7 3 Organic Chemistry. The Wax of Bacillariacee and its Connection with Petroleum. By GUSTAV KRAMER and ADOLF SPILKEE (Bey., 1899, 32, 2940--2959).-Bacillariace~! (diatoms) are known to contain drops of oil distributed i n the plasma, and from peat, in which diatoms occur largely, 1.5-4 per cent. of a wax can be extracted which contains 10-11 per cent. of sulphur. I n the Uckermark, to the west of Stettin, the bed, some 23 feet in thickness, of a lake, which was drained long ago, consists chiefly of diatoms, and from i t a wax can be extracted. This melts at 50-70°, resembles ozokerite in appearance, contains C, '73.5 ; H, 11.2 ; S, 1.0, and ash, 2.4 per cent., from which it may be concluded that the wax contains oxygen and consists of esters of organic acids. Fuming nitric acid does not attack the wax in the cold, but dissolves 38 per cent.on heating ; from the residue, lekene, which occurs in ozokerite (Beilstein and Wiegand, Abstr., 1883, 1073), can be isolated. The latter contains only 0.15 per cent. of sulphur, however ; only traces of i t are hydrolysed by alcoholic potash, and when it is distilled no water is formed and the gas evolved contains no oxides of carbon and but little hydrogen sulphide. Of the wax from the lake silt, on the other hand, about 10 per cent. undergoes hydrolysis ; and on distillation of the peat-wax, water is formed and the gas evolved contains 10 per cent. of hydrogen sulphide together with carbon dioxide and monoxide. When ozokerite is distilled under a pressure of 20-25 atmos., the gas evolved consists of methane and olefines, along with traces of hydrogen sulphide and carbon dioxide; the gas obtained from the silt-wax in similar circumstances contains hydrogen sulphide and carbon dioxide and mon- oxide, and that from carnauba- and Japan-wax contains both oxides of carbon.I n all cases, a large part of the distillate boils a t 130-290°, and this fraction has the character of the paraffins ; its composition is C, 84-4-85.0, and H, 15.1 per cent., and its molecular weight is 149-169 determined cryoscopically in benzene solution (C,,H,, requires C, 84.7; H, 15.3; molecular weight, 156). A similar fraction from petroleum (from the Tegernsee) had a like composition. It is further found that the composition of the strata overlying the ozokerite deposits of Eastern Galicia and the petroleum beds of the Tegernsee contain the same mineral constituents as the lake silt.The following theory of the origin of petroleum is then developed. Lakes became filled up in the process of time with a growth of diatoms ; over this growth other deposits were formed subsequently. The decay of the diatoms (which takes place very slowly) gave rise to ammonium carbonate, which hydrolysed the wax present ; from the resulting acids, carbon dioxide and monoxide and water were eliminated, and ozokerite formed. Where the pressure was small and the temperature low, this was converted further into a comparatively low boiling petroleum ; under greater pressure and higher temperature, the sulphur present These waxes much resemble ozokerite. VOL.LXXVIII. i. 9744 ABSTRACTS OF CHEMICAL PAPERS. also exerting an influence, a petroleum was formed which contained a large proportion OE viscid, high-boiling substances (probably formed by polymerisation of olefines); more extended action of the sulphur, and of atmospheric oxygen, gave rise to a petroleum containing much asphalt. Generally speaking, the petroleum would be absorbed by the sandy bed of the lake; occasionally it might be absorbed by a calcareous bed, a deposit of asphalt being thus formed. C. F. B. Heptane contained in Grosny Naphtha. By K. W. CHARIT- SCHKOFF (Chern. Centr., 1899, ii, 474; from J. RUN. Chern. Soc., 1899, 31, 552-!554).-The benzene boiling a t 84-100°, obtained from the naphtha of Grosny, contains an isoheptane, C7H,,, which boils at 90.5-91*5", and has a sp.gr. 0.1158 a t 15". This naphtha only con- tains a very small amount of normal heptane. The interpretation of the curves representing relationships of boiling point and specific gravity is discussed in the original paper, the author inclining t o Aschan's, rather than to Markownikoff's, views. E. W. W. Action of Acetylene on Oxides of Copper. By FRANK A. G o o c ~ and DE FOREST BALDWIN (Amer. J. Xci., 1899, [ iv], 8, 354-358). Compare Erdmann and Kothner, Abstr., 1899, i, 21).-Several errors in calculation are pointed out in Erdmann and Kothner's communica- tion. The experiments have been repeated, and the conclusion arrived at is that Erdmann and Kothner's '' Kupferacetylen " is nothing lass than a hydrocarbon or hydrocarbons mixed with copper or an oxide of copper. The amount of copper found varies considerably (1.54 to 24.21 per cent,) with the conditions of the experiment.When cuprous oxide is employed, a temperature of 225" is the most favourable; similar results may be obtained with cupric oxide, but copper itself is not acted on until much higher temperatures are reached, Oxide of silver is acted on at the ordinary temperature, and, as a rule, an explosion occurs. NoTE.-The same conclusion as t o the nature of Erdmann and Kothner's compound has been arrived at by Alexander (Abstr., 1899, i, 843). J. J. S. J. J. S. Preparation of Tetrachloromethane. By E. SERRA (Gaxxetta, 1899, 29, ii, 353--354).--Details are given of the method employed for the preparation of tetrachloromethane free from carbon disulphide and from chloroform, which are very difficult to entirely remove.T. H. P. Isomeric Compounds, C,H804N,, from Acetylmethylnitrolic Acid. By CARL STEFFENS (Annalen, 1899, 309, 241-253).-Acetyl- methylnitrolic acid, COMe*C(NOH)*NO,, obtained by oxidising acetone with nitric acid, yields two compounds having the empirical formula C,H,04N, ; one melts at 191", and is produced by converting acetyl- methylnitrolic acid into nitromethylglyoxime, and heating the latter with sodium hydrogen carbonate (Behrend and Schmitz, Abstr., 1894, i, log), whilst the other, melting at 140°, is derived by the agency of hydroxylamine from the product of heating acetylmet hylnitrolic acidORGANIC CHEMISTRY. 75 (Behrend and Tryller, Abstr., 1895, i, 201). The author has attempted to establish the constitution of these two substances.The derivative melting at 191', referred to as Schmitz's com- pound, probably has the constitution represented by the formula N O H : C M e * C ~ ~ : ~ ~ C * C M e : N O H . The hydrochloride is decomposed by hot water, yielding the original substance, which dissolves in hot hydrochloric acid, liberating carbon dioxide ; the remaining products are a-isonitrosopropionic acid, ammonia, hydroxylamine, and acetic acid. The diacetyl derivative crystallises from alcohol in needles and melts at 141" ; the dibenxoyl derivative becomes brown at 200' and melts at 220-225O, when it decomposes. The compound dissolves in alkali (2 mols.), and is reprecipitated by acids from a freshly prepared solution, but after an interval, acids do not, yield a precipitate; it immediately reduces potassium permanganate.The isomeride called Tryller's compound may have the constitution g-% . The hydrochloride readily yields N*O*O*N the original substance, which gives rise to carbon dioxide, oxalic acid, ammonia, hydroxylamine, and acetic acid when treated with boiling acids; there is produced also a small quantity of a volatile ketone, probably the ketone of which Tryller's compound is the dioxime. The dibsnxoyl derivative crystallises in slender, white needles and melts at 1555-156.5". The anhydyide, C,H,O,N,, obtained by acidifying a solution in caustic soda which has been boiled for some time, crystallises from alcohol in lustrous, yellowish leaflets and melts at 188--290", becoming brown a t 150'.M. 0. F. Phosphoric Esters. By JACQUES CAVALIER (Ann. Chiin. Phys., 1899, [vii], 18, 449-507. Compare Abstr., 1894, i, 484; 1895, i, 638; 1896, ii, 590; 1597, i, 310; 1898, i, 616, ii, 499; 1899, i, 558, ii, 13,55).