-trithiocyanide in four-sided tablets with angles of 104" and 76", belonging t o the monosymmetric system. The a-com- pound has a more intense and bluish-red colour ; the /?-compound is yellowish-red ; both compounds when warmed with a concentrated solution of alkali thiocyanate a t 100" are a t once converted into Reinecke's salt. The two compounds give precipitates with many salts of the heavy metals and with organic bases containing nitrogen, a list being given of those which can be used t o distinguish between the isomerides. For example, with cadmium chloride, a 5 per cent.aqueous solution of the a-compound yields a bright red precipitate, the P-compound no precipitate ; with guanidine nitrate, the a-compound yields a very characteristic precipitate of elliptical leaflets, the /I-com- pound no precipitate. E. C. R.ORGANIC CHEMISTRY. 59 Action of Nitric Acid on Potassiuni Cobalticyanide. By EMILE C. A. FLEURENT (Compt. rend., 1897, 125, 537-538).-When 100 parts of potassium cobalticyanide is heated at 100' for about 10 hours with 500 parts of nitric acid diluted with an equal volume of water, a deep orange-red, fluorescent liquid is obtained, and if after separation of the potassium nitrate by crystallisation this is neutralised with potassium carbonate and mixed with excess of alcohol of 66", the syrupy mass described by Jackson and Comey (Abstr., 1896, i, 402) separates, but the liquid also contains a product which gives all the reactions of nitroprussides and is most readily separated in the form of the cupric salt.Hydrates of Magnesium Platinocyanide and their Solubility. By HELLMUTH (BARON) BUXHOEVDEN and GUSTAV TAMMANN (Zeit. anoyg. Chem., 1897, 15, 319-327).--Magnesium platinocyanide is obtained by decomposing tLe copper salt, suspended in water, with hydrogen sulphide, neutralising the solution of hydrogen platinocyanide thus formed with magnesia, evaporating, and allowing it to crystallise, The red crystals thus obtained always contain less water than is required by the formula MgPt(CN), + 7H20. The vapour tension of a saturated solution at 19" of the composition IVIgPt(CN)4 + 3712H20 is 14.4 mm, ; when the vapour tension is greater, the crystals deliquesce, and a t a lower vapour tension they give off water, whilst at a pressure of 7 mm.the yellow hydrate with 5H,O is formed. Homogeneous red crystals with 6.8-6.25 H,O are obtained at 19' under a vapour tension of 14.4-7 mm. Neither the hydrate with 7H,O nor the hydrate with 6H20 crystallises from the saturated solution, but from 0-45' crystals with 6.9-6.6 H20 are obtained ; the vapour tension of these crystals is the same as that of the solutions from which they are obtained. When these red crystals are dried, the following hydrates are obtained : a t 45", a bright yellow hydrate with 5H20 ; a t 60°, a bright green hydrate with 4H,O ; a t loo', a white hydrate with 2H,O, and a t 210°, the orange-red, anhydrous salt.These hydrates are present in the saturated solutions as follows, from - 4.12-45" the red hydrate, above 45" the hydrate with 5H,O is formed, from 45-88' the green hydrate is stable, and above 88' the white hydrate is formed. Tables and curves of the solubility of the various hydrates are given. The results show that each hydrate has a characteristic solubility. E. C. R. Synthesis of Hexamethylene-glycol Diethyl Ether and other Ethers from Trimethylene Glycol. By ARTHUR A. NOYES (Amer. Chem J., 1897, 19, 766-781).-Trimethyle?zegZycol monethylic ether, produced by the action of ethylic iodide on the monosodium derivative of trimethylene glycol, is a colourless, pleasant-smelling liquid, miscible with water in all proportions; it boils a t 160-161° (corr,), has a sp.gr. = 0.915 at 25'/25", and an index of refraction 1.416 at 25". [With H. M. CHASE.]-T~~ corresponding cliethplic ether, which is a liquid insoluble in water, possesses a fruity odour, boils at 140-141" (corr.), and has sp. gr.=0*835 at 25'/25'. Ethylic y-chZoqwopp!ic ether, prepared by the action of phosphorus C. H. B. f 260 ABSTRACTS OF CHEMICAL PAPERS. trichloride on the above monethylic ether, is a liquid boiling at 130-131" (corr.) and of sp. gr. = 0.957 a t 25'/25". The corresponding bromo-compound is a n aromatic-smelling liquid, insoluble in water, boiling a t 150-151", and having a sp. gr. = 1.3 at 25"/25". [With GRACE A. VAN EVEREN] the iodo-compound boils at 130-134" (150 mm.), and has a sp.gr. = 1.585 at 25'125". Hexamefii~lene glycol diethplic ether is obtained by the action of sodium on ethylic y-chloro- (bromo- or iodo-) propylic ether, the best yield (28-30 per cent.) being obtained with either the bromo- o r iodo- compounds. It is a colourless liquid, insoluble in water, boiling a t 208" (corr.) at ordinary atmospheric pressure, and having a sp. gr. = 0.546 a t 25'/25" ; it dissolves in cold concentrated sulphuric acid, and is reprecipitated on adding water. Phosphorus trichloride has little or no action on it. [With L. H. GoODHUE.]-y-~t~Ox?~b~t~jl'ic cccid, OEt *CH,*CH ,*CH;COOH, was prepared by the action of potassium cyanide on ethylic y-bromo- propylic ether, and subsequent hydrolysis of the nitrile thus obtained ; it is a colourless liquid, soluble in water, and boils between 230-240".On submitting the potassium salt of this acid to electrolysis, small amounts of hexamethylene-glycol diethylic ether were obtained. [With H. H. TOZTER.]--E'thyliC y-phen&ropylic elher, prepared by the action of sodium on a mixture of bromobenzene and ethylic bromopro- pylic ether, is a liquid of terpene-like odour, boiling at 224" (corr.), and having a sp. gr. = 0,924 at 15"/15'. [With C. H. SToKE.]-Ethylic y-ethoxypi*opyhnalonate, obtained by the action of ethylic bromopropylic ether on ethylic sodiomalonate, is a nearly odourless liquid boiling at 273" (corr.) and of sp. gr. = 1.016 at 15'/15". On hydrolysis and subsequent elimination of carbonic anhy- dride from the dicarboxylic acid, 8-ethoxyualeric ucid is obtained as a colourless liquid, soluble in water, boiling at 252", and having a sp. gr.= 0.994 at 25"/25". Another substance was produced in this reaction, but its exact nature was not determined. A. W. C. Formaldehyde Derivatives of the Polyatomic Alcohols and Acids of the sugar Group. By K. WERER ttnd BERNHARD TOLLENS (Bey., 1897, 30, 2510-2514. Compare Abstr., 1894, i, 438; 1896, j , 645) .-With formaldehyde and hydrochloric acid, dulcitol yields tlinaeth?lZerzeduZcitol, C6H1,(CH2)20,, which is optically inactive and crystallises in needles melting at 244-245" ; the dibenxoate C,H,O,(CH,),(OBz),, melts at 328-231", and the diucetnte at 258-260". DimetJ~yleizer?~anznitol, C,H,,(CH,),O,, is pxepared from rhamnitol and crystallises in needles rrielting a t 138-139'.It is dextrorotatory, [.ID = + 9" ; the monobenzoate forms needles, which melt a t 136-1 37". ,2fo?c;orr.letl~?/Zenerhccmno?iic lactone, C,H80,: CH,? is obtained from rhamnonic lactone and crystallises in tablet,s which melt at 17s-1SO"; i t is Izvorotatory ([a],= - 85.4") and is mono- basic towards warm aqueous boda. Rhamnohexonic acid does not yield any formaldehyde derivative ; glucoheptonic lactone, on the other hand, is readily convei tcd into dimethyleneg luco7ieytonic lactone, C',H8( CH,),O,, which has been ob-ORGANIC CHEMISTRY. 61 tained in two different forms ; the less soluble of these is lmorotatory ( [aID = - 69.5") and melts at about 280°, whereas the more soluble has a greater rotation ([.ID = - 101.) and melts a t about 230'.The acid is readily decomposed by bases, and hence it is extremely difficult t o prepare its salts. When saccharin is treated with formaldehyde and hydrochloric acid, a substance is formed which has the composition of triir?zetl~yZe7zedisacc?~arin, C12H14(C€€2)30~o, crystallises in needles or plates, melts a t 139-1403, and is lmwrotatory ; [a],= - 8 2 . 8 O . The presence of the carboxyl group appears t o hinder the action of formaldehyde with the adjacent hydroxyl group, the action being further influenced by the configuration of the reacting substance. It appears that substances which yield mucic acid react much less completely than their isomerides ; thus mucic acid itself gives no formaldehyde, and the same is true of rhamnohexonic acid, which yields mucic acid on oxidation.Moreover, dulcitol only yields a dimethylene-derivative, whilst its isomerides, mannitol and sorbitol, form trimethylene compounds. A. H. Preparation of Soluble Starch and Starch Solution. By OTTO FOERSTER (Chenz. Zeit., 1897,21, 41).-To prepare soluble starch, a paste of 20 t o 25 grams of starch with water is poured in a thin stream into 200 t o 300 C.C. of hot water containing 5 C.C. of con- centrated hydrochloric acid, the liquid being stirred until i t becomes homogeneous and fairly fluid ; heat is then applied and the stirring continued until the liquid is clear and as limpid as water. After cooling, it is filtered, alcohol added to the filtrate, the precipitate which is formed washed with alcohol until free from chlorine, then with ether, allowed to dry i l l t h e air, and finally dried by gently warming, or, better, by allowing it t o remain over sulphuric acid.To prepare a solution of starch, 20 grams are dissolved as described above, the hydrochloric acid being carefully measured so that i t may afterwards be exactly neutralised. The volume of the neutral filtered solution is made up to a litre by adding glycerol. The excess of water can be evaporated after the addition of the glycerol, whereby the stability of the solution is perhaps increased. Both these preparations give blue colorations with iodine. Soluble Starch. By WIKTOR SYNIEWSKI (Ber., 1897, 30, 2415-2418) -Soluble starch may be obtained by the action of a 9 per cent. solution of sodium peroxide on potato starch suspended in water, and is purified by repeated precipitation by alcohol, when i t forms a snow-white, amorphous substance which is almost free from ash ; this has tlie composition 3C,H,00,+H20, is soluble to the extent of 12.5 per cent.in cold water, and in all proportions in hot water ; the aqueous solution is not altered by warming on the water bath, and is coloured a pure blue by iodine. The compound is dextrorotatory, but the specific rotation increases with the concentration of the solution. The yield is about 90 per cent. of the original material, the loss being purely mechanical. (Compare Wrdblewski, this vol., i, 8.) A. H. By SIEGMUND GABRIEL and GEORG ESCHENBACH (Ber ., 1 S97, 30, 2494-2497).-Sodium hydrogen E. W. W. Bromethylamine and Vinylamine.62 ABSTRACTS OF CHEMICAL PAPERS.carbonate may be used instead of silver carbonate to convert bromethylamine hydrobromide into hydroxyethylcarbamic anhydride (Abstr., 1888, 439), the two substances being warmed together at 40-60'. The anhydride, when boiled with aniline, yields ethylene- FH,*NPh phenylcarbamide, CH,. NH >GO. Bromethylamine hydrobromide can be converted, with s&isfactory yield, into p-methyloxazoline (Abstr., lS89, 1134) by b,oiling i t with acetic anhydride for 3 hours, distilling off the excess of% the anhydride a t 60' under diminished pressure, diluting the residue with water, adding excess of potassium hydroxide, cooling meanwhile, and then distilling with steam ; p-methyloxazoline boils at 109*5-110.5°, and its picrate is now foucd to melt a t 159-160'; the lemon-yellow aurochlode melts a t 184-185'.Vinylamine reacts with hydrogec sulphide, yielding thioethylamine (Abstr., 1891, 816). Rapid Polyrnerisation of Chloral. Eg JOHN W. MALLET ( A m y . Chem. J., 1897, l9,809--810).-A specimen of anhydrous chloral, con- tained in a glass vial with small, drawn-out neck hermetically sealed, poly- merised so rapidly as to cause the bursting of the vial. The occurrence is remarkable, inasmuch as the amount of heat evolved in the polymeric change must have been sufficient to produce the effect observed; also the polymeric change must have occurred with a suddenness which is surprising in view of the very gradual transition of liquid chloral into meta-chloral; and it is not easy to imagine what caused the sudden polymerisation, there having been less change of temperature or external disturbance of any kind, at the time when the change occurred, than the specimen had been previously exposed to.A. W. C. (3. F. B. Glyoxalosazone from Formaldehyde. By HANS VON PECHMANN (Bei.., 1897, 30, 2459--246l).---Five compounds have already been isolated from the product of the action of phenylhydrazone on form- aldehyde, and in the present paper a sixth is described, which is formed when the reaction takes place in acetic acid solution and the concen- tration and temperature are so arranged thst the liquid remains clear at first. The substance thus formed is identical with glyoxalosazone, and is probably formed by the aldehyde undergoing an aldol condensa- tion, either through the hydrazine or the acetic acid, with formation of glycolaldehyde.Glyoxalosotetrazone which has been previously described as an oil, crystallises from acetone or alcohol in characteristic, dark-red plates melting a t 152". Change of Butyric into Isobutyric Acid. By RUDOLF HUTZLER and VICTOR MEYER (Bey., 1897, 30, 251 9-2529).-Erlenmeyer (Arrznnlen, 1876, 181, 126) found that a tube containing a cold satu- rated solution of calcium butyrate which had been used $0 show the separation of the salt at looo, remained clear a t this temperature after about 10 years' use. By fractional crystallisation of the contents of the tube, he isolated a salt which he regarded as calcium isobutyrate, and which comprised about 2% -2g of the whole amount of salt present. J. F. T.ORGANIC CHEMISTRY. 63 The authors have found that this proportion of isobutyrate cannot be detected in this way in a mixture of the two isomeric salts.A trust- worthy method for detecting this amount of isobutyrate is to submit the mixture t o oxidation with potassium permanganate. The normal acid is chiefly converted into carbonic anhydride, whereas the iso-acid yields acetonic acid. Experiments were then made with tubes of resistant glass containing sterile solutions of pure calcium butyrate, and it was found that, after being heated for 6 months a t loo', they no longer gave a precipitate on heating. Isobutyric acid could not be detected in their contents, and the cause of the change was found to be the conversion of a small proportion of the calcium butyrate into the potassium salt by potassium silicate from the glass, calcium silicate being precipitated.The amount of calcium salt is thus diminished to such an extent that the liquid is not saturated a t loo', and hence no precipitation occurs. A. H. Conversion of Pentachloracetone into Trichloracrylic Acid and Chloromalonic Acid, By PAUL FRITSCH (Annulen, 1897, 297, 312-322. Compare Abstr., 1894, i, 4 9 0 ) . - ~ e p t a c ~ ~ l o r o ~ o p u ~ e , CHC1,- CCI,. CCI,, is obtained by heating pentachloracetone with phosphorus pentachloride in a sealed tube at 180' during 6-8 hours; it has the odour of camphor, melts a t 30°, boils at 150-151' under a pressure of 50 mm., and at. 247-248' under atmospheric pressure, slight evolution of hydrogen chloride occurring at that temperature.Bexachloyopopylene, CCl,:CCl*CCI,, prepared from the foregoing substance by the action of alcoholic potash (1 mol.), is an oil which has an odour of raspberries. I t has a sp. gr.