-A detailed account of work already published. G. T. M. Manufacture of Glycerophosphate. By MARCEL GU~DRAS (Clzem. Centr., 1899, ii, 626 ; from Mon. Xci., [iv], 13, 11,577-580). -Commercial glycerophosphate, CaPO,. O*C,H,(OH)2, prepared by heating phosphoric acid with glycerol for a day at 150" and then for 3 days at 115-1 25", and treating the glycerophosphoric acid with milk of lime, is alkaline towards litmus, but neutral to phenolphthalein, dissolves in about 25 parts of water, leaving a small quantity of in- soluble calcium phosphate, and is precipitated from its aqueous solu- tion by heating.Boiling alcohol usually extracts some glycerol and phosphoric acid. Sodium and potassium glycerophosphates are syrupy liquids. The magnesium salt is a powder, and has properties similar to those of the calcium salt. The iron salt, prepared by digesting crude glyceropbosphoric acid with iron dust below 60°, crystallises in leaflets which have a golden lustre. Quinine glycerophosphate, C8H7O2* 0 *PO(OH),,(C2,H,,0,N,), + 4H20, is slightly soluble in water, more so in alcohol, and may be used as a substitute for quinine sulphate. E. W. W. 9 276 AI3STRACTS OF CHEMICAL PAPERS. Esters of Tungstic Acid. By EDGAR F. SMITH and CLAUDE DUGAN (J. Amer. Chem. Soc., 1899, 21, 1016-1017. Compare Goessmann, Annalen, 1857, 101, 218 ; Maly, ibid., 1866, 139, 240).- When Maly's method is employed forthe preparation of estersof tungstic acid, the products obtained consist of a mixture of hydrated tungstic acid and an incompletely esterified product : for example, with tungsten oxy- chloride and isobutyl alcohol, a product, 3 WO,, 2H,O + WOCl,(OC,H,),, was obtained, which was suluble in dry ether, but was reprecipitated on the addition of pure ethyl alcohol. J.J. S. Action of Water on certain Fatty Acids. By EDWIN DE BARR (Amer. Chem. J., 1899, 22, 333--349).-The author has studied the rate of interaction of water with certain halogenated fatty acids at 150°, 3 mols. of water being used for each halogen atom present. Tables of values are given and curves plotted, which show the rate of displacement of the halogen atoms from y-chlorobutyric, P-chloropropionic, trichloroacetic, P-chlorobutyric, chloroacetic, di- chloroacetic, a-chloropropionic, a-bromopropionic, a-bromobutyric, and a-chlorobutyric acids; the relative ease with which the halogen is removed from the various acids is given by the order in which these are named.This order is, except in the cases of mono-, di-, and tri- chloroacetic acids, not the same as that of the affinity constauts. Most of the acids begin to undergo secondary change before the dis- placement of the halogen is complete ; the relative stability of the compounds at 150' under pressure and in presence of hydrogen chloride appears to be in the order, a-bromopropionic (7.06), a-chlorobutyric (7.50), a-brornobutyric (9.25), a-chloropropionic (1 1*41), dichloro- acetic (1 7*!'6), P-chlorobutyric (37.38), chloroacetic (47.1 l), P-chloro- propionic (50*49), trichloroacetic (1 OO*OO), and y-chlorobutyric acids (lOO.OO), the numbers attached to each acid showing the percentage of halogen displaced befure decomposition begins.On comparing this list with the foregoing, it appears that those acids which are most stable react the most rapidly with water, whilst those which are least stable react most slowly. It appears, moreover, that with the a-acids containing the same halogen, the rate of displacement of the latter diminishes in passing from acetic acid t o its higher homologues ; the same holds true with the @-acids, and a similar law regulates the total amount of transformation occurring before decomposition begins.It is especially noteworthy t h a t the further a halogen atom is removed from the carboxyl group i n the same acid, the more easily is i t displaced under the influence of water; thus, the amount of halogen replaced after half a n hour is 4.42 per cent. of the total in the case of a-chloro-, and 41.5 per cent, in the case of P-chloro-propionic acid. P-Chloropropionic acid is best prepared by the action of chlorine on P-iodopropionic acid, and melts at 61", not at 35.5" to 58" a s has formerly been stated; it boils a t 204". P-Chlorobutyric acid, pre- pared by saturating a n ethereal solution of crotonic acid with hydrogen chloride at 0", and subsequently leaving it in a sealed tube for 24 hours at t h e ordinary temperature, melts at 16-16*5", boils at 116" under 22 mm.pressure, and is entirely free from a-acid. y-Chloro-ORGANIC CHEMISTRY. 77 butyric acid, prepared similarly from trimethylenecarboxylic acid, melts at 12" and boils a t 196" under 22 mm. pressure. Electrolytic Oxidation of Succinic Acid. By CHARLES H. CLARKE and EDUAR F. SMITE (L Arne?.. Chem. ~ o c . , 1899,21,967-972). -The electrolytic oxidation of succinic acid in solutions containing known quantities of sodium hydroxide and of alcohol, has been studied. A divided cell was employed and a current density of from 0.034 to 1.55 amperes per 100 sq cm. of anode surface. The products found were tartaric, oxalic, and carbonic acids, oxygen, carbon monoxide, ethylene, and methane, together with some aromatic substances. A colouring matter, soluble in ether and melting a t 17S0, has also been isolated. J.J. S. By OTTO RUFF and GERHARD OLLENDORFF (Rer., 1899, 32, 3234-3237).-Phenylbenzyl- hydrazine is better adapted for the isolation of sugars than phenyl- hydrazine itself, because of the ready formation and insoluble character of the hydrazones produced, and this substance has already been em- ployed by Lobry de Bruyn and Alberda van Ekenstein (Abstr., 1896, i , 588 ; 1897, i, 41). l-Xylosep~ienylbenx~Z~y~?~c~x~nd melts a t 99' (corr.), and dissolves in about 1000 parts of water. d-Arabinose- plzenyZbenxylhyd.r*axone me1 t s at 174" (corr.), and is almost insoluble in water. The corresponding hydrazone of dextrose melts a t 165" (corr.), and not a t 150" as st:ited by these authors. The sugars are best regenerated from these hydrazones by treatment with form- aldehyde, removal of the formaldehydephenylbenzylhydrazone by ether, and repeated evaporation of the solution to remove the excess of formaldehyde.Fo~mu Zdeh y d eplt eny 1 benxy lhhy d m x o n e cry s t alli ses in white needles melting a t 41". A. H. Isomaltose. By HENRI POTTEVIN (Ann. de I'Inst. Pasteur, 1899, 13, 796--800).--From a solution of pure maltose and a non-reducing dextrin, the author has prepared an osazone which melts at 154" and crystallises in tufts of very slender needles. From this fact, and a consideration of previous work, he concludes that Lintner's iso- maltose is a mixture of maltose and a dextrin (compare Ling and Baker, Trans., 1895,67, 704,739 ; 1897,71,511 ; Brown and Morris, Trans., 1895,67, 709).By ARMINIUS BAU (Cliern. Centr., 1899, ii, 526 ; from Woch. Bmuerei, 16, 397-400).--Melibiose was prepared by fermenting a solution of melitriose by means of a pure culture of a top-fermenting yeast. After decolorising the solution of the pro- duct with animal charcoal, i t was evaporated and the melibiose precipitated from the residual syrup after filtering, by means of ether and purified by conversion into the barium compound, &c. Melibiose forms triclinic crystals containing 2H,O! is not hygroscopic, and is not changed by exposure to the air; it is easily soluble in water or methyl alcohol, and, like its aqueous solution, decomposes at 80'. It sinters a t 82-83', partially melts at 84-85', and has a specific rota- tory power [ aID + 129.38' a t 20' ; freshly prepared solutions give a W.A. D. Separation and Purification of Sugars. H. R. LE 8. Crystallised Melibiose.7s ABSTRACTS OF CREMTCAL PAPERS. slightly lower value for the last constant. Its power of reducing Fehling's solution, calculated on the dry substance, is only 92-95 per cent. as much as that of maltose, and it is neither hydrolysed nor fermented by top-yeasts, but is decomposed by bottom-yeasts, forming dextrose and d-galactose, which are completely fermented. E. w. w. Rhamninose. By CHARLES TANRET and GEORGES TANRET (Compt. rend., 1899, 129, 725-738).