=1.7652 a t 20'/4', and the refractive index nD= 1.5091 ; i t boils a t 122-123' under a pressure of 50 mm., and a t 209-210' under atmospheric pressure. Ethjlic ol.t~~otrichloracrylate, CCl,: CCl*C(OEt),, is produced when hexachloropropylene is treated with a slight excess of sodium ethoxide ; it has tt sp. gr. = 1.2183 at 20°/4', and the refractive index 72, = 1.4649. It boils at 149' under a pressure of 50 mm., and at 236-237' under atmospheric pressure. Ethylic trichlomcrylute, CCl,: CC1- COOEt, obtained by agitating ethylic orthotrichloracrylate with concentrated hydrochloric acid, is a colourless oil having the odour of peppermint, and boils at 11 2-1 14' under a pressure of 50 mm., and a t 192-194' under atmospheric pressure ; its sp.gr. = 1,3740 a t 20°/40, and the refractive index nD = 1.4839. The anhydyide of trichloracrylic acid is insoluble in water, and melts a t 39-40', whilst the umide crystallises from water in colourless needles, and melts at 96-97'; the cudamide forms stellar aggregates of needles, and melts at 165O. 3thyZic a-chlo~o-~-diet7~oxyacrylute, C( OE t),: CCl COOE t, formed from ethylic trichloracrylate by the action of sodium ethoxide, boils at 157-159' under a pressure of 50 mm., and a t 226-230' under atmospheric pressure; it has a sp. gr. = 1.0843 at 20'/4', and the refractive index n, = 1.4319. Agitation with concentrated hydro- chloric acid converts the ethereal salt into ethylic monochlormalonate.M. 0. F.64 ABSTRACTS OF CHEMJCAL PAPERS. Reaction between Ethylic Isonitrosoacetoacetate and Hydr- oxylamine Hydrochloride. By MILORAD Z. JOVITSCHITSCH (Bey., lS97, 30, 2421-2422. Compare Abstr., 1896, i, 8l).-The yield of oximidomethylisoxazolone may be increased by extracting with ether the mother liquor left after the separation of the compound. If after this treatment i t be neutralised with sodium carbonate, a precipitate is obtained, which consists of the compound first prepared by Scholl from isonitrosoacetone and hydroxylamine. By LOUIS SIMON (Compt. rend., 1897, 125, 534-536).-When a solution of pyruvic acid is mixed with potassium hydroxide and then with sodium nitroprusside, an intense violet-red coloration is produced, which is turned red by a small quantity of acetic acid, but decolorised by an excess.This reaction is not, however, characteristic, but is shown by a large number of aldehydes, ketones, and their derivatives and condensation products. On the other hand, if ammonia is substituted for the potassium hydroxide in the foregoing reaction, pyruvic acid gives a beautiful, violet-blue coloration, which is characteristic of pyruvic acid and its metallic and ethereal salts, but does not seem to be given by any other compound except acetophenone, and this is readily distinguished from pyruvic acid by Legal's reaction. A small quantity of acetic acid, but not sufficient to make the liquid acid, is essential t o the produc- tion of the blue colour, and under these conditions the limit of the reaction seems to be reached when the solution contains 1 part of pyruvic acid in 10,000.I n the absence of acetic acid, the colora- tion is green, not blue, and the limit is reached with 1 part of acid in 5,000 of water. The coloration appears gradually, and its appear- ance is accelerated by gently heating, but the colour is destroyed by boiling, and also by an excess of acetic acid. Potassium hydroxide changes the blue to deep-red, but addition of acetic acid restores the blue. When amines of the acetic series are added to a solution of pyruvic acid mixed with sodium nitroprusside, a deep-violet coloration rapidly appears and then rapidly disappears ; it is changed to blue by acetic acid, but the blue likewise rapidly disappears. All the amines of the acetic series seem to give this reaction.By ARTHUR ROSENHEIM and PAUL WOGE (Zeit. anorg. Chem., 1897, 15, 283--318).-See this vol., ii, 71. By MAURICE VBZES (Compt. rend., 1897, 125, 525--527).-When a solution of oxalic acid is added, in rather more than equal molecular proportion, to a hot concentrated solution of potassium platonitrite, the liquid becomes green, and nitro- gen oxides are liberated ; after a time, however, the liquid becomes golden-yellow, and when cooled yields pale-yellow, prismatic crystals which act on polarised light. These consist of potassium plato-oxalo- nitrite, and have the composition K,PtC,O,(NO,), + H,O,. They are stable in air, lose their water of crystallisation above loo", and at about 2 40" decompose completely, with intumescence, into platinum, potassium nitrite, and carbonic anhydride. The salt is very slightly soluble in A.H. Colour Reactions of Pyruvic Acid. C. H. B. [Beryllium Oxalates.] A New Double Platinum Salt.ORGANIC CHEMISTRY. 65 cold water, but somewhat soluble in boiling water, and is very stable in solution. When an excess of oxalic acid is used in the reaction described, the product is the potassium platoxalate, K,PtC,O, = 2H,O, which crystal- lises in copper-red needles, and was described by Soderbaum (Abstr., 1886, 532). When the platinum salt is in excess, there is no forma- tion of any intermediate compound analogous to the halogen compounds of the type K,PtX(NO,), previously described by the author.The author suggests that when platinum is separated from associated metals in the form of potassium platonitrite, the readiest method of isolating it is to precipitate it as plnto-oxalonitrite, and afterwards decompose the latter by heat. By LUDWIG KNORR (Ber., 1897, 30, 2387-2389).-The details of the work which is sum- marised in this preliminary communication will shortly appear in the Annulen. The author has succeeded in obtaining no less than five iuomerides of ethylic diacetylsuccinate. Three of these are enol-f orms (al, a,, and a3j, which probably have the configurations C. H. B. The Isomeric Ethylic Diacetylsuccinates. Me*E*OH HO*E*Me Me*E*OH COOEt*C*E*COOEt COOEt*C*g*UOOEt COOEt*C.~.COOEt The remaining two are the optically inactive keto-forms (p and 7).Neither of these has yet been resolved into optically active constituents. The following table exhibits the chief properties of these isomerides : HO.C*Me Me*C*OH Me*C*OH 89" - - 1 : 122.5 Y 68" - - 1: 15.3 P a1 liquid 1.5900 brown 1: 9.7 a3 31-32' 1,4392 - 1: 2'9 21-22" 1.4530 violet every proportion a2 The enol-forms have all a faintly acid reaction, and are soluble in aqueous sodium carbonate, but readily become ketonised in this solu- tion. All five isomerides yield the same products when submitted to various chemical reactions. They are all unstable in the liquid state and in solution, and hence, under these conditions, a state of equilibrium is attained in which the proportions of the various isomerides present can be experimentally determined for different temperatures.The author considers that the passage of one isomeride into the other is brought about by the migration of the mobile hydrogen atoms. It seems probable, in the light of these results, that liquid tautomeric substances are usually mixtures of the various desmotropic forms of the compound. Solid tautomeric substances, on the other hand, usually represent one definite form. A. H.66 ABSTRACTS OF CHEMICAL PAPERS. Compound of Titanic Acid with Malic Acid. By GEORG BERG (Zeit. nnorg. Chem., 1897, 15, 328-330).-The following organic acids do not cause a precipitate in neutral solutions of titanium chloride- malonic, succinic, citric, fumaric, maleic, amidosuccinic, benzoic, ortho- hydroxybenzoic, benzenedisul phonic, phenylacetic, meta- and para-amido- benzoic, hippuric, phthalic, hydroxybutyric, and crotonic, also phenol, trinitrophenol, and resorcinol.White, amorphous precipitates are obtained with acetic, lactic, tribromolactic, tribromacetic, and pcumene- sulphonic acids. A reddish-brown precipitate is produced by nitroso- P-naphthol, a yellow with salicylic acid, and a yellowish-brown with potassium chromate. Malic acid (also its salts) is the only compound examined which gives a crystalline precipitate ; the latter, 2TiO,,C,fT,O, + 6H,O, crystallises in minute, white prisms, is very stable, and is only slowly decomposed by boiling with water or barium hydroxide solution. It is very sparingly solnble in water, strong acetic acid, or dilute mineral acids, but less so in alcohol. It dissolves slowly in concentrated sul- phuric and nitric acids, and at once in concentrated hydrochloric acid.It dissolves at once in caustic alkalis with precipitation of titanic acid, more slowly in ammonia and alkali carbonates. When the crystals are treated with ammonia, they lose 3H,O and take up 3NH,, and if this compound is allowed t o remain exposed to the air it gives off ammonia, and is converted into the compound 2Ti0,,C,H60,.2NH, + 3H,O. Malic acid cannot be employed for the separation of titanic acid from zirconium or iron, as the last two are also precipitated. E. C. R. Compounds of Formaldehyde with Uric Acid. By K. WEBER, R. POTT, and BERNHARD TOLLENS (Ber., 1897, 30, 2514-2515)- Diformaldehyde-uric acid, C,H,N,O, + 2CH,O, is readily formed, and is monobasic towards one-third normal soda.The mother liquor from i t s preparation, when treated with alcohol and ether, yields a substance which appears t o contain 4-5 mols. of formaldehyde t o 1 of uric acid. A. H. By CARL KJELLIN and K. GUSTAV KUYLENSTJERNA (Annulen, 1897, 298, 117-129. Compare Tiemann, Abstr., 1889, 1165, and Voltmer, Abstr., 1891, 558).-H~dl..oxyethyZtiLiocar~~~m~~e: NHEt*CS*NH*OH, is obtained by carefully adding a n ethereal solution of hydroxylamine t o ethylthiocarbimide dissolved in the same medium; it forms colour- less needles or prisms, explodes slightly when touched with a hot glass rod, and melts and decomposes at 109'. The dry substance begins t o undergo decomposition after about a week, yielding a mixture of sul- phur and ethylcarbamide, but the aqueous and alcoholic solutions are very unstable, precipitation of sulphur occurring in a few minutes; silver and copper sulphides are produced by the action of silver nitrate and Fehling's solutions.Ferric chloride develops an olive-green coloration with the alcoholic solution, whilst the aqueous solution becomes violet ; both colours, however, disappear rapidly. HydroxynzetlzyZthiocurbunaide, NHMe*CS* NH*OH, which crystallises in small, colourless, six-sided plates, sinters at 95", and explodes at Aliphatic Derivatives of Hydroxythiocarbamide.ORGANIC CHEMISTRY. 67 101" ; it closely resembles the foregoing cornpound, and is consider- ably less stable than that substance. Hydroxya~Z~ZtlioccLrbanzi~le) C,H,*NH*CS*NH*OH, crystallises in microscopic, rectangular plates, forming a colourless, nacreous precipi- tate when ethereal allylthiocarbimide is added to anhydrous hydroxyl- czmine dissolved in the same medium ; it begins to soften a t 85", and fuses completely at 120'.It is extremely unstable, both in the solid state and in solution, yielding sulphur and allylcarbanlide ; the colour changes with ferric chloride are the same as those exhibited by hydroxy- ethylthiocarbamide and hydroxymethylthiocarlmrnide. is prepared by treating an ethereal solution of p-ethylhydroxylamine with ethereal ethylthiocarbimide ; it melts a t 81", dissolves sparingly in water and ether, and is readily soluble in alcohol, chlorofoibm, and hot benzene. The crystals from benzene are monosymmetric ; a : b : c = 2.8676 : 1 : 0*8809.Hydroxydiethylthiocarb- amide may be preserved for any length of time without undergoing change, and the aqueous solution does not yield sulphur when boiled ; ferric chloride develops a green coloration with the aqueous or alcoholic solution, passing into bluish-green and reddish-violet on dilution. The silvey derivative forms slender, silky needles containing 3H,O, and resists the action of light ; the gold cldo~ide derivative is red. Synzmetvical ~~ydroxydinzeth~Zthiocar~i6~?aid~, NHMe*US*NMe*OH, is prepared by adding the calculated amount of sodium methoxide dis- solved in methylic alcohol to a solution of p-methylhgdroxylamiiie hydrochloride and methylthiocarbimide in methylic alcohol ; it sepa- rates from benzene in diinorphous crystals melting a t 104'.The colour changes with ferric chloride are similar to those of the foregoing compound. The silver derivative forms slender, colourless needles, the nzercurichloyicle is dimorphous, and the au?*ochZoride is decomposed by water. Ethylic iodide converts hydroxydimethylthiocarbamide into an unstable crystalline compound, which yields ethyl mercaptan when heated with caustic soda. obtained from P-ethylhydroxylamine and allylthiocarbimide, crystallises from benzene in thin, four-sided plates, and melts a t 66-67'. Ilydrox?/metJLylaZZyZtJ~iocnrbcc.l?tide, C,H;NH.CS*NMe*OH, is pre- pared from p-methylhydroxylamine and allylthiocarbimide ; it melts at 54', and crystallises from benzene in beautiful, colourless, monosym- metric prisms. ~€~droxymetl~~Zet~~ylthiocc~rbc~nz,~de, NHMe* CS*NEt *OH, obtained from ,8-ethylhydroxylamine and methylthiocarbimide, crystallises in small, colourless needles, and melts a t 122' when heated rapidly.BenxyZoxyaZZyZthiocarbnnllide, C,H,*NK*CS*NH.O- CH,I'h, is pre- pared from P-benzylhydroxylamine and allylthiocarbimide ; i t forms prismatic crystals and melts a t 57-58", Sy ntme tricu Z J@roxyd ietl~yZt?~iocnrbnnaicle, N H E t CS NEt - 0 H , ,(3 = 8 6 O 5'. Hydrox~etltylallylt~~iocccr bamide, C,H,*N H *CS N E t OH, a : b = 0.60264 : 1. ,8 = 74" 8'. M. 0. F. Polyaspartic Acids. By HUGO SCHIFF (Ber., 1897, 30, 2449-2459).-The two anhydrides of aspartic acid prepared by Schaal by the action of carbonic anhydride on asparagine are more easily prepared by heating aspartic acid at 190--200" for 20 hours ;68 ABSTRACTS OF CHEMICAL PAPERS.on boiling the product with ten times its weight of water the octo- anhydride (octoaspwtide), C:32H26Ns017, remains undissolved, whilst the t e t ra-anh ydride (tetrcqxwtide), C],,H,,~,O,, sepR ra t es from the filtrate on cooling. The filtrate also contains two other substances, namely, tetraspcwtic acid, Ci6R22N,0i,, and a small qnan ti ty of octo- aspartic ccciil, C,,H,,N,O,,,. the latter can also be obtained from its copper salt by treatment with hydrogen siilphide ; it forms a vitreous mass which a t 1 90-200' passes quantitatively into octoaspartide. Octoaspsrtide combines with 8 mols. of phenylhydrazine with the for- ination of a yellow, crystalline phenylhydraxide, me1 ting partidly and decomposing at 200-205". I t also combines with aniline with the production of various products, those containing less than 8 mols.of aniline dissolving in alkali with the formation of the corresponding octoaspartanilic acids ; on heating with aniline, ammonia is evolved. Tetruspicrtic acid crystallises from water in clusters of needles, and is very similar to the octo-acid in its properties. The author considers the constitution of octoaspartic acid and tetr- aspartic acid t o be respectively and that of tetraspartide and octoaspartide to be J. F. T. ) NH ~ r u ( c o 9 c n , ( l O ,H. HO ( *C!O*b*CH2b0 :Hp ) ,H Aliphatic Sulphonic Acids. By ELMER P. KOHLER (Amer. Chem. J., 1897, 19, 72S-'752).-From the study of the behaviour of some 23 sulphonic acids towards phosphorus pentachloride, and of the corres- ponding chlorides towards water, the details of which will appear in subsequent papers, the author is led to the following general conclu- sions, to which no exceptions have so f a r been observed.Monosulphonic acids and aa-chloro- or bromo-monosubstitution pro- ducts of monosulphonic acids react readily with phosphorus penta- chloride in the cold with production of a normal sulphone chloride, which on treatment with water passes back into the acid. With phosphorus pentachloride, 1 : 2-chloro- or bromo-sulphonic acid reacts in the same way; the chloride, on treatment with water, passes back for the most part into the acid, but at the same time an unsaturated sulphonic acid is formed, CH,Br*CH,* S02C1+ H20 = UH2:CH* SO,H + HCI + HBr. Neither aa- nor a@-disulphonic acids react with phosphorus penta- chloride in the cold.On heating, in the first case, the product is mainly an aa-chlorsulphonic chloride, together with other chlorine sub- stitution products; and in the second case a disulphonic chloride is formed, which on treatment with water gives principally an unsatu- rated sulphonic acid, and to a minor extent the regenerated acid. aa- and up-Sulphocarboxylic acids slowly react with phosphorus penta- chloride in the cold. The product is always a chlorine substitutionORGANIC CHEMISTRY. 