--Tt has been previously shown that xanthorhamnin, the glucoside of Rhamnus infectoria, is converted by the action of dilute acids into a mixture of rhamnetin, rhamnose, and galactose, the las t-named compounds being themselves the products of hydrolysis of a n intermediate saccharose, for which the name &am- ninose is now proposed. Rhamninose, which is best obtained by the action of the ferment rhamnase, or, as i t is more properly termed, rhamninase, on xanthorhamnin a t 70°, is slowly hydrolysed by dilute acids into two mols.of rhamnose and one of galactose. It has a slightly sweet taste, and is soluble in all proportions in water, and very soluble in strong alcohol. It has a rotatory power [a], -41°, and melts and slowly decomposes a t 140'; it has not been obtained crystalline. Rharnninose has one-third the reducing power of dex- trose. Ordinary yeast, invertase, emulsin, and the ferments of Aspergillus have no action on it.No insoluble osazone or phenylhydr- azone could be obtained from it. When treated with sodium amalgam in the cold, rhamninose takes up two atoms of hydrogen and is con- verted into a new sugar, rhamninite, C,,H,,O,,, which has a rotatory power [a], - 57", and yields rhamnose and dulcitol on hydrolysis. Rhamninose is oxidised by nitric acid to mucic and galactonic acids, and by bromine to rhamninot~ionic acid, ClsH32015. This acid is monobasic and bears the same relation to rhamninose that lactobionic acid does to lactose. It has a rotatory power [a], - 94O, but does not reduce Fehling's solution ; both it and its salts are amorphous. On hydrolysis, it yields two mols. of rhamnose and one of gslac- tonic acid.N. L. By WIKTOR SYNIEWSKI (Alznalen, lE99, 309, 282-315. Compare Abst,r., 1898, i, 551).-From experiments with potato starch, the author draws the following conclusions : 1. Potato starch granules consist of an individual substance having the empirical formula C,H,,O,. 2. Hydrolysis of potato starch can proceed in two wags, namely, carbinol-hydrolysis, in which addition of water t o the anhydride of two carbinol groups takes place, and carbon yl-hydrolysis, in which at least one of the two groups forming the anhydride is a carbonyl radicle. 3. The compound obtained from potato starch by the action of boiling water under atmospheric or increased pressures, caustic potash, or sodium peroxide, is the result of carbinol-hydrolysis; it does not reduce Fehling's solution. 4.The simplest product of carbinol-hydrolysis is amylogen, C,,H,,04,. The molecules of starch, and of all products of carbinol-hydrolysis standing between starch and arnylogen, consist of a number of amyl- Constitution of Starch,0 Ra AN I C C E l EM I S T R 1'. 79 agen molecules associated in the form of anhydrides by elimination of water from carbinol groups. 5. The composition of all such compounds may be expressed by the general formula (C54H96048)n -(3n - x)H20, in which n is unknown, and 2 is variable from 0 to 3n. 6. Amylogen consists of three maltose residues, combined with a dextrin containing 18 atoms of carbon. The dextrin is composed of three glucose residues, of which two are in the form of an isomaltose residue. 7. The first stage in the hydrolysis of amylogen is the separation of the maltose molecules from one another and from the dextrin; further action of malt extract on the latter resolves it into glucose and isomaltose, which finally yields a further quantity of glucose, 8.Diastatic hydrolysis of amylogen gives rise to intermediate pro- ducts, the changes being represented by the following equations : C18H,7012i 03(~12H231311)3 + 2H20 = Am ylogen. C18H30014: 02(c12H23011)2 + C12H22011 + H'2°' Dextrin-residue I. Maltose. C18H30014: 02(c12H23011)2 + H2° = C18H31015* 0(C12H23011) + C12H22011 -k H2°' Dextrin-residue 11. Maltose. C18H31015* O ( C l , H 2 , O , l ) + H 2 O = Cl8H32O1, + C12H2201, + H2O. Dextrin- Maltose. residue 111. C18H32016 + H2° = C12H22011 + C6H120,' Isomaltose. Pextrose.C,,H2,011 + H20 = 2C6HI2O6. Dextrose. 9. Diastatic decomposition of those products of carbinol-hydrolysis of starch which contain many amylogen molecules yields a large number of dextrinous compounds, of which those containing the dextrin-residues I, 11, and 111 are typical. The author uses the name dextrin for all products of starch hydro- lysis excepting sugars, and indicates as amylodextrins those which proceed from starch by carbinol-hydro1 ysis, and are therefore in- different towards Fehling's solution, and develop the familiar starch blue with a solution of iodine in potassium iodide ; the residual dex- trin produced from arnylodextrin by eliminating all the maltose is called '' Grenzdextrin." Dextrins between the latter and amylo- dextrins are called maltodextrins, and those derived from (' Grenx- dextrin " by withdrawing dextrose residues are called glucodextrins. M.0. F. Preparation of Starch Solutions and Separation of Starch Granules froin such Solutions. By HERMANN RODEWALD and A. KATTEIN (Chern. Centr., 1899, ii, 419 ; from Sitzungsbes*. Akad. FViss. Berlin, 24, 628--630).--When a solution of iodine in potassium iodideSO AESTRACTS OF CHEMICAL PAPERS. is poured over potato, wheat, or rice starch and the mixture (which should contain 15 parts of iodine and 200-300 of water for every 100 of starch) heated for 15 minutes a t 130°, a greenish-brown liquid is formed which consists mainly of excess of iodine solution with very small quantities of starch iodide and some sugar. The starch iodide grains, when examined under the microscope, appear to have been changed, and are soluble in water.The starch iodide may be separated by dialysing, and the blue solution so obtained forms a clear fi1- trate. This solution contains about 2 per cent. of the iodide and an amount of iodine corresponding with 14.3-14.85 per cent. of iodine in the iodide. When the solution is evaporated over a naked flame, the starch iodide separates and iodine is liberated ; the latter may be removed by treatment with steam, and a clear or very slightly turbid solution of starch is then obtained. When the solution is slowly cooled, a white precipitate is formed, and this, when examined under the microscope, appears t o consist of almost spherical starch granules. A similar precipitate is formed by all varieties of starch.The filtrate contains starch and gives an intense blue coloration with iodine; the blue compound may be separated by adding potassium iodide, The starch granules which separate from the solution also give a blue coloration with iodine, and after drying are insoluble in cold water, and are only gelatinised with difficulty by boiling ma ter. Potass- ium hydroxide also reduces the granules to paste. E. W. W. Saccharification of Starch, By HENRI POTTEVIN (Ann. de Z’lnst. Pasteur, 13, 1899, 665-688).-The dextrins obtained from starch by the action of amylase may be divided into three groups. (1) Achroo- dextrins, (2) amylodextrins, and (3) erythrodextrins. With the first, starch produces no coloration, but with the second, a blue, and with the third a red coloration is obbained.No red coloration is produced when starch is added to a mixture of achroodextrin and amylodextrin, so that Solomon’s statement that erythrodextrins do not exist, but are mixtures of achroodextrins and amylodextrins is erroneous. Musculus’ statement that amylodextrins in concentrated solutions give a blue coloration with starch and a red coloration in dilute solutions is also erroneous, because, whatever the dilution, a blue colour is always produced. Amylodextrin itself is not a single substance, for by careful precipitation with alcohol two dextrins have been obtained from it. The first, a-amylodextrin, gives opalescent solutions, which on warming become somewhat viscous, but on cooling again become opalescent. Its blue compound with iodine is readily precipitated by a 1 per cent.solution of sodium chloride. The second, or /3-amylodextrin, gives solutions which are viscous in the cold, and i t s compound with iodine is not precipitated by even a 20 per cent. solution of sodium chloride. The formation of dextrin from starch by the action of amylase is quite independent and distinct from the formation of maltose from the dextrin, for a solution may be prepared in which the formation of dextrin is still going on whilst that of maltose has completely stopped. When amylase acts on starch, the rate of saccharification rapidlyORGANIC CHEMISTRY 81 decreases. This is due to the fact that the starch granules are not all of the same size, the larger ones being readily attacked by amylase, whereas the smaller are only attacked with difficulty. H.R. LE S. Maltodextrin. By H.ENRI POTTEVIN (Ann. de I'lnst. Pastew, 1899, 13, 728-734).-The method of fermentation adopted by Brown and Morris to show that maltodextrin is not fermentable with yeast, is here objected to, since no precautions were taken to render the fer- menting liquid aseptic, or to prevent the subsequent introduction of microbes during the fermentation. Using carefully sterilised and aseptic solutions, the author confirms the statement of Brown and Morris that maltodextrin is not fermentable, but points out that this is no evidence that maltodextrin is not a mixture, because a mixture can be made of pure maltose and a suitable dextrin, which, like malto- dextrin, is not fermentable with yeast.Dextrins soluble in 70 per cent. alcohol retard the fermentation of maltose much more than those which are soluble in more dilute alcohol solutions. By careful frac- tional precipitation of a solution of maltodextrin by means of alcoholic solutions of varying strengths, precipitates of different composition are obtained, those obtained by precipitation with 58 per cent. alcohol consisting of 20 per cent. of maltose and 80 per cent. of dextrin, whereas with 94 per cent. alcohol the precipitate contains 70 per cent. of maltose and 30 per cent. of dextrin. A mixture of pure maltose and a dextrin (soluble in 70 per cent. alcohol) dialyses in exactly the same way as a solution of maltodextrin. The mere fact that maltodextrin dialyses as a whole is therefore no proof that i t is a single substance.Those dextrins soluble in dilute alcohol dialyse more quickly than Preparation and Estimation of Glycogen. By ARMAND GAUTIER (Compt. rend., 1899, 129, 701 -705).-The process described, which serves for both the preparation and estimation of glycogen, is based on the fact that the nitrogenous substances with which glycogen is associated are completely precipitated by mercuric acetate in neutral solution. The well-bruised liver, muscle, or other material is thoroughly extracted with boiling water (addition of acid or alkali serves no useful purpose) and the liquid concentrated by evaporation, mixed with a little potassium acetate and a slight excess of mercuric acetate, filtered, and poured into an equal volume of 85 per cent. alcohol.The precipitated glycogen is purified by repeated solution in water and reprecipitation with alcohol, washed with a mixture of alcohol and ether, and finally dried a t 110-120°. Glycogen is thus obtained as a perfectly homogeneous substance having the composi- tion (C6Hlo05)n, It is not truly soluble in water, since it is more or less completely separated from the liquid by filtration. I n the presence of a trace of salts, it is wholly insoluble in 36 per cent. alcohol. Glycogen is not hydrolysed by heating a t looo with 3 per cent. potassium hydroxide solution or with 5 per cent. acetic acid, but when heated with 5-6 per cent. mineral acid a t 115-120", it is converted into a mixture of sugars having a reducing power slightly those which are only soluble in strong alcohol.H. R. L E S.82 ARSTRACTS OF CHEMICAL PAPERS. greater than that of dextrose. Glycogen from t h e human liver yields products having a notably higher reducing power than those obtained from rabbit’s liver, and from this and other considerations i t is concluded that different varieties of glycogen are contained in the different organs of the same animal and also in the same organs of different animals. N. L. Composition of the Gum of Grevillea Robusta. By REBER and PUAUX (J. Pharm., 1899, [vi], 10, 398--400).-The fresh gum is soft, and of a whitish colour, but on keeping it becomes hard, and of a yellowish, and often of a reddish, colour. It is odourless and pos- sesses a n astringent taste, It entirely dissolves in water, from which it is precipitated by 95 per cent.alcohol, and by basic lead acetate, after the addition of ammonia, until slightly alkaline. Its aqueous solution reduces Fehling’s solution, and when warmed with ferric chloride, its colour deepens, but no precipitate is produced. When the gum is treated with mineral acids, galact,ose and arabinose are pro- duced. A complete analysis of the gum is given. H. R. LE s. Nitroacetone. By AD. LUCAS (Bey., 1899, 32, 3179-3182. Compare Abstr., 1899, i, 401 and 433).-When silver nitrite is agitated for 24 hours with a dilute ethereal solution of iodoacetone, the nitroacetone produced remains insoluble, whilst the impurities dissolve ; the nitroacetone, separated and dissolved in a larger quantity of ether, crystallises from the concentrated solution in well defined plates, melts at 49O, is soluble in water and alcohol, and crystallises from benzene in needles.Cry oscopic determinations of its molecular weight show that this corresponds with the simple formula C,H,?,N. When dissolved in water, it reacts as a monobasic acid, and determina- tions of its electrical conductivity indicate that its strength is half that of acetic acid, the value of K for nitroacetone being 0.001026. Aminoacetone (Abstr., 1 S93,734) is obtained by reducing nitroacetone, and this result indicates t h a t the latter is a nitro-compound and not a nitrite. In aqueous solutions, both nitroacetophenone and nitroacetone behave like isonitroso-derivatives (Hantzsch and Veit, Abstr., 1899, i, 401), but the latter substauce does not appear to have any close con- nection with the compound described as a nitroacetone by Henry (Abstr., 1899, i, 475).When treated with phenylhydrazine, nitro- acetone yields a n oily phenyllkydyuxone. G. T. M. y-Amino-PP-dimethylbutane. By WASSILY SOLONINA (Chem. Centr., 1899, ii, 474; from J. Russ. CJzem. Xoc., 1899, 31, 541-542). --y-Aniino-~,&dimetJ~yZbutc~,ne, prepared by reducing a boiling alcoholic solution of pinacoline oxime, CMe,*CMe:NOH, with sodium, is a mobile liquid, has the odour of ammonia, boils at 103-104°, and is very slightly soluble in water. At - 20°, it forms a crystalline mass. The hydrochloride forms long needles, and the plutinichloride is prys- talline ; the aurichloride cryst’allises from dilute alcohol in long, pale yellow needles, and melts at 1 7 8 O .By the action of benzenesulphonic chloride on aminodimethylbutane dissolved in ether, the compound C,N,,*NH+3O2l’h is formed which cryst:tllises from aqueous alcoholORGANIC CHEMISTRY. 