69 product of a diacid chloride, which reacts with water in a complicated manner, with different results in different cases. The special subject treated in this paper is the behaviour of ap-ethanedisulphonic chloride towards a number of reagents in order to determine what conditions a r e most favourable for the production of a n unsaturated acid, or the regeneration of the saturated acid.ap-~thanedisu~iionic acid is produced by the oxidation.of ethylenic thiocyanate with nitric acid, and crystallises from glacial acetic acid in slender needles melting at 100'. The sodiunz salt is best obtained by boiling ethylenic dibromide and sodium sulphite in concentrated aqueous solution ; if the solution is dilute, then sodium monobromethanesul- phonate is produced. ap-Ethnnedisul~l~onic chloride, prepared either from the free acid by treatment with phosphorus pentachloride or carbonyl chloride, or from the sodium salt of the acid by warming with phosphorus pentachloride, crystallises from chloroform in large, compact orthorhombic tables melting at 9 1 O .When pure, it can be heated to 150' without a trace of decomposition, but at 160' sulphurous anhydride is slowly evolved and a@-chlorethanesulphonic chloride distils over. All attempts to prepavo Q n unsymmetrical disulphonic chloride failed. When ethanedisulphwic chloride is acted on by vater, a n amount of ethylenesulphonic acid corresponding with 90 per cent. of the original substance and 10 per cent. of ap-ethanedisulphonic acid are produced. Methylic, ethylic, propylic and amylic alcohols react with the sul- phonic chloride in the same way as water ; the amount of unsaturated acid formed diminishes, however, with the increase in the molecular weight of the alcohol. Acids and alkalis also react in the same manner. Dry ammonia does not act on the sulphonic chloride with production of the corresponding amide, and in alcoholic solution ammonium ethanedisulphonate and anhydrotaurine are formed.Substituted ammonias behave in a similar manner, aniline, for example, giving rise to anhydrophenyltaurine and anilidoe~hanesulphonacanilicle, NHPh*CH,*CH,*SO,*NHPh; the latter is a n oil which can with difficulty be obtained in colourless plates melting a t 75". The hydro- chloride crystallises from alcohol in long, colourless needles melting at 171°, and the monacetyl derivative melts a t 152". Acetamide, and acid amides in general, act on the chloride in glacial acetic acid solution, producing mainly ammonium ethanesul- phonate. When the chloride is acted on by sodium acetate (or saltsof organic acids in general), sulphurous anhydride is eliminat,ed ancl 95 per cent.of the original substance is recovered in the forin of the sodium salt of ethylenesulphonic acid, and the rcriiainder as sodium ethanedisul- phonate. Zinc dust converts 53 per cent. of the chloride into the zinc salt of ap-ethanedisulphinic acid, anot,her substance not fully investigated being also produced. A. W. C. Constitution of Meconic Acid. By A LBERTO PERATONER (Chenz. Zeit., 1897, 21, 40).---Meconic acid, when boiled with alkalis or70 ABSTRACTS OF CHEMICAL PAPERS. alkaline earths, yields carbonic anhydride, oxalic acid, formic acid, and substances of a gummy nature whose isolation is rendered difficult by the presence of the acids.By the action of barium hydroxide on triethylic meconate, which was prepared by boiling the dry yellow trisilver salt with ethylic iodide and crystallising the product from light petroleum and ethylic alcohol, the author obtained barium oxalate, alcohol, and acetylcarbinylic ethylic ether, but neither car- bonic nor formic acid. Since meconic acid belongs to the pyrone group as shown by its conversion into comenic acid (Ost) and since chelidonic acid, which is a pyronedicarboxylic acid, when treated with alkaline earths, splits up into oxalic acid and acetone, the above decomposition indicates the following formula for triethvlic meconate cooEi*~-o-!?cooEt, and henesthat the free acii is hydroxy- CH*CO*COEt chelidonic acid. Similar experiments with pyromeconic acid show that this acid probably decomposes into formic acid and acetylcarbinol.E. W. W. Nitroketones, Hydroxyketones, Ketochlorides and Reto- bromides. By E. C. THEODOR ZINCKE (J. pr. Chenz., 1897, [ii], 56, 157--178).-This paper is chiefly theoretical in character, and con- tains no description of new compounds. By chlorinating tetrachloro- paracresol in acetic acid solution, a ketochloride, CMe< CCl*CCl cc1: ccPC0, is obtained; at LZ higher temperature and without solvent, the isomeride, ccl:ccl>CO. A ketobromide, CMeBr<CCl:CC1>CO, CCI'CCl CMeC1<cC1: c c 1 analogous to the last compound, can be obtained in a similar way; it appears to exist only in this configuration, but it sometimes reacts as if it had the constitution CH2Br*C<cCl:CC1 CC1*CC1>C*OH.When oxidised with nitric acid, it yields a compound OH*CH2* CBr<&ccl>CO ; CC1' CCl alkalis convert this into 7% o->c<~:~$:~>CO, whilst reduction changes it to CMe<E$s;;>C*OH. Many other reactions of these and similar substances are enumerated, and compared with similar ones observed by Auwers ; it is not possible, however, to give a satisfactory abstract of them. It may be said that the ketobromide of tetrabromo- paracresol is also considered, as well as the pentabromides from ortho- and meta-cresol, and from metaxylenol. The formation ol a parshgdroxy- ketone by the action of nitric acid on tetrachloroparacresol, &c., has been shobn to be preceded by the formation of 'a paranitroketone, C. F. B. CCI'CCI NO,* c ~ ~ < ~ ~ l ~ ~ c ~ > " o .Reversible Transformation of Styrene and Metastyrene under the Influence of Heat. By GEORGES LEMOINE (Compt. rend., 1897, 125, 530-533).--The author has investigated the effect ofORGANIC CHEMISTRY. 71 heat on styrene at 97', 160', 240", 310' and 350" the styrene and metastyrene in the product being separated by distillation under low pressure at a temperature not exceeding 100'. The styrene used boiled a t 142-144' under a pressure of 751 mm., a t about 53-54' under a pressure of 1.8 mm. and 48.5 a t 0.9 mm. Its sp. gr. was 0.920 a t O', 0,910 a t 12*1', 0.908 a t 16.5', 0,899 a t 27*lo, 0.879 a t 51 -5' and 0.852 a t 87'. Whether the original substance is styrene or metastyrene, the com- position of the product tends towards the same limit under a given set of conditions; provided the temperature is the same through- out the whole of the apparatus, the quantity of styrene that remains unaltered depends on the volume of matter heated, or, in other words, the limit corresponds with a given vapour pressure, as in cases of dissociation. The rate of change is at first somewhat rapid but gradually becomes slower and slower.The limit as determined in flasks of somewhat considerable capacity is not quite the same as the limit determined in narrow glass tubes, the difference being most probably due to the disturbing influence of the walls. At aboiit 97', the conversion of styrene into metastyrene is practi- cally complete, but the proportion of styrene remaining increases slightly with the temperature and is 0.9 gram per litre at 310", the corresponding vapoar pressure being 0.4 atmos.Details of the observations are given in the paper. Nitroso-derivatives of Catechol Methyl Ether [Guaiacol]. By A. PFOB (Moncctsh., 1897, 18, 467-480).-Guaiacol (catechol methyl ether, OH*C,H,* OMe = 1 : 2) can be made to yield a nitroso-derivative by dissolving it in alcohol, adding acetic acid, cooling to - 2", adding potassium nitrite gradually, allowing to remain a t this temperature, and finally diluting with ice and water, The product, 2-methoxy- 1 : 4-quinone-4-monoxime, O:C6H,(0311e):NOH or OH*C,H,(OMe)*NO, is identical wlth Best's paranitrosoguaiacol (Abstr., 1890, 60S), and yields the same 2-methoxy-1 : 4-quinonedioxime when treated with hydroxylamine hydrochloride.When boiled with excess of acetic anhydride, it yields a rnonacetyl derivative, O:C,H,(OMe):NOAc, which melts and decomposes at 156-158' ; when reduced with stannous chloride, it yields 4-amido-2-rneti5oxyphenoZ, OH-C,H,( OMe)*NH,, an unstable base the ?hydrochloride of which was prepared, as also the triucetyl derivative, OAc*C,H,(OMe)*NAc,, which melts a t lolo, and yields the hydrochloride of the methoxyamidophenol when it is treated with hydrochloric acid. When the monoxime is heated with water for several hours at 150-160', a small quantity of 2-methoxy-1 :4- quinol, OH*C,H,(OMe)-OH, is perhaps formed ; when it is heated at 100" with potassium methoxide and methylic iodide in the presence of ether, it yields a methyl ether, O:C,H3(0Me):NOMe, which meIts a t 105-106', and forms amidomethoxyphenol when reduced with stannom chloride.From catechol ethyl ether, yellow 2-ethoxy-1 : 4-puinone-4-rnonoxime can be obtained ; when heated, it decomposes without melting. C, H. B. C. F. E.72 ABSTRACTS OF CHEMICAL PAPERS. Derivatives of Guaiacol. By HAPI'S RUPE (Bey., 1897, 30, 2444--2449).-The author has prepared several derivatives of guaiacol containing nitrogen groups in the para-position relatively to the hydroxyl. I'ara-?zitrosoguaiacol is most conveniently prepared by heating guaia- co1, methylic alcohol, sodium methoxide and ethylic nitrite in a closed tube for 12 hours a t 100". Ya~~anitroguaiacoZ, OH*C,H,(NO,)*OMe [NO, : O H : OMe = 4 : 1 : 2]? formed from the nitroso-compound on oxida- tion with alkaline potassium ferricyanide, crystallises from hot water in slender, yellow needles melting at 103-104°.Dinitropaiacol, OH*C,H,(NO,), [OH : OMe : (NO,),= I : 2 : 4 : 61, melts at 123-124" and is formed when nitric acid acts on nitrosoguaiacol. Pararnido- guc~icicoZ, OH*C,H,(NH,)*OMe,can be prepared either by reducingtheazo- compound produced by the combination of diazobenzene chloride with guaiacol by means of tin and hydrochloric acid, or by reducing nitroso- guaiacol with stannous chloride and hydrochloric acid ; it crystallises in glistening prisms melting and decomposing at 176-177"; the hydi-ocldoride separates from hydrochloric acid in large, pale green crystals. Paracyanoguaiacol, OH*C,H,( CN).OMe, prepared from the diazo-compound, is identical with the substance obtained by Markus from vanillin. J.F. T. Sitosterol. By RICHARD BURILN (Nonatsh., 1 897, 18, 551-574). -The '' germs " of wheat or rye (a refuse product of flour-mills) are extracted with ether, the extracted f a t is hydrolysed with alcoholic potash, and the solution is precipitated with calcium chloride. The pre- cipitate of calcium soap and other substances thus obtained is extracted with acetone, the extract is evaporated to dryness and dissolved in other, the ethereal solution is washed cautiously with dilute hydro- chloric acid and potassium hydroxide in succession, and is then evaporated to dryness ; the residue is finally crystallised from metjhylic alcohol. In this way, a substance, Cz7H,,O + H,O, is obtained which resembles the cholesterol of bile in external appearance and in com- position, but melts a t 137.5', and in ethereal solution has the specific rotation [.ID = - 26-71' ; it is named sitosteyol (aiios= wheat, corn).I t is a n unsaturated substance, for it forms a dibromide, which does not crystwllise easily, and is difficult to purify ; i t melts and decom- poses a t about 98". It also forms a monacetate; this melts at 127" after softening at 124*5", and yields a dibromide which also crystnllises with difficulty ; a propionate and benzoate, melting respectively at 1 0 8 5 O and 145-1 45.5", were also prepared. Sitosterylic chloride, C,;H,,Cl, can be obtained by the action of phosphorus pentactiloride on sitosterol ; it melts a t €37.5' after softening at 82". and is reduced by sodium in boiling amy 1 alcoholic solution t o sitostene, C27H44, which melts between 61" and 68", according to the rapidity with which i t is heated, has in ethereal solution the specific rotation [ aID = - 38-79", and is a n unsaturated hydrocarbon, forming a dibromide which crgstal- lises with difficulty, and melts between 105-110° after softening a t 70".The methyl alcoholic mother liquor from the sitosterol contains another substance, parusitosterol, which melted at 132.5' ; after con-ORGANIC CHEMISTRY. 7 3 __ 92.2 17.6 7 - 2 4-2 2.7 1.4 28.4 20.4 14.1 14.5 0 version into the acetate and recovery from the latter by hydrolysis with sodium methoxide, a t 127.5' ; it resembles siiosterol in appearance. This substance appears also t o have the composition C27H440, but in ethereal solution it has the specific rotation [ a JD = - 20*S0, and its rnonucetute melts a t 115-120', and forms a dibromide which melts a t 112' after softening a t 104.5".Finally, a tabulated list is given of all the phytosterols (vegetable cholesterols) a t present known, with their specific rotations, and the melting points and ,crystalline form of themselves and their acetates and benzoates. C. F. B. -1- 95 94'6 31.6 26.2 11.9 3'6 1.8 3.0 0.9 3.4 0.3 0 .o 44.6 20-4 26.5 11'8 14.7 6-1 4.9 1-2 2'4 Formation of Chains : XVII. Orthotoluidine and Meta- toluidine ; XVIII. Paratoluidine ; XIX. Metaxylidine. By CARL A. B1scHo~F( Ber., 1897,30 2464-2468,2469-2475,2476-2480. Compare this vol., i, lO).-Aromatic amines, R;NH,, were heated with ethylic salts of a-bromo-acids, CR,,R,,,Br*COOEt.The products of the reaction are R;NH*CR,,R,,;COOEt and R;NH3Br ; to determine the extent to which the reaction has taken place, the amine hydrobromide was washed with chloroform and weighed; the error was not greater than +,2 per cent. As a rule, the temperature employed was 120', and the heating was continued for 4 hours; experiments were also made at 130-135' and at 180°, and the products of these were sub- mitted t o fractional distillation, the fractions being weighed and a fractionation curve constructed. Some experiments were also made at 100'. The numbers in Table I. give the extent, in percentages of the theoretical maximum, to which the reaction takes place between the amines and ethylic salts there tabulated ; the amount of reaction be- tween the amines and certain acids, R,,*COOH, was also determined, each pair of substances being heated together for 1 hour a t loo', the product being, of course, a substance of Table 11.gives the results. Bromopropionate ...... H Bromophenylacetate.. ' Bromisobutyrate ...... 0 - 0 TABLE I. 95 54 94 92 ~ 91 68 43 47 43 68 29 19 62 38 , 19 ----__ ----- I Bromopropionate ......I 94 1 97 1 94 1 93 1 96 the type R,;CO*NHR, ; TABLE 11. R,, (R,;COOH). H CH3 CH,ble CH,Et *CH, CH,Et CHMe, CHMe,*CW, OH* CH, 0 H CH Me OH*CHPh OH* CHEt OH*CMe, 974 ABSTRACTS OF CHEMICAL PAPERS. The following new substances were prepared in the course of the in- vestigation. Ethylic a-oythotoluidoisovalenxte, C,H,Me.NH* CH(C HJIe,)-COOEt, melts at 3G" and boils at 282-284' under 763 mm.pressure; the corresponding cccicl melts at 101', and loses carbonic anhydride when distilled, yielding isobutylorthotoluidine, which boils at 230-235" under 758 mm. pressure. C,H,Me.NH*CHMe* COOEt, boils at 271-276' under 767 mm. pressure ; ethylic metntoluido- butyrate, C,H,Me*NH*CHEt*COOEt, at 281-285' under 745 ram. ; and ethylic nzetutoluidoisobutyrute at 270-273" under 753 mm., and at 205-2 10' under 104 mm. pressure ; ethylic a-metcctoluidophentjlacetate, C,H,Me*NH.CHPh*COOEt, melts a t 109'. Ethylic a-pccrutoluidoiso- vulerate boils at 295" under 753 mm. pressure ; the corresponding acid melts at 110'. Zthylic a-parato~uidopheny~acetate melts at 85-86". When paratoluidine is heated with chloracetamide, eventually to 150', p~ratolylimidodiucetinzide, C6H,MeoN: (CH,-CO),:NH, melting a t 195', is produced ; whilst in the presence of sodium acetate, paratoluidoacet- amide is formed instead.Paratoluidine with a-bromopropionamide at 80" yields toluidopropionamide, and at 150-1 80", a-puratoluidopro- pionic parutoluidide, C,H,Me*NIS* CHMe*CO*NH*C,H,Me, which melts at 158'. With a-bromobutyramide and a-bromisobutyramide at 120-1 30", it yields respectively a-parutoZuidobutg/ric and a-partctoluido- isobutyric pamtoluidicles, melting at 138" and 144". Ethylic a-metuxylido- pyopionute, C,H,Me,*NH*CHMe*COOEt, melts at 42" and boils at 274 -275" under 753 mm. pressure. Ethylic a-wetaxylidobutyrate, C,H,Me,*NH*CHEt*COOEt, boils at 285-290' under 753 mm. h'thylic rnetuxyZiidophenyZacetate, C,H,Me,*NH*CHPh*COOEt, melts at 90.5'.By 31. C. SCHUYTEN (Chem. Zeit., 1897, 21, 24). --By passing nitric oxide gas through an alcoholic solution of aniline, the author obtained nitraniline, but no nitroso-derivative. Ethylic metccto~uidoprop~onccte, C. F. 16. Nitrosoanilines. E. W. W. Paratolyltrimethylenediamine and y-Iodopropylamine. By MARTIN FR~NKEL (Bey., 1897, 30, 2497-251O).