83 in thick plates, melts a t 96.5", and is insoluble in water, but easily SO in alcohol, ether, or benzene. By THOMAS CLARKE (J. Amey. Chem. Soc., 1899, 21, 1027-1031. Compare Cahours and Pelouse, Jahwsber., 1863,528 ; Schorlemmer, AnnaZen, 1863, 12'7, 318)-When P-heptyl bromide (Abstr., 1881, 82) is heated: with an excess of alcoholic ammonia a t 1 00", the products are primary P-heptylamine hydrobromide, heptylene, and ammonium bromide. The hydrobyomide, CH3*[CH,j4*CHMe*NH,HBr, crystallises from a mixture of benzene and light petroleum in slender, silky needles melting a t 163', and dissolves readily in alcohol, water, or benzene, and also in large quantities of dry ether.The amine is a slightly brown liquid boiling at 142-144' under atmospheric pressure, and of sp. gr. 0.7667 a t 24O/24". It dissolves readily in alcohol, ether, or light petroleum, is extremely hygroscopic, and has strongly alkaline properties, The Icydrocldoride crystallises in colourless, silky, somewhat deliquescent needles melting at 133' ; the pZatinichZoi*ide crystallises from warm water in large, *yellow plates decomposing a t 195" ; the ccurichlos-ide also crystallises in large, yellow plates melting a t 63-64', and the oxdate, (C7H,7N)2,H,C,04, in colourless plates which melt and decompose a t 204--205", and also decompose when boiled with water.Behaviour of Diamines on Neutralisation. By MARCELLIN P. E. BERTHELOT (Compt. rend., l899,129,694--70O).-The differences observed i n the heats of neutralisation for successive equivalents of acid afford a method of distinguishing betwoen monoacid and polyacid bases, and of fixing their molecular weight. The same end is more quickly attained by titrating the base with standard acid and ob- serving the behaviour of different indicators ; ethylenediamine and diethylenediamine are thus shown to be monoacid towards phenol- phthalein, and diacid towards methyl-orange. Both these bases may be estimated alkalimetricdly with considerable accuracy, but the end points are not so delicate with diethylenediamine as with ethylene- diamine, a fact which is in harmony with the lower heat of neutral- isation of the former base.Diarnines. Diethylenediarnine (Piperazine). By MARCELLIN P. E. BERTHELOT (Compt. rend., 1899, 129, 687-694).-Diethylene- diamine hydrate, C,Hl0K2 + 6H20, melts at 44' ; when distilled, a mixure of water and diethylenediamine passes over, the proportion of the latter gradually increasing as the temperature rises until, above 135O, the anhydrous base is obtained. This is a crystslline, tenacious, waxy substance which melts at 104" and dissolves very slowly in water, but is nevertheless very hygroscopic. The heat of dissolution of the base is +5.16 Cal. at 14', and of the hydrate - 9.15 Cal. a t 16'. The heat of hydration is therefore +14.31 Cal. (liquid water) or 4.9 Cal. (solid water). No evidence was found for the existence of more than one hydrate.The heat of combustion of diethylenediamine hydrate is 69 1.14 Cal. a t constant volume, and 691.3 Cul. at constant pressure. The heat of formation of the base E. W. W. P-Heptylamine. J. J. S. N. L.84 ABSTRACTS OF CHEMICAL PSPERS. from its elements is 16.6 CaI., and its heat of combustion is calculated as 705.6 Cal. Comparison of the heat of formation of diethylenediamine with that of ethylenediamine (8.8 Gal.) shows t h a t the conversion of the latter compound into the former, by the fixation of a C2H2 group, is accom- panied by the development of + 7.8 Cal., whereas this transformation, instances of which are cited, is always accompanied by the absorption of heat when the general function of the compound remains un- altered.These facts are in harmony with the view that diethylene- diamine is a cyclic compound. The heat of neutralisation of diethylenediamine is 10.36 Cal. for the first, and 7.05 Cd. for the second, equivalent of hydrochloric acid, all the substances being in solution ; diethylenediamine is therefore a weaker base than ethylenediamine, the corresponding figures for which are 12.52 and 11.0 respectively. The heat of dissolution of the hydrated dihydrochloride, C,H,oN2,2HC1 + H,O, is + 6.0 Cal., and of the anhy- drous salt, - 4.09 Cal. ; the heat of hydration is therefore + 1.91 Gal. (liquid water) and +0.3 Cal. (solid water). The heat of formation of the solid anhydrous dihydrochloride from the solid base and the gaseous acid is + 61.4 Cal. I n the activity of i t s basic function, diethylene- diarnine is inferior t o ammonia, ethylamine, and methylamine, but superior t o aniline.N. L. Amic Acids and Irnides of Aliphatic Dicarboxylic Acids. By KARL AUWERS [FRITZ MAYER, and F. SCHLEICHER] (Annoden, 1899, 309, 31 6-347).-The author’s method for identifying di- Larboxylic acids of the aliphatic series (Abstr., 1895, i, 504) meets with certain difficulties (compare Abstr., 1896, i, 639, and 1898, i, 126) which are discussed in the present paper, particularly with regard t o the struetarally isomeric amic acids of monoalkylsuccinic acids, CO,H*CHR*CH,-CONHR and CONHR*CHR*CH,*CO,H, of as-dialkylsuccinic acids, and t o those s-dialkylsuccinic acids which occur in two stereoisomeric forms. It is found that the imides obtained from the structurally isomeric amic acids of monoalkyl- succinic acids by heating them alone, or with acetyl chloride, are identical, and the same remark applies to the amic acids of ns-di- alkylsuccinic acids ; when the imides are hydrolysed with alkali, the amic acids produced are either the original ones, their structural isomerides, or mixtures of the two.The following facts in con- nection with s-dialkylsuccinic acids have been ascertained : 1. The fumaroid acid is converted into the fumaroid imide by heating it with a base during a short period, or by heating the fumaroid anilic acid above its melting point ; this does not apply to the anil, tolil, and P-naphthil of fumaroid diethylsuccinic acid, because these imides are very labile, and thus become converted into the corresponding maleoid derivatives.2. Hot acetyl chloride converts the fumaroid anilic acids into the maleoid compounds. 3. Boiling dilute acids con- vert the fumaroid and maleoid imides into the corresponding fumaroid and maleoid dicarboxylic acids, with a small proportion of the stereo- isomeric modifications. 4. Boiling, dilute, aqueous alkalis resolve the nnils into t h e corresponding anilic acids. The p-tolil of maleoidOKCIANIC CHEMISTRY. 85 dimethylsuccinic acid yields the maleoid p-tolilic acid with aqueous caustic soda, and t h e fumaroid p-tolilic acid witb baryta. 5. Alcoholic soda and potash also convert imides into amic acids, but at the same time change t h e fumaroid compound into the maleoid, the converse taking place to only a slight extent; in some cases, however, the rearrangement does not occur.6. On the other hand, hot, concen- trated aqueous alkalis invariably convert the maleoid amic acids into the fumaric modification ; this action is nut reversible. The following melting points a r e recorded : Methylsuccinic acid ptolilic acid, 164', p-tolil, 109-1 lo", P-naphthilic acid, 154*5", P-uaphthil, 160.5'. Isopropylsuccinic acid anilic acid, 143O, and, 9 1-92', p-tolilic acid, 143-144', p-tolil, 139-140', P-naphthilic acid, 198", P-naphthil, 132-1 32.5'. as-Dimethylsuccinic acid anilic acid, 84-86", p-tolil, 1 I 3'. Fuma.roid s-dimethylsuccinic acid p-tolilic wid, 194', p-tolil, 120-121", P-naphthilic acid, 209" ; maleoid s-dimethylsuccinic acid p-tolilic acid, 164", p-tolil, 153', P-naphthilic acid, 140°, P-naphthil, 220".Fumaroid s-methylethylsuccinic acid snilic acid, 164-165', anil, 76-77", p-tolilic acid, 175', p-tolil, 87-88*5', P-naphthilic acid, 191-192", P-naphthil, 148-150" ; inaleoid s-methylethylsuccinic acid anilic acids, 1 39-140', and 100-102°, anil, 103-1043,p-tolilic acid, 147-1 48', p-tolil 109--110', P-naphthil 159-160". Fumaroid s-diethylsuccinic acid anilic acid, 183-184', p-tolilic acid, 189-190', P-naphthilic acid, 202--203', maleoid s-diethylsuccinic acid anilic acid, 124-1 25', anil, 84-85", p-tolilic acid, 148- 149', p-tolil, 92-93', P-naphthilic acid, 145-146", P-naphthil, 118-1 19'. d-Camphornnilic acid, 203--1"04', d-cam- ptioranil, 117-1 18' ; I-iso-camphoranilic acid, 183-183.5'. Succinic acid p-tolilic acid, 1 79-1803, p-tolylsmide, 207' (compare Auwera and YHBr-CO Harger, Abstr., 1896, i, 640) ; dibromosuccinanil, CHBr.CO >NPh, prepared from bromine and the anil of maleic acid, 171" (compare Auwers and &nghof, Abstr., 1896, i, 644), chlorosuccinanil, - YH2-C0 CHCl*CO >NPlr, 1 17-1 1 So.1%. 0. F. Methyleneasparagine and Allied Compounds. By HUGO SCHIFF (G'ccxaettcc, 1899, 29, ii, 285-303. Compare Abstr., 1899, i, 870).-When exposed t o the air, dimethyleneasparagine gives up formaldehjde, the residual substance having a composition correspond- ing to a se,squinzet~~~yleneas~~aragi~e, CH,(C,H,0,N,:CH2)2 ; its copper compound has the composition C,,H,,O,N,Cu + H,O. Methyleneasparagine acts as a monobasic acid ; at 14', it dissolves in water t o the extent of 2.38 per cent., but i t is scarcely soluble in alcohol.On allowing its solution in alcoholic hydrochloric acid t o evaporate over sulphuric acid, i t deposits colourless needles of the hydrochloride of rnonoethyl aspartate. I n aqueous solution, [a], has a mean value - 47.58" ; a solution containing methyleneasparagine and potassium hydroxide in molecular proportion gives for potassium methyleneasparaginate [a], - 69.01'. The presence of a large quantity of water hinders the formaticn of methyleneasparagine ;86 ABSTRACTS OF CHFKMICAL PAPEIIS. on diluting a solution of methyleneasparagine, however, it is not decomposed. A solution of a-asparagine required for neutralisation 0.63 mol. of potash per mol. of the asparagine, whilst after adding formaldehyde the quantity of potash necessary mas increased t o 0.95 mol.The author prefers Piutti’s formula, NH,*CO*CH2*CMe(NH2)*C02H, for homoasparagine, since it resembles /3-asparagine in having a feeble acid reaction and in giving an azure-violet biuret reaction. Metl~yZenel~on~oc~s~~~~~g~ne,NH2*CO~CH2~CMe(*N:CH2)~CO2H + H20, is a colourless, crystalline compound which dissolves readily in water, but only slightly in alcohol, and does not give the biuret reaction. It behaves as a monobasic acid and forms a copper compound, Methyl-a-ssparagine gives a reddish-violet biuret reaction, but if formaldehyde is present, no coloration is obtained; it acts as a monobasic acid. Dimethyl-a-asparagine, however, has much feebler acid properties ; a concentrated solution neutralises 0.2 mol.of potash per mol. The addition of formaldehyde makes the solution strongly acid again, so that a further 0.6 mol. of potash is required for neutral- isation; in the course of an hour, further addition of 0.2 mol. of potash is necessary, the total amount of potash added being 1 mol. for each mol. of the dimethylasparagine. A solution of 1 mol. of di- methylasparagine in 1320 mols. .of water, is, however, neutral, but on adding formaldehyde neutralises a t once 0.6 mol. of potash, and in the course of the day the remaining 0.4 mol. must be added to keep the solution neutral. I n concentrated aqueous solution, 1 mol. of glutamine neutralises @l to 0.15 mol. of potash ; on adding formaldehyde, methyleneglutamine is formed, and acts as a monobasic acid, neutralising a molecular propor- tion of potash. Methyleneglutamine is a colourless, crystalline mass which dissolves readily in water and decomposes carbonates ; with copper hydroxide, it forms a dark azure-blue compound apparently very soluble in water.(C,H903N,),Cu. T. H. P. Nitrosoalkylurethanes. By ARTHUR HANTZSCR (Ber., 189 9, 32, 314S-3149).-A reply to Briihl (Abstr., 1899, i, 871). T. M. L. Constitution of Inorganic Compounds. XX. Thiocyanocobalt Salts and Structural Isomerides. By ALFRED WERNER, HERBERT MULLER, R. KLIEN, and F. BRAUNLICH (Zeit. unorg. Chem., 1899, 22, 91 --157).-lsothiocyanopentunamine salts, [Co(NH,),NCS] X,, are ob- tained by the action of potassium thiocyanate on concentrated hot solutions of aquopentammine salts, the slilphate being most advan- tageously employed ; blackish-green additive products of thiocyanic acid and the isothiocyano-salt are formed, but are decomposed on addition of water.The thiocyano-group in these compounds is not dissociated even in dilute aqueous solution, and the characteristic reaction with ferric chloride does not take place. The thiocyano-group is also un- altered by the action of mineral acids, whereby the other acid groups undergo substitution. With silver nitrate, additive compounds of the formula Co(NH,),(N03),SCNAg are formed, which, when treated withORGANIC CHEMISTRY. 87 hydrochloric acid, do not give a precipitate of silver chloride, but are converted into the corresponding chloride of the formula Co( NH3)SCl,SCNAg. IsothiocpanopentamminecobaZt sulphate, [Co(NH,),NCS]SO, + 2H,O, crystallises in four-sided, thin, yellow plates, and is conGerted into the hexammin e chloride when oxidised with chlorine.The nitrate, chloride, bromide, iodide, platinichloride, platinosochloride, thiocyanate, and nityite, obtained by treating the sulphate with the corresponding acids, are also described. Nitritotl~iocyccnotet~~am~inesalts, [CON O,(NH,),SCN]X .-The cldop-ide is obtained by the action of potassium thiocyanate on a hot solution of chloronitritotetramminecobalt chloride and subsequent treatment with hydrochloric acid. The thiocyano-group in these compounds is not so firmly combined as in the preceding series, and is gradually completely dissociated in dilute solution ; with silver nitrate, similar additive products of the formula [CoN0,(NH3),SCNAg]C1N03 are oh- tained, which, however, when boiled with water, are decomposed into silver chloride and nitritothiocyanotetramminecobalt nitrate ; when shaken with silver oxide, the corresponding base is not obtained, but decomposition takes place with the formation of silver chloride and thiocyanate and the base of the nitritoaquotetrammine series. Nitp.itothiocyanotetramminecobaZt c?doyide crystallises in lustrous leaflets when precipitated from aqueous solution by hydrochloric acid, and in needles and tabular prisms from neutral aqueoiis solution, is soluble in 33 parts of water, and when oxidised with chlorine yields chloronitritotetrammine chloride. The bromide, iodide, thiocyccnate, and nitrate are a h described.Dithiocya.nodiethylenediami~ecobccZt sults, [Co(C2H,N,),(SCN),]X.- By the action of potassium thiocyanate on dichlorodiethylenediamine- cobalt chloride and subsequent evaporation with hydrochloric acid, the chlorides of two isomeric dithiocyanodiethylenedjaminecobalt salts are obtained.This isomerism is determined by the isomerism of the dichlorodiethylenediamine salts, since the 1 : 2-dichlorodiethylene- diamine salts (violeo-salts) yield only one dithiocyano-series, the easily soluble salts containing iso-thiocyano-groups, whereas 1 : 6-di- chlorodietbylenediamine salts (praseo-series) yield both series of salts and more of the sparingly soluble series, containing thiocyano-groups, as the concentration of the solution to which the potassium thiocyanate is added increases. The easily soluble dithiocyanochloride, when oxidised with chlorine, is converted into diamminediethylenediamine- cobalt chloride, that is, the nitrogen atom of the thiocyano-group in direct combination with the cobalt atom is converted into ammonia.The sparingly soluble isomeric chloride, however, when oxidised with chlorine, yields dichlorodiethylenediaminecobalt chloride, in which the thiocyano-group is completely oxidised. As regards the thiocyano- groups, the isomerism is evidently similar to that between