-By heating y-bromo- propylphthalimide, C,H,O,:N* [CH2'J2* CH,Br (1 mol.), with para- toluidine (2 mols.), eventually at 1 50', yellow paratoluidopropylphthali- mide, C,H,02:N.[CH,],.NH*C,H7, melting at 134-1 36O, is obtained ; the white hydyochloride melts at 198", and is decomposed by water. If a relatively smaller amount of the toluidine is used, the product is yellow pus.atoluidodipropyldiphthalimide, (C8H,O2:N*[CH,],*),N- C,H,, melting at 124".When paratoluidopropylphthalimide is boiled with 20 per cent. hydrochloric acid, pap.atolyltrimethylenediamine, NH2*[CH2],*NH=C7H7, is formed (Balbiano, Abstr., 1889, 1216) ; this boils at 383" under 763 mm. pressure, and has a sp. gr. = 1.0253 at 15" ; the hydrochloride, with 2HC1, melts at 257", the yellow platinochloride at 205", and the greenish-yellow picrute at 11 3' ; the base absorbs car- bonic anhydride from the air. With potassium cyanate and hydro- chloric acid, it forms paratoluidopropylccrbccmid~, NH,.CO*NH.[CH,I,.NH. C',H,,ORGANIC CHEMISTRY. 75 which melts at 152" losing ammonia ; after prolonged heating a t 212") the residue is found to be par~to~?~~tr~rnethylenecarban~~de, melting a t 207O. a t 1 40", it yields pccrutolyltrimethylenethiocarbamide, With potassium thiocianate and hydrochloric acid c s<N (C7HT) 'CH2)C H, , NH -CH, melting a t 1 $So.With carbon bisulphide, it forms the dithiocarbamate, NH(C7H7)*[CH,],*NH*CS*SNH,-[CH2],*BH*C,H7, which melts at 125O, and decomposes at that temperature, or when boiled with water, into hydrogen sulphide, paratolyltrimethylenediamine, and paratolyltri- me th ylenethiocarbamide. With nitrous acid, it yields amidopropyl- puratolglnitrosamine, NH2*[CH,],*N(C7H7)*N0, the hydvochloride of which melts a t 175" ; the nitrosamine itself is an oil which decomposes when distilled, and absorbs carbonic anhydride from the air. When paratoluidopropylphthalimide is heated with methylic iodide at 125O, the product is y-iodo~opyZphtl7L~li~aide, C,H,O,:N*[CH,],*I, melting a t 8 8 O , and methylparatoluidine.By heating 7-bromopropylphthalimide with methylparatoluidine at 170°, yellow rnethyZparatoluidopopyZphthali,m<de, melting at 125", is obtained. y-Iodopropylphthalimide (see above) is more conveniently obtained by boiling y-bromopropylphthalirnide with aqueous alcoholic sodium bromide. When boiled with hydriodic acid of boiling point 127') it yields y-iodopropylunzine, NH,*[CH,],*CH,I, isomeric with a compound previously prepared by Hofmann and by Gabriel (Abstr., 1897, i, 136). This is an unstable oil ; the hydriodide melts a t 166O, the yellow picyafe at 134-1 35' ; its benzoyl derivative, y-iodopropylbenxamide, PC'HBz*[CH,J,* CH,I, melts a t 6S0, and reacts with paratoluidine at 170", forming crystal- line benxoparcctolyltvimethyle.nediarnide, NHBz*[ CH,],*NH*C7H7.With paratolylthiocarbimide, CS:NC,H,, in ethereal solution, y-iodopropyl- amine yields a substance which is probably paratol;yltrirnethylene-$- thiocarbamide, C H , < ~ ~ : ~ > C * N H * C , H , ; this melts at 135') the hydriodide a t 200°, the reddish-yellow plutinochloride at 208", and the yellow picrate at 170°. C,H,O,:N* [ CH,],*NRle* C,H7, C. F. B. Action of Diazomethane on Nitrosobenzene. By HANS VON PECHMANN (Ber., 1897, 30, 2461-2463).--The action of diazomethane on nitrosobenzene in ethereal solution leads to the formation of a yellow, crystalline substance melting a t 182-183', which is apparently glyoxime-3-phenylether, kph>C,H2<hph ; the yield is about 50 per cent, of the theoretical, and phenylhydroxylamine is formed as a bye-pro- duct, which makes it probable that part of the nitrosobenzene has acted as an oxidising agent.This new substance has been prepared by Bam- berger from formaldehyde and phenylhydroxylamine ( Vierteljnhrschr. O-- 0 y 276 ABSTRACTS OF CHEMICAL PAPERS. d. natuiforsch. Ges. in Zurich, 1896, 178); acids decompose i t into glyoxaldehyde and phenylhydroxylamine, from which two substances i t can be prepared synthetically; heating with acetic anhydride con- verts i t into oxanilide, or derivatives of this. Diazocyanides and Double Salts of Diazonium Cyanides. By ARTHUR R. HANTZSCH and KARL DANZIGER (Bey-., 189'7, 30, 9529-2548. Compare Abstr., 1895, i, 348).-The diazonium cyanides cannot be obtained in the pure state, but their double salts are €ormed when a solution of a diazonium chloride is treated with silver cyanide or a neutralised solution of potassium cyanide.The presence of hydroxyl ions, which are invariably present in ordinary potassium cyanide solution, causes, the formation of the insoluble syn-diazo- cyanide. The double salts with silver cyanide are colourless, soluble in water, and of neutral reaction, and are at once decomposed by acetic acid, whilst in aqueous solution they gradually decompose, forming nitrogen, hydrogen cyanide, silver cyanide, and a phenol. They thus closely resemble the double cyanide of silver and potassium. This behaviour also renders it probable that the free diazonium cyanide itself would resemble potassium cyanide, and therefore differ essentially from the normal diazocyanide, which is stable towards acids.$-Cumenediaxonizcrrt. silver cyanide, UGH,Me,* N BCN, AgCN, has only been obtained in aqueous solution and is prepared from the diazonium iodide and silver cyanide. It readily forms azo-colouring matters. Yayabromodiaxonium sillrer cyanide, C,H4Br* N *CN,AgCN, has been obtained in small quantity in the form of a crystalline powder, which explodes a t 119-120'. Of the stereoisomeric diazocyanides, R*N=N.CN, the syn- or normal compounds, 8, are the primary products of reaction, are labile, have a low melting point, readily form azo-colouring matters, and can be directly decomposed into nitrogen and a nitrile. The anti- or iso- diazocyanides, on the other hand, are stable, have a high melting point, and do not easily form azo-colouring matters or decompose into nitro- gen and a iiitrile.As will be seen from the description of the various compounds, the presence of negative groups increases the stability of the syn-form, a group having a greater effect in the ortho- than in the para-position ; the presence of halogens also diminishes the readiness with which both series undergo reaction. Diorthocyanides are decom- posed into nitrogen and a dihalogen derivative of benzene by alcohol and an alkali, whereas all other halogen diazocyanides are thus con- verted into diazoimido-ethers. Alcohol radicle3 appear to be unfavourable to the formation of stable cyanides of either series. Sy n-pnmbromobenxenecliaxocyanide, Cf5R4Br 'M, is obtained by add- ing aqueous potassium cyanide to parabromobenzenediazonium chloride solution at - 10' ; it forms yellow needles melting a t 4 2 O , reacts C.F. B. ... N ... N CN*N CN-NORGANIC CHEMISTRY. 77 violently with precipitated copper, and forms bromobenzeneazonaphthol with #3-naphthol. If kept for a day, or dissolved in alcohol and pre- cipitated by water, a t the ordinary temperature, it passes into the anti-cyanide, Br*C6H4*8 which crystallises from light petroleum in brown needles melting at 129-130' ; this is indifferent towards p- napht hol and copper powder. Syn-paraiodobenaenediazocyanicle is yellowish-brown and melts a t 48' ; the anti-cyanide crystallises in reddish-brown needles and melts a t 152'. Syn-oi.thobromobenzenecZiccxo- cyanide forms yellow needles and melts at 51'; it does not pass into the isomeride a t the ordinary temperature, but when precipitated by water from alcoholic solution a t the ordinary temperature, a small quantity of the anti-compound is formed, which melts a t l07--108'.Syn-metabromobenxenediaxocyanide forms very unstable needles melting a t 25-96'. Syn-2 : 4-dibromobenxenediazocyanide melts a t 70---71', is stable, and only passes into the anti-salt a t the summer temperature ; the latter crystallises from dilute alcohol in reddish-brown plates melting at 141'. Both forms are converted by alcohol and hydrogen chloride into 2 : 4-dibromodiaxocu~bccmide, C,H,Br,*N,. CO *NH,, which crystal- lises in orange-coloured needles melting at 194'. Alcoholic potash converts it into potassium dibromodiaaocarboxylate, which forms golden- yellow plates and yields a yellow precipitate of the free acid on acidificabion.The syn-dichlorocyanide changes more readily t,han the d ibromo- compound in to the anti-com pound. Sy 1 1-2 : 4-di-iodo benxenediuxo- cganide melts at 96', the anti-cyanide a t 186'. Syn-3 : 4-dibromobenxene- diuzocynnide melts at 56-57'; it changes in a few days into the anti-cyanide, which crystallises from light petroleum in small, brown needles melting a t 100-101'. Syn-2 : 5-dibromobenxenediuxocyanitle melts at 42-43', and in a few days changes into the anti-cyanide, which crystallises from dilute alcohol in brick-red needles melting a t 122-123'. Syn-3 : 5-dibromobenxenediazocyunide melts a t 60', and decomposes if kept ; the unti-compound melts a t 85'.Syn-2 : 6-di- byornobernzenediazocyanide melts a t 44- 45', and decomposes completely when kept, or if i t is precipitated from alcoholic solution at the ordinary temperature. The anti-compound has not been obtained. Syn-2 : 4 : 6-tribromobenxenediaxocyanide, which forms yellow plates melting at 59-60', is remarkably stable, does not change when kept, and only reacts slowly with ,@naphthol and with copper ; with alcohol aud soda, i t yields tribromobenzene and nitrogen. The anti-salt can only be obtained with difficulty and forms brownish-red crystals melt- ing a t 147'; alcohol and caustic soda convert it into the correspond- ing diazoimidoether. Syn-symnzetrical-2 : 4 : 6-t~ichlorobenxenecliaxo- cyanide is much less stable than the tribromo-compound ; the anti- compound has not been obtained.Syn-2 : 4 : 5-trichlorobenxenediaxo- cyanide melts a t 5 5 O and is very stable ; the anti-cyanide crystallises in red needles melting a t 100-101'. Alkyl-diazocyanides can only be prepared by adding the diazonium salt t o an excess of potassium cyanide solution a t - 12'. The toluene-derivative is oily, the U S ? J ~ L - metrical nzetccxylenediaxocyanide is solid, but rapidly decomposes. N* C" The unti-salt has not yet been obtained.78 ABSTRACTS OF CHEMICAL PAPERS. Syn-+-cumenediaxocyanide forms dark red crystals melting a t 38-39'; the anti-compound has not been prepared. Syn-brornometaxylenediaxo- cyanide melts at 49-50' and readily passes into the anti-compound which melts a t 64-65'.Syn-paramethoxybenxenediccxocyanide melts at 50', and changes in a few days into the anti-cyanide melting a t 122O. Xyn-a-nuphthaZenediuxocpnide melts at 57-58' and changes com- pletely and readily into the anti-cyanide, which crystallises in reddish- brown needles and melts a t 116'. Syn-/3-naphthaZenediaxocyanide melts at 51-52' and rapidly passes into the anti-compound, which crystallises from hot alcohol in yellowish red needles melting a t 131'. A. H. Additive Products of Azo- and Diazo-compounds with Ben- zenesulphinic Acid. By ARTHUR R. HANTZSCH and R. GLOGAUER (Bey., 1897, 30, 2548-2559. Compare Abstr., 1897, i, 222).-Azo- compounds and both,normal and iso-diazo-compounds unite with benzene- sulphinic acid to form colourless compounds when an alcoholic solution of the azo- or diazo-compound is added to a similar solution of benzene- sulphinic acid.These are stable towards acids, but are decomposed by alkalis, are probably derivatives of hydrazobenzene, and are formed by direct addition. When the solutions are mixed in the inverse order, phenylsulphones are formed as a rule. Diazonium com- pounds, on the other hand, only react with benzenesulphinic acid t o form diazosulphones, so that this reaction affords a purely chemical proof of the constitution of the normal diazocyanides, which combine with benzenesulphinic acid, and therefore cannot have the diazonium formula. Both syn- and anti-diazocornpounds yield the same additive product, the asymmetry of the azo-group disappearing when a derivative of ammonia is produced.On decomposition with alkalis, the additive product formed from either diazocyanide yields benzenesulphinic acid and the anti-diazocyanide, so that the syn-cyanide can in this way be converted into its isomeride. PhenylsuZphonehydvaxobenxen,s (benzenesulphinic acid azobenzene), NHPh*NPh*SO,Ph, is obtained by adding an alcoholic solution of azo- benzene to a similar solution of benzenesulphinic acid ; it crystallises in pure white, silky needles melting at 107'. Plzenylsulphonehydraxo- chlorobenxene cyanide, PhSO,*N( C,H,Cl}*NH.CN, is prepared from para- chlorobenzenediazocyanide and decomposes a t 13 1' ; the corresponding bromo-derivative decomposes at 127'. h'yn-2 : 6-dibromobenzenediazocyanide, which is itself very unstable, yields a remarkably stable iqdraxo-compound with benzenesulphinic acid which melts at 168" ; aqueous potash converts it into a coloured stable substance which also melts at 168', and is probably the anti-cyanide.,S'p-tribromobenzenediazocyanide readily unites with benzenesulphinic acid, in whatever order the solutions are mixed, to form a colourless compound, which decomposes a t 162' ; treatment with aqueous potash produces the anti-cyanide, which is best prepared ir, this way. Pa?~ab~~omo6onxcznodiaxocarbcc~ide-ben~e~a~s~i~hinic acid, PhS0,-N(C6H,Br) *NH* CO*NH,, is formed by the combination of itsconstituents and melts a t 151'; theORGANIC' CHEJIISTltY. 79 additive compound formed from chlorobenzenediazoimido-ether melts at 138". Eenzenediazophenylsulphone and bromobenzenediazoimidocyanide also form similar- compounds, the derivative of the latter decompos- ing a t 1 18".The two stereoisomeric nitrobenzenediazocyanides do not appear to behave in this way; phenylenediazosulphide does not unite with benzenesulphinic acid, whilst ethylic diazoacetate is decom- posed by it even a t low temperatures. The compound formed from orthodiazobenzoic acid and benzenesulphinic acid, which mas previously described by Hantzsch and Singer, probably possesses the hydrazo-con- Orthodiaxo- st it u tion, c,H,<" -- O or C6H4< c0.y N(SO,Ph)*hH NH*N*SO,Ph' 6enzo~~ccratolueizeszl Zphinic acid, C,H4<"-- (? melts and N(SO,C,H,)*NH ' decomposes a t 160°, and is at once decompose2 by 'daustic alkalis into toluenesulphinic acid and salicylic acid. Orthodiaxobenxopurub~o~obenxenesu~p~in~c cccid melts a t 18 lo, and yields a very unstable, yellow salt with concentrated aqueous soda.A. H. Tetrazotic, Oxytetrazotic, and Dioxytetrazotic Acids. By WILHELM C. LOSSEN (Annulen, 1897, 297, 322-325. Compare Abstr., 1892,51).-Ferric chloride is a useful agent for recognising many dioxytetrazotic acids, as, for example, benzenyldioxytetrazotic acid and paratolenyldioxytetrazotic acid, with which it develops a red coloration, and forms an iron derivative which dissolves in ether. Benzenyldioxytetrazotic acid and many of its salts are decomposed in accordance with the equation C6H5* CN40,H = C6H5* CN + N, + HNO, under the influence of feeble bases. In the case of dioxytetrazotic acid, this decomposition is spontaneous, nitrous acid being set free, more- over, potassium benzenyldioxytetrazotate liberates nitrogen and yields potassium benzoate when the solution is boiled; the occurrence of one or other of these changes depends, not only on the circumstances of the experiment, but also on the nature of the acid.It is noteworthy that benzenyldioxytetrazotic and paratolenyl- dioxytetrazotic acids are readily converted into the amidines from whence they are derived; treatment of the former substance with hydrochloric acid followed by ammonia gives rise to the benzenyl- amidine salt of benzenyldioxytetrazotic acid. In spite of the fact that all attempts to couple the dioxytetrazotic acids with phenols have proved unsuccessful, the formula NO N :C( C,H,)*N :NOH, most nearly expresses their chemical behaviour, although it must be admitted that they differ from other diazo-compounds in forming additive compounds, instead of diazoamido-derivatives, with amines.&I. 0. F. Benzenyldioxytetrazotic Acid. By WILHELM C. LOSSEN and MAX GRONEBERG (Annulen, 1897, 297, 325'-349. Compare Lossen and Mierau, Abstr., iS91, 1038).