the thio- carbimides and the thiocyano-est ers. DiisothiocyanodiethyZenediamine- cobalt chloride crystallises, with 1H,O, in thin, triclinic, ruby-red tablets of rhomboidal habit, and, with l&H,O, i n thick, rhomboidal t'ablets which appear black in reflected light, 1s easily soluble in cold water,88 ABSTRACTS OF CHEMICAL PAPERS. yielding a bright ruby-red solution.The thiocyanate, hydjsogen sulphate, nityate, bromide, and iodide are also described. A normal sulphate cannot be prepared, and this forms a marked distinction between this series and the sparingly solitble series from which only the normal sulphate is obtained. Dithiocy~nodiethylened~u~in~cobult chloride crystallises, with 1H20, in thin, yellowish-red needles or prisms hrtving a bronze lustre, and in 5at, rhomboidal prisms which appear almost black in reflected light, is practically insoluble in cold water, fairly soluble in hot water, and gives a yellowish-red solution. The thiocyanate, sulphate, nitrute, bromide, and iodide are also described.Diumminediethylenediam~necobcclt chloride, [CO( NH,),( C,H,~,),]Cl, + H,O, obtained by oxidising the above diisothiocyanochlorlde with chlorine, cry stallises in triclinic, many-sided tablets, and in four-sided, yellow pyramids. The aqueous solution is completely precipitated by alcohol, and gives the typical luteo-salt reactions. With cobaltous chloride, similarly to the triethylenediaminecobnlt chloride, it yields a double salt which crystallises, with 2H20, in thin, four-sided plates. The thiocyano-group is generally combined in the normal manner. I n the four series of compounds, thiocyanopentammine salts, nitrothio- cyanotetrammine salts, chlorothiocyanodiethylenediamine salts, and oxalothiocyanotriammine salts, only the first series are derivatives of isocyanic acid, since, when oxidised with chlorine, they yield hexammine salts.The remaining salts, when oxidised with chlorine, yield respectively chloronitritotetrammine salts, trichlorodiethylenediamine salts, and oxaloaquotriammine salts. Further, the thiocyano- residues in Reinecke’s salt, Cr(NH,),(SCN)4K, and in potassium platinithiocyanate, are completely oxidised and eliminated by chlorine. The conversion of isothiocyano-group into the ammonia group which remains in direct combination with the cobalt atom, shows that the ammonia molecules in the complex radicle are combined with the metal atom in the same manner as acid groups which are in direct combination with the metal atom. The direct substitution of ammonia by acid groups and the converse substitution cannot be effected, as a rule, in the cobaltammonia compounds.When, how- ever, chloroarnminediethylenediaminecobalt chloride is treated with potassium thiocyanate, the ammonia group is replaced by the thio- cyano-group, and chlorothiocyanodiethylenediaminecobalt thiocyanate is formed. Dichloi~ocliethylenediuminecobalt thiocyccnate, [Co(C,N,H,)CI,]CNS, obtained by adding potassium thiocyanate to an aqueous solution of the diethylenediaminepraseo-chloride, crystallises in small, lustrous, green, six-sided prisms. Cl~lorot~iocyanodietl~ylenediuminecobcclt thiocyanate, [CO( C,N,H,)Cl*SCN]SCN, obtained by boiling dichlorodiethylenediaminecobalt chloride with potassium thiocyanate, is a brownish-violet, crystalline powder which, when heated with water, decomposes into the isomeric dithio- cyanochlorides, and when evaporated with hydrochloric acid yields the salt [ Co( C,N,H,)ClSCN 3 C1.E. C. R.Organo-mercuric Compounds. By GEORGES DENIC~S ( A m . Chirn. Plqs., 1899, [ vii], 18, 382-432. Compare Abstr., 1895, i, 411 ; 1898, i, 546, 549, 618; 1899, i, 22, 414, ii, 256).-Citric acid, even when in dilute solution, is readily oxidised by potassium permanganate t o acetonedicarboxylic acid ; the latter combines readily with mercuric sulphate, forming an insoluble compound (Abstr., 1899, ii, 454); this reaction may be utilised in detecting small quantities of the former acid in the juices of plants, wines, milk, &c. Glycerol, gum, dextrose, sucrose, and acetic, tartaric, malic, succinic, and lactic acids do not interfere with the reaction, but oxalic acid must be removed either by a preliminary oxidation with excess of permanganate or by precipitation as mercuric oxalate.G. T. M. Tungsten Alkyls. By EDGAR F. SMITH, E. A. BARNETT, and CLARENCE HALL (J. A,mer. Chem. Xoc., 1899, 21, 1013--1016).-1t has not been found possible to obtain the compound, WMe,T, described by Riche (Compt. rend., 1856, 42, 303) and by Cahours (Annalen, 1862, 122, 70) ; the authors obtained a black substance, containing over 94 per cent. of tungsten, together with small quantities of carbon and iodine. No tungsten alkyl i s obtained when tungsten hexa- chloride is treated with mercuric ethyl or zinc methyl, nor yet by the action of methyl iodide on tungsten prepared by varioixs methods. J.J. S. Cyclic Compounds, Ethylhexanaphthene and Mercuro- heptanaphthene Iodide. By N. KURSANOFF (Chenz. Centr., 1899, ii, 477; from J. Buss. Chem Soc., 1899, 31, 534--535).-By the action of zinc ethyl on chloro- or iodo-naphthene, about 30 per cent. of ethylnaphthene is obtained ; i t boils a t 132-133' and has a sp. gr. 0.7913 a t O"/O' and 0.7772 at 2Oo/O0. A vapour density determina- tion gave 4.04. Naphthylene (cyclohexene), ethylene, ethane, and saturated condensation products boiling a t 242-243' under 755 mm. pressure are also formed. '< Mercixro-heptanaphthene iodide," C6H,,HgI, prepared. by the action of sodium amalgam on iodohexamethylene, crystallises from hot alcohol in lustrous, white scales, melts a t 142', and is decomposed by prolonged heating with liberation of mercuric iodide.Derivatives of Nitroic Acids. Reactions of Nitro-com- pounds. By ARTHUR HANTZSCH and HERMANN KISSEL (Bey., 1899, 32, 3137-3148. Compare Abstr., 1899, i, 404).-The names ' nitroic acid ' and ' nitroic ester-acid ' are given t o the acids R*NO(OH), and R*NO(OR')*OH, formed by the addition of water and alcohols t o cer- tain nitro-compounds. Trinitrotoluene potnssiuna met?Loxide (potassium nrethgl dirzit~otoluene- nitroute), C,H,Me(NO,),*NO(OMe)*OK + H,O, is a dark violet salt, which explodes when heated; pG4 96.0 and plOz4 113.0, at 25', showing that the salt is hydrolysed t o a considerable extent. The ester-acid, hydrogen methyl dinitrotoluenenitroate, is a dark red sub- stance which dissolves only slightly in water or in organic solvents, except acetic acid, in which i t has a normal molecular weight ; it is st E.W. W. VOL. LXXVIII. i. h90 ABSTRACTS OF CHEMICAL PAPERS. feebke acid, plaza 15 at 25O, and is stable in aqueous solution, but evolves nitrous acid when boiled with dilute acids, and gives trinitro- toluene and methyl alcohol when dissolved in concentrated sulphuric acid ; i t is not attacked by phosphorus pentachloride, and crystallises unchanged from acetic acid, but acetyl chloride converts it into acetyl methyl diniti-otoluenenitroccte, a microcrystalline substance which ex- plodes o n gentle warming, and is hydrolysed by alkalis. Potassium methyl dinitrobenzenenitroate (trinitrobenzene potassium methoxide) and potassium methyl dinitroxylenenitroccte (trinitroxylene potassium methoxide) are immediately decolorised by acids, and do not give nitroic ester-acids.CGH,!N02)3*C02K,MeOK,MeOH, gives an unstable n.ztTozc ester-acid, from which trinitrobenzoic acid is regenerated on evaporating the solution. p-Xitrobenzylnitramine (Hantzsch and Hilland, Ber., 31, 2068) interacts with 2 mols. sodium ethoxide to form the sodium ethyl nitroate, N,O,Na*CH,* C6H;NO(OEt)*ONa, a deep-red, soluble salt which de- composes in moist air, cannot be recrystallised, and sometimes inflames spontaneously in the desiccator. The ester-acid is also extremely unstable, and changes quickly into a yellow resin, from