-The benzenylamidine salt of benzenyldioxytetrazotic acid crystallises from alcohol in regular quad- ratic leaflets, and from water in yellowish, prismatic crystals; it80 ABSTRACTS OF CHEMICAL PAPERS. explodes at 1 7 8 O , or a t 171' when heated slowly. The potassium salt is also yellowish, and when the aqueous solution is boiled, yields nitrogen and potassium benzoate in quantitative amount. The ammonium salt, obtained by adding ammonium chloride to a solution of the potassium salt, crystallises in long, colourless prisms; it dissolves readily in water and alcohol, explodes a t 13'7", and when heated with water yields nitrogen and ammonium benzoate.The hydvaxine salt forms microscopic, six-sided plates, scarcely soluble in cold water or alcohol, and insoluble in ether; i t explodes a t 60°, and also when rubbed in a mortar. When an alcoholic solution of the hydrazine salt is heated on the water-bath, nitrogen is liberated at 35', two-fifths of the theoretical amount being obtained; benzo- nitrile is also produced, along with ammonium benzenyltetrazotate, whilst, on one occasion, benzeny lamidine benzenyldioxytetrazotate was formed. The aniline salt of benzenyldioxytetrazotate is obtained as a yellowish-white powder which is insoluble in ether, and dissolves with difficulty in water ; it crystallises from alcohol in white needles, and explodes a t 93'.When the salt is treated with boiling water, nitrogen, benzonitrile, and phenol are produced, along with an amor- phous compound having the formula C,,Hl7N,O. The pa~atoluidine salt also crystallises from alcohol in colourless needles, decomposes a t 1 0 5 O , and when boiled with water yields benzonitrile, paracresol, and nitrogen. No definite product is obtained by the action of dimethylaniline on dioxytetrazotic acid. When a solution of the base in normal sulphuric acid is added to an aqueous solution of the potassium salt, and the liquid boiled, an intense green coloration is developed, and gas is evolved, whilst a brown, tarry substance separates; this com- pound is precipitated from chloroform by light petroleum, and has the composition C,,H,,N,O.The phenylhydraxine salt of benzenyldioxytetrazotic acid is very sparingly soluble in water, and crystallises from alcohol in needles which explode a t 90°; when heated with water, it yields benzonitrile, and the same change occurs spontaneously. The behaviour of benzenyldioxytetrazotic acid towards ferric chloride is very characteristic. On treating the potassium salt with neutral ferric chloride, a dark, violet-brown precipitate is a t once formed, and yields a dark, reddish-brown solution on agitation with ether; the ethereal solution, however, is very unst,able, and if separated from the aqueous liquid, gradually deposits a reddish-brown powder, and becomes colourless, yielding benzoic acid on evaporation. If the original precipitate is filtered before agitation with ether, it explodes feebly when heated in the dry state; treatment with caustic potash gives rise to potassium dioxytetrazotate.Experimental details relating to the decomposition of benzenyl- dioxytetrazotic acid by acids, and the regeneration of benzenylamidine (compare foregoing abstract) are described in the paper. M. 0. F. Paratolenyldioxytetrazotic Acid. By WILHELM C. LOSSEN, FRANZ HESS, CARL KIRSCHNICK, and PAUL SCHNEIDER (Annalen, 1897, 297, 349 -353. Compare foregoing abstracts).-The paratolenyl-ORGANIC CHEMISTRY. 81 amidine salt of paratolenyldioxytetrazotic acid, C,H,N,O,,C,H,,N,, is obtained by adding a concentrated solution of potassium nitrite (38 grams) to a concentrated solution of paratolenylarnidine hydro- chloride (20 grams), dissolving the crystalline precipitate in cold water, and treating the solution with 63 per cent.nitric acid (1 1 grams). It crystallises from boiling water in yellowish, rhombic leaflets, a,nd yields rectangular prisms when recrystallised from alcohol ; in the latter form, i t explodes a t 195-198°. The potassium salt separates from concentrated, aqueous solutions in colourless leaflets containing lH,O, which is removed in the desiccator ; even in the moist condition, the salt is highly explosive, and the aqueous solution yields nitrogen and paratoluic acid when boiled or submitted to the influence of sunlight.The ammonium salt crystallises in colourless needles, and explodes a t 130' ; the alcoholic and aqueous solutions, when boiled, liberate nitrogen, and yield ammonium toluate on evaporation. The pyridine salt is crystalline, and explodes when heated ; it dissolves in water and alcohol, but is insoluble in ether. The hydroxylamine, aniline, bu&um, and silver salts are explosive solids. Ferric chloride has the same action on the potassium salt as on the potassium salt of benzenyldioxytetrazotic acid, yielding a highly unstable precipitate which forms a brownish-red solution in ether. M. 0. F. Decomposition of Potassium Paratolenyldioxytetrazotate by Hydrochloric Acid. By WILHELM C. LOSSEN and FRANZ HESS (Annulen, 1897,297, 354-370. Compare foregoing abstracts).-The action of mineral acids on salts of paratolenyldioxytetrazotic acid proceeds in the same direction as in the case of benzenyldioxytetrazotic acid, the chief product being paratoluonitrile. If, however, a cold, saturated solution of potassium paratolenyldioxytetrazotate is treated with 1 mol.proportion of a normal solution of hydrochloric acid, and agi- tated during five minutes, a dark green substance is precipitated, which, if allowed to remain in the liquid, gradually becomes converted into toluonitrile, yielding nitrogen. The greenish-yellow compound (Xuure- fulbung) must be collected, washed with alcohol and ether, rapidly dried in a current of air, and preserved in thin, interrupted layers, protected from thelight ; even then the substance becomes colourless spontaneously, but if these precautions are not observed, a violent explosion takes place.It isevident that this substance doesnot consist of free paratolenyldioxy- tetrazotic acid, as the precipitation is slow, although the product is in- soluble in water ; moreover, i t is found that the filtrate contains in the unaltered state upwards of one-half the dioxytetrazotic acid employed. The unstable compound obtained by the action of hydrochloric acid on potassium paratolenyldioxytetrazotate becomes yellowish-white when treated with chloroform, which is caused to boil by the vigour of the action; nitric oxide is evolved in this change, but if the chloroform is artificially cooled, nitrogen is the sole gaseous product. The insoluble residue consists of pnratolenylamidine paratolenyldioxytetrazotate, the filtrate containing paratoluonitrile with 10 per cent.of paratoluic acid. The same products arise when the compound undergoes spontaneous decomposition. Under the influence of ammonia, added to the liquid in which the compound has been precipitated, it yields paratolenylamidine82 ABSTR.ACTS OF CHEMICAL PAPERS. paratolenyldioxytetrazotate, but if the substance is first isolated, and then treated with dilute ammonia until the alkaline action persists, ammonium paratolenyldioxytetrazotate passes into solution, and a red compound remains undissolved. Rubccnaidicle, C8 H9N,0, is the name given by the authors to this substance, which has the empirical formula of paratolenylamidine paratolenyldioxytetrazotate; i t is also produced by the action of aniline, and the filtrate, on evaporation, yields paratoluic acid and ammonium paratolenyldioxytetrazotate. Rubamidide explodes somewhat violently at 60-65', and is slowly decomposed by cold water ; the solution in alcohol is red but rapidly becomes colonrless, yielding paratoluonitrile.It is insoluble in ether, but yields gas when kept in contact with it, forming paratolenylarnidine ; alcoholic potash also libe- rates gas, and gives rise to toluonitrile and a small proportion of potas- sium dioxytetrazotate. The action of hot water converts rubamidide into toluonitrile and a small proportion of amidine paratolenyldioxgtetr- azotate, nitrogen being set free. From these facts, it is clear that paratolenylamidine paratolenyl- dioxytetrazotate and rubsmidide are distinct substances, although having the same empirical formula, which is also that of a nitroso- paratolenylamidine ; it is quite possible, therefore, that rubamidide is a compound of the latter class.M. 0. F. Phenylglycolenyldioxytetrazotic Acid and Phenylglyoxenyl- dioxytetrazotic Acid. By WILHELM C. LOSSEN and FRANZ BOGDAHN (Awnalen, 1897, 29'7, 371-380. Compare foregoing abstracts).- PhenylgZycoZenyZamidi?ze (phenylhydroxyacetamidine) has been prepared by C. Beyer (Abstr., 1885, 983) ; the nitrute forms rhombic or mono- clinic crystals, and melts and decomposes at 154'. Phenylglycolenylamidine phenylglycolewyl~ioxytet~a~otccte, CsH8N403 > C8H,()N20, is obtained by adding potassium nitrite solution and a small quantity of nitric acid to a warm, aqueous solution of phenylglycolenylamidine hydrochloride (I mol.), the product being treated alternately with potassium nitrite and nitric acid until a molecular proportion of each has been added.It is a crystalline powder which explodes when heated ; it dissolves in alcohol, but is insoluble in alcohol and ether. The potassium salt crystallises from water, but decomposes on boiling the solution; it is highly explosive, and detonates when heated, or rubbed, or treated with concentrated sulphuric acid. The barium salt crystallises in aggregates ; it is less explosive than the potassium salt. The silver salt is amorphous and colourless ; it is an explosive substance, and rapidly darkens when exposed to light. The uniline salt crystal- lises in white leaflets, but rapidly becomes brown, and acquires the odour of aniline ; it explodes when heated on platinum foil.When an aqueous solution of potassium phenylglycolenyldioxytetr- azotate is boiled, nitrogen is set free, and potassiummandelate produced ; hot dilute sulphuric acid liberates a mixture of nitrogen and nitric oxide, and gives rise t o mandelonitrile. The potassium salt of phenylglyoxenyldioxytetrszotic acid, COPh C ru' 402K, is obtained by oxidising potassium phenylglycolenyldioxytetrazotateORGANIC CHEMISTRY. 83 with potassium permanganate at 60" ; it crystallises in long, lustrous, white needles, which become greenish-yellow in the desiccator, and forms a greenish-yellow solution in water. The salt explodes when heated, and also on treatment with concentrated sulphuric acid ; a very dilute solution (1 : 7000) has a sweet, astringent taste.The silver salt is a yellowish-brown, amorphous compound which is highly explosive. The potassium salt of phenylglyoxenyldioxytetrazotic acid undergoes a characteristic change when the aqueous solution is boiled, yielding nitric oxide, nitrogen, benzoic acid, and hydrogen cyanide; the two last named are probably due t o the intermediate production of the nitrile of benzoylformic acid. 31. 0. F. P-Naphthenyldioxytetrazotic Acid. By WILHELM C. LOSSEN and GUSTAV GRABOWSKI (Annulen, 1897, 297, 380-385. Compare foregoing abstracts). - P-Nc~phthe.lzylamidine P-nuphthen yldioxytetr- axotate, Cl,H8N,0,,C,lH,,N2, is prepared by adding potassium nitrite (2 mols.) t o aqueous P-naphthenylamidine hydrochloride (1 mol.), dis- solving in water the precipitate so formed, and treating the solution with concentrated nitric acid (1 mol.) ; it explodes a t 180', and gives Liebermann's reaction for ni troso-compounds.The potassium salt crystallises from water in yellowish needles, and explodes with excep- tional violence when heated, or on treatment with concentrated sul- phuric acid. P-Naphthenylamidine, employed in the production of the foregoing salts, has been prepared by Lohmann (Ber., 1878, 11, 1486), and melts a t 145' ; the nitrite crystallises from alcohol in colourless needles and melts a t 122'. The nitrate is also crystalline, and the platinochloride forms slender, yellowish needles and melts at 216-217'. It is noteworthy that anisenylamidine does not give rise to a dioxy- tetrazotic acid.M. 0. F. The siluey salt is also explosive. Tetrasotic, Oxytetrazotic, and Dioxytetrazotic Acids. By WILHELM C. LOSSEN (Annulen, lS97,298,54--55).-A summary of tthe results described in the following abstracts. M. 0. F. Benzenyloxytetrazotic Acid, By WILHELM C. LossENand FRIEDRICH Fucrrs (Annulen, lS97, 298, 55-67. Compare Lossen, Abstr., 1891, 1041). -Benzenyloxytetrazotic acid separates from a mixture of ether with a small quantity of alcohol in rhombic, hemihedral crystals; cr, :6: c = 0.9506 : 1 : 0.6236. Concentrated hydrochloric acid at 160' resolves the substance into benzonitrile, benzoic acid, and ammonium chloride, whilst concentrated sulphuric acid at 185' gives rise t o metasulpho- benzoic acid; nitric acid (sp. gr.= 1.53) acts vigorously on the corn- pound, producing nitrobenzoic acid. The culcium salt of benzenyloxytetrazotic acid crystallises from water in cubes, containing 3H20, and the sodium salt contains 1H,O; the cobult salt forms large, reddish crystals containing 2H20, and the copper salt, which contains 3H,O, crystallises in green, microscopic needles. The methylic salt is crystalline, and melts at 40'; the ethylic salt is a yellowish oil, and yields benzoic acid, benzonitrile, ethylic chloride,84 ABSTRACTS OF CHEMICAL PAPERS. and ammonium chloride when heated in a sealed tube with concen- trated hydrochloric acid at 160". The nitromethylic salt, obtained by dissolving the methylic salt in nitric acid (sp. gr. = 1-53}, crystal- lises from alcohol in long needles melting at 118"; reduction with stannous chloride and hydrochloric acid converts this substance into the amiclomethylic salt, which crystallises from hot water in slender needles, and melts a t 110'; the hydrochloride forms yellow plates.M. 0. F. Paratolenyloxytetrazotic Acid. By WILHELM C. LOSSEN and PAUL SCHNEIDER (Annalen, 1 89 7, 298, 6 7-78).-Puratolenyloxytetrccxotic acid, C,H,N,O, obtained by reducing paratolenyldioxytetrazotic acid with 10 per cent. sodium amalgam, crystallises from water in slender, colourless needles, and from a mixture of ether and alcohol in lustrous prisms ; it contains 1H20, which is removed at 120°, and melts and decomposes at 1 72', yielding paratoluonitrile, nitrogen, and nitrous oxide. Concentrated hydrochloric acid a t 155" resolves the compound into paratoluic and paratolenyloxytetrazotic acids, the same effect being produced by concentrated sulphuric acid a t 170'; nitric acid (sp. gr.= 1.105) gives rise t o toluonitrile and paratoluic acid, the latter being also produced when paratolenyloxytetrazotic acid is heated with alcoholic ammonia at 160". The acid, C,H,N,O, a bye-product in the preparation of paratolenyloxytetrazotic acid, melts at 154' ; the culcium salt contains 3H,O, and the silver salt is somewhat soluble in ether, alcohol, and hot water. The potc~ssiurn salt of paratolenyloxg tetrazotic acid is anhydrous, and the sodium salt, which crystallises from alcohol in slender needles, contains 1$H20 ; the buriurn and calcium salts contain 3H,O, the cobalt salt, which separates from water in small, red crystals, 2H20, whilst the copper and silve?* salts are anhydrous. The ethy2ic salt is a colourless liquid, yielding paratoluonitrile, paratoluic acid, and ammonium chloride when heated with hydrochloric acid a t 170'; the methylic salt is crystalline and melts at 44".M. 0. F. Phenethenyloxy tetrazotic Acid. By WILHELM C. LOSSEN and ERNST KAMNER (Annalen, 189 7,298,78--88).-P?~ene~henyloxytetraaotic acid, C,H,N,O, prepared by reducing phenethenyldioxytetrazotic acid with 10 per cent. sodium amalgam, crystallises from water in con- centric groups of colourless needles ; it melts a t 135', and explodes a t higher temperatures. Caustic potash at 250" converts the substance into phenylacetic acid, but concentrated hydrochloric acid at 155O leaves t h e substance for the most part unchanged, a small quantity of nitrile and ammonium chloride being produced ; concentrated sulphuric acid at 180" gives rise to sulphophenylacetic acid.The silver salt of phenethenyloxytetrazotic acid is a white, amorphous powder, and melts a t about 73"; the copper salt contains 3H,O. The ammonium salt crystallises in small, colourless needles, and melts at 145", the aniline salt separates from ether in plates, and melts a t 142O, and the phenylhydraxine salt melts a t 157.5". The methylic salt, which is a highly explosive, yellow liquid, yields a nitro-derivative when treated with nitric acid (sp. gr. = 1.53). M, 0. F.ORGANIC CHEMISTRY. 85 Phenylglycolenyloxytetrazotic Acid.By WILHELX C. LOSSEN and FRANZ BOGDAHN (Annalen, 1897,298, 88-9 l).-Phenylglycolefi$- oxytetrccxotic acid, C8H8N402, obtained by reducing phenylglycolenyl- dioxytetrazotic acid with 2 per cent. sodium amalgam, separates in small crystals on adding light petroleum to the alcoholic solution, and melts a t 141'. The silver salt is white, and resists the action of light ; the barium salt crystallises in thin leaflets, and is anhydrous. M. 0. F. Beneenyltetrazotic Acid. By WILHELM C. LOSSEN and FRANZ STATIUS (Annalerz, 1897,2!38, 91-105. Compare Lossen, Abstr., 1891, 1041).~Benzenyltetrazotic acid is most conveniently prepared by Pinner's method (Abstr., 1894, i, 386). The sodium salt crystallises in lustrous, highly refractive leaflets containing 3H20, and the calcium salt, which forms transparent prisms, contains 4H,O ; the copper salt is anhydrous, and the ammonium salt, which crystallises in white leaflets, undergoes dissociation when heated.The methylic salt separates from a mixture of alcohol and ether in transparent, prismatic crystals, and melts at 40'. When benzenyltetrazotic acid is heated alone a t 218', nitrogen is evolved, and a mixture of diphenyltriazole and diphenyl- tetrazine produced. Bromobenxenyltetraxotic acid, C7H5N4Br, is obtained by heating benzenyltetrazotic acid with bromine and water at 160' during 16 hours ; it crystallises from dilute alcohol in flat, transparent prisms, and melts a t 265'. Nitrobenxenyltetraxotic acid, NO,* CiH5N4, is formed when benzenyltetrazotic acid is dissolved in nitric acid (sp.gr. = 1.55) mixed with concentrated sulphuric acid; it cystallises from water, and melts at 145O. The barium salt contains 3H,O, and the silver salt, which is yellowish-white, resists the action of light. M. 0. F. Paratolenyltetraeotic Acid. By WILHELM C. LOSSEN and CARL KIRSCHNICK (Annalen, 1897, 298, 105-107).-Paratolenyltetrazotic acid, C8H8N4, obtained by reducing paratolenyldioxytetrazotic acid with sodium amalgam, crystallises from alcohol in small needles, and melts a t 248". (Compare Pinner and Caro, Abstr., 1895, i, 137.) 31. 0. F Anisenyltetraeotic Acid. By WILHELN C. LOSSEN and JAMES COLMAN (Annalen, 1897, 298, 107-1 16).-AnisenyZtetraxotic cccicl, OMe*CGH,* CN4H, which is best prepared by Pinner's method (Abstr., 1895, i, 137), crystallises from dilute alcohol in white needles melting a t 228'.The potassium salt crystallises in long needles, and is readily soluble in water, the ammonium salt forms leaflets, and the bcirium salt crystallises from alcohol in thin, quadratic plates. The methylic salt crystallises from dilute alcohol in long needles, and melts at 93'; the ethylic salt also forms long needles, and melts at 62'. Nitroanisenyltetraxot~c mid is obtained by heating anisenyltetrazotic acid with nitric acid (sp. gr. = 1.4) in boiling water for 1; minutes, and pouring the liquid into cold water after an interval of ten minutes ; it crystallises from hot water in long, yellow needles containing 1H20, and melts a t 203'. The bccrium salt crystallises from water in86 ABSTRACTS OF CHEMICAL PAPERS.Ortho- .............. Meta- ............... Para- ............... plates, and contains 3H,O. Amidounisenyltetmzotic acid, prepared by reducing the nitro-acid with stannous chloride and hydrochloric acid, crystallises from hot water in needles containing 1H,O and melts a t 223". The hydrochloride forms needles containing. lH,O, and C1-. Rr--. I-. NO,-. CHS-. -OH. ~ ~ _ _ _ _ 35.7 7.0 9 - 3 4'2 28'4 15'3 55.2 18'4 28.3 22.3 63.8 55.9 53.1 17'2 26'8 22.3 71.0 51'3 the potassium salt cr$tallises in long needles containing TH20.A ' M. 0. E. Etherification of Mono-substituted Benzoic Acids. By VICTOR MEYER (Zeit. physikuZ. Chem., 1897, 24, 219--220).-The author had previously stated, as a general law, that, in the case of the mono-substituted benzoic acids, the velocity of etherification is least €or the ortho-acids, and that their ethereal salts are the most difficult to hydrolyse (Abstr., 1895, ii, 466).The results of Kellas' experiments (following abstract) are in complete accord with this law, and, further, indicate the marked influence of the molecular weight of the acid, in the case of compounds with analogons substituents ; thus, chlorobenzoic acid is etherified more rapidly than the brominated compound, and this again more rapidly than the iodo-compound. L. M. J. Velocity of Etherification of Mono-substituted Benzoic Acids, and Hydrolysis of their Ethereal Salts, By ALEXANDER M. KELLAS (Zed. physikcd. Chem., 1897, 24, 221-252). The re- searches of Meyer (Abstr., 1895, ii, 466) have shown that, in general, ortho-aromatic acids are more rapidly etherified than the corresponding metx- or para-derivatives.The author, therefore, determined the velocity of etherification for a large number of mono-substitution derivatives of benzoic acid in order to prove the general law and determine the influence of temperature, and of the nature of the substituent. The acids employed were, toluic acids, nitro-, chloro-, bromo-, iodo-, and hydroxy-benzoic acids, the three isomerides being used in each case. The effect of the position of the substituent is seen from the accompanying table, which gives the quantity of ethereal salt produced under similar conditions ; the vertical sets alone being comparable. Experiments were then made a t a series of temperatures varying from 0" to 51" ; the velocity was found to increase with temperature, and tables and curves are given for each acid, the curve in all cases being convex to the temperature axis and considerably steeper for the meta- and para- than for the ortho-derivatives, so that the values approach a t 0'.To determine the influence of the substitiient, simultaneous experiments were made with various acids, equivalent quantities being used; the order of the velocities was found t o be benzoic, chlorobenzoic, toluic, bromobenzoic, iodobenzoic, nitrobenzoicORGANIC CHEMISTRY. 87 for the ortho-compounds, but toluic acid comes before chlorobenzoic acid in the meta- and para-compounds, and the nitro- before the iodo- acid in the meta-compounds ; the effect of molecular weight is there- fore only comparable for analogous compounds.The order of the velocities of hydrolysis were not found to be the same as, or the reverse of, those of etherification, for, although the chlorbromo- and iodo-derivatives are still in t‘he same order, yet the velocity of hydro- lysis of toluic acids is much smaller than that of the iodo-acids, whilst the velocity in the case of the nitro-acid is greater than that of the chloro-derivative. I n all cases, however, the velocity is least for the ort ho-acid s. L. M. J. Hemipinic Acid, and t h e Isomeric Alkylic Hydrogen Papa- verates. By ALFRED KIRPAL (Moncctsh., lS97, 18, 461-466).- The hemipinic acid of which Ostwald determined the conductivity constant (Zeit. physiknl. Chem., 1889, 3, 268) was in reality meta- hemipinic acid ; the true acid, C,H,(OMe),(COOW), [ 3 : 4 : I : 21, which has been prepared from opianic acid, has the conductivity constant K=0.110. Ostwald found that a-methylic hydrogen hemipinate, in which the free COOH group has COOMe on one side of it, and H on the other, has a higher conductivity constant than the P-isomeride, in which the free COOH group has on one side OMe, on the other COOMe.I n the case of the corresponding derivatives of papaveric acid, C(CO0H) :$J*COOH N*CH=CH C,H,( OM e)2. CO* C< 9 that methylic hydrogen salt which has the free COOH in the 4’-position with respect to the nitrogen has a higher constant than the isomeride, where it is in the 3’-position : contrary to expectation, the author says, for reasons which it is not easy to see. These two salts, in more concentrated solutions, have a smaller conductivity than the acid, but at a greater dilution their bonductivity becomes greater than that of the acid.The same is true of P-methylic hydrogen hemipinate as compared with hemipinic acid ; the a-isomeride, on the other hand, has always a smaller conductivity than the acid. Behaviour of Acetylgallic Acid and Acetyltannin with Hubl’s Reagent. Ey CARL BOETTINGER (Chem. Zeit., 1897, 21, 57). -Triacetylgallic acid and pentacetyltannin are scarcely attacked by Hubl’a reagent, the former giving an iodine number from 1.2 to 2.4, the latter from 2 to 3.1. These compounds dissolve easily in chloro- form, but the acetyltannin which is insoluble in a dilute aqueous solution of sodium carbonate is precipitated from its solution in chloroform by adding Hubl’s reagent or alcohol. Since, however, gallic acid and tannin both give large iodine numbers, this reaction would seem to be dependent on the presence of unsubstituted hydroxyl groups. Such being the case, if the composition of gallic acid and tannin be assumed to be represented by formula obtained by doubling the ordinary formuls, then the former might be expected to give a larger iodine number than the latter, which contains only five instead of six hydroxyl groups, and this is in accordance with the fact.But on C. F. E.88 ABSTRACTS OF CHEMICAL PAPER.S. this assumption, however, pentacetyltannin would contain a carboxyl group and should be of acid character, whereas it is only slowly attacked and decomposed by dilute sodium carbonate solution.It is evident that Hubl's iodine reaction in the case of gallic acid and tannin cannot be attributed to the same cause as the similar reaction afforded by fats. E. W. W. Diacyl Anilides. By HENRY L. WHEELER, T. E. SMITH, and C. H. WARREN (Amer. Chem. J., 1897, 10, 757-766).-Beizxenesu@h- acetanilide, C,H,*SO,*NPhhc, obtained by the action of acetic anhy- dride on sodium benzenesulphanilide, separates from dilute solution in the form of large, colourless monoclinic plates melting a t 116.5'. Benxenesul~~~o~opionun~lide, prepared in a similar manner, separates from alcohol in very large crystals melting a t 115'. Benxenesulpho- butyranilide crystallises in stout prisms melting a t 89-90". Ben- xenesulphobenxa~ilide forms long, thin, monoclinic needles melting a t Benxenesulph-a-ncqhthalicle, Cl,H7NHS02C,H,, prepared by t be Baumann-Schotten reaction in the usual manner, crystallises from alcohol in needles melting at 168-169".The corresponding P+aaph- thulide crystallises in oblong plates or flattened prisms melting a t 97". Benxenesu~hobenzo-a-nuphthalide forms minute crystals melting a t 193-1 94", and the corresponding #3-compound fine, white needles melt- ing at 161-162". As the group -C<: exists in the diacyl anilide, the formyl derivative of the above series has been compared crystallo- graphically with its homologues. The results show that ncetyl and propionyl derivatives of benzenesulphanilide exhibit close crystallo. graphic analogy, the compounds being monoclinic, hemimorphic, and pyroelectric, their crystallographic axes and the angle p being similar.On the other hand, bezenesulphoformanilide is orthorhombic, and shows no analogy whatever with these compounds. Moreover, crystals of formanilide showed no analogy with those of acetanilide. Natural Resins (" Uberwallungsharzeyy). 111. By MAX BAM- BERGER and ANTON LANDSIEDL (Monatsh., 1897, 18, 481-509. Compare Abstr., 1895, i, 109). -Pinoresinol, from the resin of Pinus layicio, has now been obtained by crystallisation from a con- centrated alcoholic solution, in large rhombic prisms [a : b : c = 0.8689 : 1 : 0.38171 ; it melts a t 1 2 2 O , and is now found to have the composition C,,H,,O,. The '' Uberwallung " resin from pines can also be separated by etber into a soluble a- and an insoluble /3-resin, present respectively to the extent of 80 and 20 per cent.The a-resin consists of the pino- resinol salts of paracoumaric and abietic acids, the first of which is present in much larger amount ; i t also contains a little paracoumaric acid, and some vanillaldehyde, the pinoresinol obtained from it is in all respects identical with that described above, C,Hl,02(OH)2(0Me),, and yields the same diacetyl and dimethyl derivatives. A diethyl- pinoresinol was also obtained by acting on the potassium salt with ethylic iodide and methyl alcoholic potash ; i t melts at 118'. Con- 114-1 15'. A. W. C .ORGANIC CHEMISTRY. 89 centrated nitric acid converts pinoresinol in acetic acid solution a t - 15" into dinitrogusiacol OH* C,H,(OMe)( NO,), (Herzig, Abstr., 1883, 464).Bromine, in cooled acetic acid solution, converts it in to dibrornoresinol dibronzide, C, ,H,,Br,O,, which melted a t any tem- perature between 225" and 2 5 4 O , and mas possibly not pure. The p-resin was purified by dissolving it in alcohol, reprecipitating with very dilute hydrochloric acid, boiling for several days with 10 pel* cent. alcoholic potash, precipitating with sulphuric acid, redissolving in aqueous potash, precipitating the potassium salt by the addition of solid potassium hydroxide, and decomposing it with very dilute hydrochloric acid. It forms a chocolate-brown powder, has the methyl number 56, and appears to have the composition C 3 ~ I ~ ~ 3 0 0 ~ ( O ~ ~ e ) 2 ; its properties are those of a tannol, whence it is named pzizoi*esi?zo- tnnnol.Jt yields a benxoyl derivative when it is treated with 10 per cent. aqueous soda and benzoic chloride, and a naethylic derivative when it is boiled with methylic iodide and methyl alcoholic potash ; it is uncertain, in both cases, whether two or three benzoyl or methyl groups enter the molecule; both the products are brown and amorphous. The '' Uberwallungs " resin of the larch contains caffeic acid, vanillaldehyde, and a n acid resembling ferulic acid. The resinol, separated from it by the methods used in the case of pinoresinol, is named lnriciresinol, melts at 164", and appears to have the composi- tion C,,H,,O, ; it forms a potassium derivative, C,,H17K,0, + 2H20. Lariciresinol gives the methyl number 73-5-§1*4, but from this it is impossible to decide whether it contains two or three methoxyl groups.When it is boiled with acetic chloride, it forms an cccetyl derivative, melting at 159", of which the composition could not be determined satisfactorily ; when its potassium salt is boiled with excess of acetic anhydride, a substance is formed which melts a t S5", and appears to be a triacetyl derivative. C. F. B. Compounds from Lichens. By WILHELM ZOPF (Annulen, 1897, 297, 271-312. Compare Abstr., 1897, i, 362, 436).-The first instance of the occurrence of a derivative of rnethylamine in lichens is afforded by 8tictn fuliyinosa (Dickson), which contains trimethyl- amine. Erythric acid has been hitherto found only in Roccella tinctoria (Ach.), R. fucijformis (Ach.), and Lecanora (Ochrolecl~iu) turturecc (L.) ; it occurs also in Parmelia olivetorum (Nyl.), and in Evernicc fuifunxecc (L.), giving rise to the red coloration produced on treating the medulla of these lichens with a solution of bleaching powder.Evernic acid, first obtained by Stenhouse from Evernia ps.unccstyi (L.), is only to be found in one variety of this lichen, namely, vnr. uulgaris (Korber), and does not occur in var. tlmmnodes (Flotow), which must be, therefore, regarded as a separate species (Eve~nicc tharnnodes). This acid has been isolated by the author from IZccmalina pollinaria (Westr.), and Evernia tlharnnodes also contains divarictic acid, obtained by Hease from Evemtia divaricutu (L.). Gyulolechia uurella (Hoff m.) contains callopismic (ethylpulvic) acid, which occurs also in Callopisnau vitellinum (Ehrh.), Gasparrinia medians VOL. LXSIV.i. h9 0 ABSTRACTS OF CHEMICAL PAPERS, (Nyl.), and Cundelaria concolor (Dickson) ; when the acid is heated with methylic alcohol in closed tubes a t 150-160°, i t yields a yellowish-green nzethylic salt. Rochleder and Heldt's cbrysophanic acid occurs in Gaspccrrinia cirrhoclwoa (Ach.), and in Gallopisma Javovirescens (Mass.) ; the same substance has been described as parietin by Thompson, physciacic acid by Yaternb, chrysophyscin by Lilienthal, and physcion by Hesse. The author confirms the observation of Hesse regarding the occur- rence of ramalic acid in Rumalincc pollinuria (Westr.) ; barbatic acid, hitherto found only in Usnecc barbata (L.), occurs also in Uwen Zongissima (Ach. ). The presence of usnic acid has been established in the following lichens : Usnea longissinaa (Ach.), Ranzalincc polymorpha (A ch.), Evernia thumnodes (Elotow), 3.prunaslri (L.) oar. vulgaris (Korber), 8. divaricuta (L.), Paymelia conspersa (Ehrh.), Placodium gypsciceum (Sm.), and P. chrysoleucum (Sm.). Squamaric mid, which occurs in Placodiurn gypsaceum (Sm.), crystal- lises from alcohol in rosettes of slender, white needles, melting a t 262-264'; it is insoluble in water, and dissolves with difficulty in chloroform and cold alcohol. The solution in concentrated sulphuric acid is yellow, and in dilute alkalis yellowish-green, the substance being somewhat soluble in sodium carbonate ; the alcoholic solution reddens litmus, and develops a deep red coloration with ferric chloride. Although it resembles psoromic acid in crystalline form, melting point, and solubility, it differs from it in its behaviour towards alkalis, which do not give rise to red salts.Plucocliolin has been isolated from Plucodiurn chrysoleucunz (Sm.), and crystallises from ether in long, highly lustrous prisms, or in thin plates when quickly crystallised; i t melts a t 154-156'. It is very soluble in chloroform, but dissolves less readily in ether, benzene, and glacial acetic acid ; concentrated sulphuric acid develops a red, and alkalis a yellowish-green coloration. The alcoholic solu- tion is feebly acidic, and does not develop coloiir with ferric chloride ; bleaching powder has no effect on the substance. I n addition to the seven species which have been mentioned in previous papers, zeorin occurs in Anupt@a speciosa (Wulfen), and salazinic acid, hitherto recognised in Stei*eocccuZon salctxinuna (Bory}, is present in Alectoyea cunu (Ach.), Pawneliu perforata (Ach.), P.excrescens (Arnold), P. conspersa (Ehrh.), and Evewaiopsis Trulla (Ach.). The presence of atranoric acid has been already established in no fewer than thirty-five species of lichens; to this number must be added the six following, Purrneliu olivetomm (Nyl.), P. perlatu vccr. excrescens (Arnold), P. peiforatu (Ach.), P. Nilgl~ewensis (Nyl.), Everniu punastri (L.) var. vulgaris (Korber), Everniopsis Fidla (Ach., Nyl.). Hesse's statement (Abstr., 1897, i, 257), that Candelaria concoloq- (Dickson) contains chrysophanic acid is, in the author's opinion, erroneous. 31. 0.F. Indolinones, 111. By KARL BRUIWER (ilfonatsh., 1897, 18, Compare Abstr., 1897, i, 100, 438).-1J7he11 acetic, pro- 527-549.0 RGAN IC CHEMISTRY, 91 pionic, butyric or phenylacetic hydrazide, C,H,* NH*NH* CO* CH,R, is heated with four times its weight of recently ignited lime f o r about an hour a t 1 90-200°, ammonia is evolved and a 3'-R-2'-indolinone, is formed, the yield varying from 70-85 per cent. of the theoretical. When R = H , however, i t is necessary to heat to 200-220°, and the yield is only 4.5 per cent. Preliminary experiments have shown that the phenylhydrazide of isopropylacetic acid and the methylphenyl- hydrazide of phenylacetic acid react in the same way. 2'-Indolinone, from acetic phenyl hydrazide, was found to bc identical with oxindole prepared by von Baeyer's method (Abstr., 1878, 587).3'-Methyl 2'-indolinone, from propionic phenylhydrazide, is identical with the atroxindole of Trinius (Abstr., 1885, 529) ; when crystallised from benzene it melts a t 123", from water a t 113O, and each modifica- tion is converted into the other by contact with a crystal of the latter. When boiled with excess of acetic anhydride, it yields a moncccetyl derivative melting a t '79"; when it is dissolved in dilute sulphuric acid and heated with excess of bromine-water, a dibromo-derivative, C,H2Br2:C,NH,0, melting a t 171" is formed ; heated with methylic iodide and a methyl alcoholic solution of sodium methoxide in a sealed tube at 110-120°, a 1'-methylindolinone is not formed, but I' : 3' : 3'- trimethyl-2'-indolinone (Abstr., 1896, i, 625, and lS97, i, 100) together with some 3' : 3'-dirnethyl-2'-iudolinone (Abstr., 1897, i, 438).3'-Ethyl-2'-indolinone, from butyric phenylhydrazide, crystallises in monoclinic plates (fundamental angles : 100*110 = 54" 10'; 001.110 = 81" 6' ; 001.011 = 51" 16' ; p= 74" 47'), melts at 102*5", and boils a t 200-220" under 44 mm., a t 320-323' under 742 mm., pressure. Its aionacet~l derivative melts at 45" ; it yields a yellow dinit9.o-derivative melting a t 176", when it is dissolved in acetic acid and the solution warmed with strong nitric acid ; i t also forms a dibromo-derivative, C,H213r2: C4NH,0, which melts at 150". Unlike its methyl analogue, it does undergo substitution in the 1'-position when it is heated with methylic iodide and sodium methoxide in methyl alcoholic solution.l'-MetAy1-3'-etkyl-2'-indolinone boils at 280-285" under 745 mm. pres- sure; it yields a bromo-derivative, melting a t 161", which gives up some, or all, of its bromine when boiled with alcoholic potash, and must there- fore contain the bromine in the pyrrolidone, and not in the benzene, ring. 3'-Phenyl-2'-indolinone, from phenylacetic phenylhydrazide, melts a t 183"; it forms a rnonacetyl derivative, melting at 103", and a monobromo-derivative, CGH,Br: C,NH70, me1 ting a t 19 1". C. F. B. Action of Sulphur Chloride on Aromatic Amines. By ALBERT EDINGER (Ber., 189'7, 30, 2418-2420. Compare Abstr., 1897, i, 103). -The compound previously obtained by the action of sulphur chloride on quinoline has the molecular formula C,,H,,N,S, and is very stable towards oxidising agents.Nitric acid converts it into mono- and di- csrboxylic acids of pyridine, and it has therefore the constitution C,NH,<~>C,NH,. The substance is not poisonous. h 292 ABSTRACTS OF CHEMICAL PAPERS. The application of this reaction t o a number of a~omatic amines has shown that similar compounds are only formed when the arnine belongs t o the quinoline series, .and not when i t is a derirative of pyridine, iso- quinoline, or hydroxyquinoline. Orthon~zthylquinoliat?, when treated with sulphur monochloride or dichloride, yields a szcbstnnce of the same composition as that obtained from quinoline itself, the methylic group being eliminated ; this sub- stance melts above 360" and is converted by nitric acid into nicotinic acid. I t is accompanied by halogen derivatives of quinoline : 1 : 3-di- chloroquinoline melting a t 104O, and a tetrachloroquinoline melting at 121'.Orthohyclroxyquinoline only yields a dichloro-compound melting at 179" ; parahydroxyquinoline, a nionochloro-compound melt- ing at 1S7O, and isoquinoline, a trichloro-compound melting at 1 2 4 O , no sulphur compound being formed. It has not been found possible to obtain any pure product by the application of the reaction to pyridine. A U Additive Compounds and Substitution Derivatives of Phenyldimethylpyrazolone. By M. C. SCHUYTEN (Chenz. Zeit., 1897, 21, ll).-By the action of nitrous acid, that is, of a solution of sodium nitrite with glacial acetic acid, on the additive compounds of antipyrine with thiocyanic acid, cadmium chloride, zinc chloride, resorcinol, salicylic acid and chloral hydrate respectively, the blaish- green coloration characteristic of the nitroso-derivative was produced, except in the case of the resorcinol compound, which gave a yellow solution.In every case, however, more or less speedy decomposition followed and no nitroso-derivative could be isolated. From the pro- ducts of the reaction with the zinc chloride compound, a, yellow, floccn- lent precipitate which became black at 185', and decomposed with violence a t 1 8 8 O , and a dark red powder were obtained. Similar negative results were obtained by passing nitric oxide gas over the above-mentioned additive compounds or their solutions. Attempts to prepare additive compounds of nitroso-antipyrine analogous to those of antipyrine also failed, E.W. W. Action of Bases on Aposafranine. By OTTO FISCHER and C. GIESEN (Bey,, 1897, 30, 2489-2494. Compare Abstr., 1896, i, 323). -By heating aposafraniiie hydrochloride wilh methy lamine hydro- chloride and iuethylamine in alcoholic solution for 5-6 hours at loo", NHMe N -- rrzetl~?llnmidosufranir~e, NH>CBH,<Sph>C$4, is obtained ; its hydrobromide, Cl,H16N,,H Br, was analysed. Solutions of the salts are orange coloured, but are turned pink by the addition of strong acids; the iodide is only sparingly soluble. With paranisidine, green, crystal- line puyccnisidouposccfi*unine, C25H20N40, is formed ; solutions of this are brown ; the hydyochloride is yellowish-green. With ethylenedi- amine in boiling alcoholic solution, the product is a brown, crystalline substance with bluish-green surface-lustre, which forms orange-red solutions, coloured violet by mineral acids.ORGANIC CHEMlSTRY. 93 When it is heated, best with mercuric oxide, or when aposafranine is heated with ethylenediamine at 150-1 60', a brownish-yellow, crystal- line substance with a greenish surface-lustre is obtained ; the alcoholic solution is turned first red and eventually blue by the addition of mineral acids; the solution in benzene has a greenish-yellow fluor- escence.The substance yields a mon-acetyl derivative and is possibly ~ H , ~ ~ ~ ~ ~ C , H , ~ ~ ~ ~ ~ line substance, possibly C , H ~ < N ~ C , H ~ ~ ~ ~ ~ > C G H ~ ; 0 With orthamidophenol, aposafranine yields a brownish-red crystal- this forms a cherry-red solution in alcohol, with a blood-red fluorescence.Naphthyl- eneorthodinmine also reacts with aposafranine. (3. F. B. A New Cyclic Compound. By ~IILORAD Z . JOVITSCIIITSCH (Bey., 1897,30, 2426-2431).-A substance having a ring formation differing only from t h a t cf the peroxides in that i t contains cz nitrogen atom in place of carbon and that the two remaining nitrogen atoms are directly joined, is formed when the aniline derivative of ethylic oximido- acetate is treated with nitrous acid; that this substance is in reality represented by the formula 7 H-y-? is deduced NPh-N-O from the fact that of the only other two possible formulae, NO *NPh*C( NOH).COOEt and. NO *XPh*CH(NO)*COOEt, the former is improbable, since hydroxylainine is not eliiniiiated when the substance is heated as in Liebermann's reaction, and the latter owing to the fact that no amido-derivative is formed on reduction ; the a n i l i n e derimtive of ethylic oxin2idocicetic cicid, NHPh*C( XOH).COOEt, is formed by the action of aniline on ethylic chloroximeacetic in alcoholic solution, and crystallises from hot dilute alcohol in long, slender prisms melting at 109'; it is nearly insoluble in cold water, but dissolves readily in alcohol and ether; the action of the calculated quantity of potassium nitrite and sulphuric acid, on an ethereal solution of this ethylic salt, gives rise to the cyclic compound above mentioned, which, after the addition of the sulphuric acid, separates from the solution in slender, orange-yellow crystals which decompose a t 169' ; its solution in dilute alkali is coloured deep violet, gradually changing to deep red when boiled, owing t o t h e elimination of the carbethoxy-group and formation of the &alkali salt of the substunce I for which, as also for its carbethoxy-derivstive, the author does not attempt to propose a name ; the free substance, which can be separated by acidify- ing, crystallises from dilute alcohol in slender needles containing 1H,O, which i t loses at 140-190", finally decomposing at 206'.The red alkali salt loses its colour on prolonged exposure t o the air, and almost instantly in the presence of carbonic anhydride. ,4 substuwe, Ci4Hi8T203, is also formed by the action of nitrous acid on the aniline derivative ; this crystallises from water in slender, yellow, fluorescent prisms melting a t 69-70'.C H2-lf-? NPh-N-O J. F. T.94 ABSTRACTS OF CHEMICAL PAPERS. Phenyltriazoles. 11. By ASTRID CLEVE (Ber., 1897,30,2433-2438). -A continuation of a former paper in which the preparation of phenyl- triazoles from Widman's 3-hydroxy-1-phenyl-1 : 2 : 4-triazoles by substi- tution with chlorine and subsequent reduction with hydriodic acid and red phosphorus, was described (Abstr., 1897, i, 172). ~~ c Cl=N 3-Cl~lo7.0-l-phen?lL5-prop?ll-l : 2 ; 4-triaxole, & ; CPra >NPii, is a toler- ably mobile oil boiling at 322*5', and having a sp. gr. = 1.1884 ; it does not yield salts with acids, but on distillation is partially converted into its Ibydvochloride which separates in glistening scales.1-Pl~enyZ-5-l~ropyl-1 : 2 : $-trimole, N: CPra >NPh, formed from the above by reduction, is a colourless oil boiling a t 285-286', and of sp. gr. = 1.0S27. The rnemwrochlom2e crystallises from alcohol in colourless prisms melting at 11 1-1 12'. ) >NPh, is a pale yellow oil boiling a t 327-438' (corr.), and of sp. gr. = 1.1547; on reduc- tion, it yields 1-phenyl-5-butyl-l : 2 :4-t&xoZe, an oil boiling a t 288-289', and yielding a picrate crystallising from dilute alcohol in needles melting at 136', and a nzercwrochloride consisting of colourless prisms melting at 116O. yH=N CC1:-N 3-Cl~loro-l-p~~enyl-5-but?/Z-l : 2 : 4-t&xoZe, &:c(C 4 9 3-C~i~o180-~-p~~en?/Z-~~~en~Zc~Zorethyl-l : 2 ; 4-t.l.iccxole, N N: ycl==== C (C,H,PhCl) >NPh, which i s produced when hydroxyphenylstyryltriazole is treated with phosphorus pen tachloride, consists of flat needles melting a t 112-1 13'; on reduction, i t yields l-pl~enyl-5-~~en~letl~?/l-l : 2 : 4-triaxole, YH==N >NPh, a colourless oil boiling a t 3 40-350') the N: C(C, H4 Ph) pZatinochloride forms yellowish-red crystals decomposing at 180-1 90'.1-~lzenyl-5-styry~-l : 2 : 4-triaxole, &:g(CH:CHph)>NPh, prepared from phenylphenyethyltriazole by treating it with bromine, separates from a mixture of light petrolenm and benzene in colourless prisms melting at 119-120O. The hydrochlode consists of colourless needles, the pZcdinocldos.icle of yellowish-red leaflets, whilst the picrate separates from alcohol in yellow prisms melting at 167'. l-Pi~enyl-5-phenyldi- dyornethyl-1 : 2 : 4-trinxole, which is an intermediate product in this re- action, forms silky needles melting a t 152'.Action of Hydrazine on Imido-ethers. By ADOLF PINNER (Annalen, 1897, 297, 221-271. Cumpare Abstr., 1897, i, 637, and 1894, i, 385).-The author discusses at some length the action of liydrazine derivatives on irnido-ethers. The experimental portion of the paper has been already published (Zoc. cit.). Action of Hydrazine on Imido-ethers. By ADOLF PINNER (AmnaZen, 1897, 298, 1-53. Compare foregoing abstract).-The CH:=N J. F. T. M. 0. F.ORGANIC! CHEMISTRY. 95 hydrochloride of paratolenylhydrazidine (Abstr., 1895, i, 136) forms lustrous, colourless prisms. l'olyltetrcmole is the compound described as paratolyltetrazotic acid (loc.cit.), obtained by the action of nitrous acid on paratolenylhydrazidine. [With C. GOBEL.]-T~~ compounds dealt with in this portion of the paper have been already described (Abstr., 1897, i, 639). [With JAXIES C o ~ ~ ~ ~ ~ . ] - D i i ~ y d r o x y b e n x ~ Z d i ~ ~ y d r o t e t y a ~ i n e , OH*CHPh*C<~H"~>C*CHPh*OH, is obtained by the action of hydrazine on the imido-ether prepared from mandelonitrile, it not having been found possible to produce the intermediate hydrazidine derivative ; it cryst'allises from alcohol in yellowish needles and melts a t 193'. Hydrochloric acid resolves the substance into benzaldehyde, formic acid, and hydrazine hydrochloride. The tetracetyl derivative forms colourless crystals and melts at 203'. Furfuryltetmxole is the name now given to furfuryltetrazotic acid (Abstr., 1895, i, 270).[With ALFRED SALOMON.]-T~~ compounds enumerated in this portion of the paper have been already described (Abstr., 1897, i, 6%). [With FELIX GRADENWITz.]-~n?'anitrOberEXil)lid0-et?~er, NH:C(C,H;NOJ*OEt, crystallises in stellar aggregates of needles and melts a t 78'. The hydrochloride forms large, lustrous prisms and melts at 197", yielding ethylic chloride and paranitrobenzamide ; water converts it into ammonium cbloride and ethylic paranitrobenzoate. The platinochloyide crystallises in lustrous, yellow needles, and melts at 141' ; the sulphute is unstable, and crystallises in needles. Paranitrobenzccmidine, NH:C(C6H;1JO,)*NH,, arises from the action of ammonia on the imido-ether ; it crystallises in needles, and melts at 215'. The hydrochloride forms highly refractive, rhombic needles.Acetoparanitro betwamide, NO,* C,H,* CO-NHAc, produced when the hydrochloride of the imido-ether is heated with sodium acetate and acetic anhydride, crystallises from alcohol in six-sided plates, and melts a t 165'. Fccl.ccnitrobenzenyllLyclraxidine, NH,* N:C(XH,)*CGH,* NO,, is ob- tained by the action of hydrazine on the imido-ether, and crystailises from alcohol in lustrous, reddish needles me1 ting at 195'. The yicrate crystallises in yellow needles, and melts a t 17'7". PccrcciLitro~)~enyltetrcLxoZe, NO,* C,H,* CGNHm?f, is produced by the N--N action of nitrous acid on the hydrazidine, and crystallises from alcohol in white needles; it melts and becomes red a t 219'.Diparanitrobenxeny lhydmxidine, NH,* C( C,H,*NO,): N*N :C(C,H,*NO,)*NH,, is obtained by the action of alcoholic hydrazine (1 mol.) on the imido- ether (1; mols.) and forms small, reddish, rhombic crystals insoluble in common solvents; it darkens at 230°, and melts at 257'. The hydrochlovide yields diparanitrophenyltriazole when heated ; the nitrute melts and effervesces at 143".96 ABSTRACTS OF CHEMICAL PAPERS. i s prepared by heating the hydrazidine with glacial acetic acid, and crystallises from alcohol in colourless needles melting a t 257". The acetyl derkative also forms colourless needles and melts at 237". Bipuraniti-opheny Zd~?~?ldroteti.ccxine, C6H4* '<N NH*N1x>C*C6H4* N NO,, is obtained from the imido-ether (1 mol.) and hydrazine (14 mols.) i~ somewhat less concentrated solution; it forms red needles soluble in alcohol, benzene, and acetone, and melts a t 215'. Dipuranitl.ophenyZtetrccxine, i s produced on oxidising the foregoing compound ; it crystnllises in flat, red needles, and melts a t 218".Action of a-Brorninated Acids and Ketones on Ortharnido- thiophenol. By OSKAR UNGER and G. GRAFF (Ber., 1897, 30, 2389-2399. Compare Abstr., 1897, i, 302).-Ketodihydrobenzo- parathiazine is also formed by the action of ethylic chloracetate on amidothiophenol. When treated with aqueous potash, glistening crystals of potcwium ortl~arnidop~enylthioglycollute, are formed. Nitrous acid yields a diazo-salt which yields a colouring matter with P-naphthol. The thjazine compound is converted by oxidation into a compou~zdwhichmelts indefinitely between 140' and 150" and yields a phen&dmxone, crystallishg in yellow needles and melt- ing a t 137'.When distillcd with zinc dust, the thiazine yields a small quantity of indole. , obtained by the action of a-bromopropionic acid on amidothiophenol, crystal- lises in concentrically grouped needles melting at 128'. The ethyb derivative is prepared by means of a-bromobutyric acid, and crystal- lises in porcelain white prisms melting a t 105-106', whilst ~-phenpt'- 31. 0. F. NH2* CGH,*S*CH,* COOK, 8-YHMe a-Methy Zketodihydro benxoparccthiccxine, C,H,<= H. co - ketodihyd~obenxopcirat?~iwxi~ze, C , H , < ~ ~ ~ ~ ~ h , is obtained from phenylbromacetic acid and crystallises in colourless needles melting at 204'. Ethylic a-chloracetacetate reacts with orthamidothiophenol to form a compound, C,,H,,NO,S, which crystallises in slender, golden yellow needles and melts a t 145"; it dissolves in hydrochloric acid, yielding a solution which, on treatment with sodium nitrite, forms phenylene diazosulphide.When heated with phenylhydrazine on the water bath, it yields diamidodiphen ylic bisulphide and 4-isonitroso- l-phenyl-3-methyl-5-pyrazolone. The condensation product is com- pletely decomposed by aqueous potash, yielding a compound which crystallises in colourless needles melting a t 159'. I t s composition has not yet been ascertained. Bromacetic bromide reacts with orthamidothiophenol to form a substance of the composition C,,H12N,S,, its molecular weight as determined by the boiling point method being about 272.It hasORGANIC CHEMISTRY. 97 decided basic properties, and yields a diazo-salt with sodium nitrite. As i t yields benzothiazole on oxidation with potassium permanganate, i t is probable t h a t the original compound has the constitution A. H. Synthesis of Heteroxanthine and Paraxanthine. By EMIL FISCHER (Bey., 1897, 30, 2400-2415. Compare Abstr., 1897, i, 641, and this vol., i, 48).-Theobromine is converted by a mixture of phosphorus oxychloride and pentachloride into 7-methyltrichloro- purine, but when i t is heated with the oxychloride alone, the ch1oi-i. nation does not proceed so far and 2 : 6-dichloro 7-methtJyurine, is produced ; this crystallises in slender, colourless needles, melting a t 199-200' (corr.), and is only sparingly soluble in water.Phosphorus pentachloride at 1'70" converts it into trichloromethylpurine. When i t is heated with hydrochloric acid (sp. gr. 1-19> a t 120-125", i t yields the I~?ytl~ochloi*ide of 7-methylxanthine, which crystnllises in yH* CO $*NhTe>CH, is c 0 *N€€.C --N almost coloui*less prisms. The free base identical with heteroxanthine ; this has no definite melting point, but softens at 360" and melts and deconiposes at 330"; when quite pure, i t dissolves in 142 parts of boiling water, the greater solu- bility found by Bondzyliski and Gottlieb (hbstr., 1895, i, 434) being probably due to the presence of a small amount of impurity. 2 : 6-I)i- chloro-7-methylpurine is converted by sodium etlioxide into a coiii- Y L pound which is most pro hably 2 - c ~ ~ Z o ~ ~ o ~ 6 - e t ~ o x ~ - 7 - m e t h ~ ~ z ~ r i r z e , : C( OEt)*s *NMe CCl:N--C---N >CH ; this dissolves in about 800 parts of boiling water and crystallises in slender needles which melt and decompose at about 240" ; hydrochloric acid convcrts i t into heteroxanthine.2-CI~Zoro-6-0~~-7-met?~y~urine is obtained by warming dichloromethylpurine with a n aqueous a1 kali and is best purified by means of the bnrizcnz salt, which crystallises in slender prisms. The compound, which crystallises in short prisms and com- mences to decompose at 310°, dissolves in about 150 parts of boil- ing water or 250 parts of boiling alcohol. %Chloro-B-oxy-l : 7-dinaethyZ- >CH, is prepared by the action of aqueous purine , I N Me - C: 0 # .N 11 e CC1: N C --N' potash and methylic iodide on c1ilor.oxymethylpiirine ; it dissolves in about 50 parts of boiling water and melts and decomposes at about 270" when rapidly heated.r;SMe*CO* g* IS Me I : 7-Dimethylxanthine 017- paraxanthiiie, N>CH, obtained by heating the foregoing compound GO *NH* C -- with hydroch1or.i~ acid of sp. gr. 1.19 at 125-1303, is identical with the paraxanthine isolated by Salomon from urine (Abstr., 1883, 601 ; 1886, 266) ; when treated with potash and metliylic iodide, i t is con- veyted into cttffeine. 2-Chloro-6-0~~-7-methylpurine, on reduction with hydriodic acid, yields98 ABSTRACTS OF CHEMICAL PAPERS. >CH, r K * CO *#*NMe 6-oxy-7 methy7pyine (7-methylhypoxanthine), CH:N-C --N which crystallises in slender, colourless needles, melts a t about 355' when rapidly heated, and is readily soluble in hydrochloric and sul- yhuric acids. The nitrate forms large, compact crystals ; the plutino- chloyide is readily soluble in hot water, the aui-ochloride more sparingly ; the silver salt is a fine, white, crystalline powder.On methylation, the base yields dirnethylhypoxanthine. 2 - Amido-6-oxy-7-.nzeth?/ll,urine NH - CO # N Me\ (7-methylguanine), I 2CH, is obt'ained by the action C(NH,) :N C= N of ammonia on chloroxymethylpurine, and crystallises in slender, colourless needles which decompose a t about 390'; it readily forms cryet,alline salts with acids, the hydrochloride, sulphute, nitrate, ylutino- chloride and aurochloyide having been prepared. It also dissolves in cold dilute alkalis, but is reprecipitated by carbonic anhydride. The sodium salt crystallises in very slender needles, whilst the silvey salt is an amorphous precipitate.When treated with hydrochloric acid and potassium chlorate, it yields guanidine. 2-itmido-6-0xy-l: '7-dimethyl- purine (1 : 7-dimethylguanine), ? Me'Co*~"Me>CH,obtained by the action of ammonia on chloroxydimethylpurine, separates from water in crystals which contain water of crystallisation, but become anhydrous at 100' and then melt a.t 343-345" (corr.). The nitrate crystallises in plates, the hydrochloride and sulphate in needles. The pkatinochloride and uurochloride are both sparingly soluble. Potassium chlorate and hydrochloric acid convert it into methylguanidine. NH,*C=N---C--N A. H. Non-nitrogenous Decomposition Products of Morphine.By EDUARD VONGERICHTEN (Belie., 1897, 30, 2439--2444).-Bromo- morphenol methyl ether, is formed when bromomethylmorphimethin- methyl iodide, is heated with concentrated sodium hydroxide solution under certain conditions, the yield being about 10 per cent. On oxidation with chromic acid, it does not yield a phenanthraquinone derivative, but is converted into a substance melting above 315' and crystallising from quinoline in glistening, reddish-brown needles having the same empirical formula as the original brominated ether. On reduction, it yields the corresponding nzorphenol, C,,H,O*OH, which crystallises from alcohol or ether in needles and melts at 135'. The acetate crystallises from alcohol and acetic acid in white needles. From these and other considerations, the author considers the formula of the compound C,,H,O to be either (?6H4*(?6H4 S)6H4.(?GH4 o r co - c=c----co J.F. T. Specific Rotatory Power of P-Glutin. By FRIEDRICH FRAMM (PJiiger's Amhiv., 1897, 68, 144-1 67).-/3-glutin is strongly lsevo- rotatory and shows no birotation. Numerous tables are given showing the effect on the rotation of concentration, temperature, and the influence of various reagents, salts, acids, and alkalis. W. D. H.ORGANIC CHEMISTRY. 99 Halogen Derivatives from Proteids. By F. GOWLAND HOPKINS and FRANCIS W. BROOK (J. Yh?/sioZ., 1897, 22, 184--197).-The halogens are eff ect,ive reagents for the precipitation of proteids, the present paper relating t o the precipitates obtained from diluted egg white. The substances obtained, which resemble proteids in being indif- fusible and of high molecular weight, give the xanthoproteic and violet biuret reactions; after gastric digestion, they give a pink biuret reaction. They are soluble in dilute alkaline solutions, from which they are precipitable by acetic acid.They differ from proteids in not giving Millon’s reaction, and in being soluble in absolute alcohol ; the iodine derivative is least soluble in alcohol. From their alcoholic solutions, they are precipitated by the addition of ether, the substance thus obtained containing a higher percentage of halogen than that pre- cipitated by acid from an alkaline solution. Thus : I’rodnct after treatment with sodiuui carbonate ................................. Product precipitated from alcoholic solutioii .................................... Chlorine per cent. (3.6 and) 1-89 6-07 Bromine 1 Jodine per cent. per cent. 3.92 , 6.28 I 14-89 1 1 Taking the lower series, the bromine percentage is very nearly the mean of the chlorine and iodine percentages, in accordance with the relation that holds between the atomic weights of the halogens. It is believed that, after treatment with alkalis, one has to deal with substi- tuted bromine, whereas after treatment with alcohol there is additive bromine as well. Since aromatic substances like tyrosine no longer give Millon’s reaction when halogen has entered the ring, it seems probable that, in these derivatives of proteid, the halogen has entered an aromatic nucleus in the proteid molecule. The halogen derivatives of proteid yield no trace of lead sulphide when heated with alkaline solutions of lead salts; the sulphur is still all present, but probably in a sulphonic or other oxidised group. Efforts to obtain the original proteid from the halogen derivatives have hitherto proved fruitless. W. D. H. The Biuret Reaction of Albumin. By HUGO SCRIFF (Chenz. Zeit., 1897, 21, 55--56).-1n answer to Loew’s criticism (Chem. Zeit., 1896, 20, lOOO), that the anhydride of aspartic acid gives the biuret reaction, whereas, according to the author’s theory, it should not do so, the author points out that the composition of this anhydride is unknown, since i t is derived from 4 to 8 molecules of aspartic acid. It is characteristic, however, that aspartic acid does not give this reaction, whilst asparagine gives a reaction very similar to the biuret reaction, the coloration being only a little more bluish-violet. The product obtained by the action of formaldehyde and hydrochloric acid on albumin, which is insoluble in water and alkalis, gives the biuret reaction, for fragments of it placed in the almost colourless solution100 ABSTRACTS OF CHEMICAL PAPERS. become reddish-violet after a time. Moreover, Blum’s solution of albumin (hbstr., 1896, 658), prepared by the action of formaldehyde alone, although i t does not coagulate on heating, also gives this reaction. If this substance is a methylene-albumin, then, according to the author, it does not contain the symmetrical group, 1gE>CH2, for derivatives of biuret, oxaniide, and malonamide in which two hydrogen atoms of each amido-group are symmetrically substituted do not give the biuret reaction. E. W. W. Precipitation of Caseinogen, a Simple Means of Estimating Acidity. By PAUL GRUTZNER (P’iiger’s A~chiv., 1897,68, 168-1’75). -When milk is added gradually to various acids, the precipitate which first forms redissolves on shaking it up. The first appearance of a permanent precipitate is a measure of the strength and acidity of the acid; the stronger acids need much more milk for this purpose, and precipitate more caseinogen than the weaker ones, thus a molecule of hydrochloric acid in dilute aqueous solution precipitates five or six times as much caseinogen as a molecule of acetic acid. W. D. H. Decomposition Products of Carniferrin. By PAUL BALKE (Zeit. physiol. CILem., 1896, 22, 248-264. Compare Siegfried, Abstr., 1895, i, 76 and 313).--It is shown that Siegfried’s carnic acid is identical with ICiiline’s antipeptone, considerable quantities of which the author prepared by a method differing somewhat from t h a t described by Kuhne ; both compounds give similar numbers 011 analysis and yield identical saltas. By the oxidation of barium carnate (1 equivalent) with barium permanganate (1 equivalent) at temperatures below 5O, a new acid, oxyccwnic mid, C30H41N9015, is obtained ; it is best purified by evaporating its aqueous solution t o a syrup, then pouring it into alcohol, and washing the precipitate successively with alcohol and with ether. The zinc salt, C,oH,9N,015Zn ; barium salt, C,oH,,N~015Bit, and silver salt, C30H3,N901,Ag, + 2H,O, are described. ‘I’he uczd itself is a snow-white, hygroscopic powder, readily soluble in water, sparingly in alcohol, and insoluble in ether. It reddens blue litmus, is capable of decomposing carbonates, and gives precipitates with picric, phospho- tungstic, and tannic acids, but not with lead acetate, acetic acid, or potassium ferrocyanide. Siegfried has shown that carniferrin obtained from milk has the same percentage composition as that obtained from meat extract, but that when hydrolysed with barium hydroxide it yields, besides lactic and succinic acids, a n acid closely related to carnie acid, which he bermed -orylic acid. According to the author, orylic acid has the com- position Cl,H,8N408. When dry, it is a yellowish-white powder, which is extremely hpgroscopir: and, when freshly prepared, readily soluble in water ; it is sparingly soluble in alcohol but insoluble in ether, and is a strong dibasic acid, resembling carnie acid. The zinc salt, C1SH26N40SZn, andsilver salt, ClsH,5N408hg, + 3H,q, are described. When heated with hydrochloric acid at 130°, orylic acid yields leucine :is one of its decomposition products. J. J. S.