which p-nitro- benzoic acid was obtained. Sodium trinitrobenzoate combines, at least partially, in solution with another molecule OF sodium hydroxide t o form a sodium nitroate, which could not be isolated, but was shown to be present by the con- ductivity and colour of the solution.Barium dinitrobenxonitroate, [ Ba<~>NO.C,H,(NO,),* CO, Ba, prepared by the action of barium hydroxide on trinitrobenzoic acid, is a dark, brownish-red salt, very slightly soluble in water, and very explosive ; the nitroic acid is un- stable. Trinitrobenzene and trinitrotoluene dissolve in caustic alkalis, giving deep red solutions, but the formation of nitroates appears t o be only very partial; on acidifying the alkaline solutions at Oo, red solutions are obtained which appear to contain the nitroic acids, but these are unstable at the ordinary temperature. Hepp's trinitrobenzene potassium cyanide (Anncclen, 1 SS3,215, 360), t o which the formula C,H,(NO,),*NO(CN)*OK is assigned, is a deep- violet, crystalline, explosive salt ; dinitrobenxeqzecyanonitroic acid (trinitrobenxene cynnhydrin), which is precipitated by mineral acids from a solution of the potassium salt, crystallises from ether or benzene in red needles, and decomposes at 175O; it is not acted on by phos- phorus pentachloride or acetyl chloride.The characteristic reactions of the nitro-paraffins are shown t o be really those of the isonitro-compounds. Nitroethane is scarcely attacked by bromine in aqueous solution, but a solution of isonitro- ethane, freshly prepared at 0' by the action of hydrochloric acid on the sodium salt, brominates completely and smoothly. A solution of nitro- ethane gives no nitrolic acid with nitrous acid, but isonitroethane- interacts readily with it.Isonitroethane and diazonium hydroxide interact immediately at Oo, whilst t r u e nitroethane is inactive ; simi- larly, phenylisonitromethane interacts readily with diazonium hydroxide and isonitroethane with p-bromodiazonium hydroxide, The conclu- Lobrg de Bruyn's salt, 1 2O#GANIC CHEMISTRY. 9 1 sion is drawn that the true nitro-compounds are, of themselves, no more active than the corresponding halogen compounds, and owe their apparent chemical activity entirely to the formation of the labile isonitro-compounds, and not to the negative character of the -NO2 group. T. M. L. Transformation of Styrene into Metastyrene under the Influence of Light, By GEORGES LEMOINE (Compt. rend., 1899,129, 719-722.Compare Abstr., 1898, i, 70).-The polymerisstion of styrene is effected by the action of heat in the dark, and also under the influence of sunlight a t the ordinary temperature ; in the latter case, the action is slower, 1-3 per cent. of the substance being trans- formed in an hour. In this change, the blue and ultra-violet rays are principally concerned ; their activity does not extend much below 5t depth of 4 mm., and is greatly decreased by cooling the insolated liquid; the action does not continue after removal from the influence of light, or only to a very small extent. The velocity of transforma- tion in the light is approximately equal t o that observed in the dark at a temperature 50" higher. The general conclusion arrived a t is that, in the conversion of styrene into metastyrene, light exerts an accelerating action on an exothermic transformation which takes place in the dark at the same temperature, although more slowly.N. L. Naphthalene-1 : 3 : 5-trisulphonic Acid. By HUGO ERDMANN (Bey., 1899, 32, 3186-3191. Compare Armstrong and Wynne, Proc,, 1887, 146, and 1893, 166).-Polysulphonic acids containing two or three sulphonic groups in P-positions are obtained when naphthalene is sulphoiiated with fuming sulphuric acid at high temperatures ; of these, the 1 : 3 : 6-trisulphonic acid, recognised by its sodium and lead salts and its chloride, is the chief product (Proc., 1587, 146). Naphthalene-1 : 3 : 5-trisulphonic acid, the original product of sulphon- ation, is only obtained when the whole of the reaction is carried out below 90".Sodium naphthalene-1 : 5-disulphonate is mixed with fum- ing sulphuric acid a t 50°, and the reaction completed a t 90'; the 1 : 3 :5-acid which is thus produced is separated in the form of its sodium salt; this compound is converted into the sulphonic chloride (m. p. 145-148'), which is then boiled with methyl alcohol, and the solution evaporated to dryness; in this way, the acid is obtained as a colourless syrup. Naphthalene-1 : 3 : 5-trisulphonic acid resembles the non-volatile mineral acids ; it is very hygroscopic, destroys cellulose with liberation of carbon, and decomposes sodium chloride. The aniline salt, C,,H,(SO,H),,SNH,Ph, produced by adding aniline to an aqueous solution of the acid, or by double decomposition from aniline hydrochloride and sodium naphthalenetrisulphonate, crystaldises from water in aggregates of white, silky needles.The salt is not hygroscopic, and is readily soluble in water, but less so in brine solution. The p-toluidine salt is more soluble than the aniline compound ; the benzidine salt, 2Cl,H,(80,H),,3Cl,H,(NH,),, crystal- h 292 ABSTRAC2S OF CHEMICAL PAPERS, lises with 4H20, and the dianisidine salt separates slowly from its solution in glacial acetic acid in short, hard needles. G. T. M. Polymerisation of Inorganic Chloroanhydrides. 11. By GIUSEPPE ODDO (Gctxxetta, 1899, 29, ii, 330-343. Compare also this vol., ii, 74).-The products obtained on heating phosphorus penta- chloride and oxychloride, in a reflux apparatus, with varying quanti- ties of water are as follows : With 2PC1, + H,O, half of the penta- chloride is converted into oxychloride, the rest being unchanged ; 2PC1, + 2H20 yields the theoretical amount of oxychloride ; 2PC1, + 3H20 or (POCI,), + H,O gives mainly oxychloride accompanied by a little pyrophosphoryl chloride, P,O,Cl,, and phosphoric oxide ; with the proportions 2PC1, + 4H,O or (POCl,), + 2H,O, the same products as in the previous case are obtained, the amount of oxychloride being considerably diminished, and that of phosphoric oxide correspondingly increased.The interaction of phosphorus pentachloride (3 mols.) on phosphoric oxide (1 mol.), yields a little oxychloride and a considerable quantity of pyrophosphoryl chloride, and is recommended as a good method for preparing the latter.Potassium chlorate reacts with phosphorus oxychloride according to the equation (POCl,), + KC10, = P,O, + KC1 + 3c1,. This reaction offers a convenient method of chlorination where a definite quantity of chlorine is required. By heating together phosphorus oxychloride and aniline hydro- chloride in molecular proportions in a reflux apparatus, hydrogen chloride is evolved and dichlorophosphoxymonoanilide, NHPh*POCI,, obtained. The molecular weight of the latter in boiling benzene varies from 215 with a concentration 0.7944 to 276 when the concen- tration is 5,2183; using the same solvent, the numbers given by the cryoscopic method are 221 (concentration 0.9676) and 252 (concentra- tion 1.8323). The calculated value is 210. Michaelis and Schulze (Abstr., 1894, i, 128) state that this compound distils in a vacuum with partial decomposition; the author finds, however, that a t 90' evolution of hydrogen chloride commences, and at 180" continues until 1 mol.HC1 is lost per molecule of the substance, the residue being a new compound to be described later. Using three mols. of aniline hydrochloride to one of phosphorus oxychloride, two products are obtained. The first, monochlorophos- phoxydianilide, POCl(PhNH),, gives, in boiling alcohol, a molecular weight varying from 270 with a concentration of 1.3856 to 184 when the concentration is 3.6192 ; the molecular weight falls if t h e boiling be prolonged. These observations are at variance with those of Michaelis and Schulxe (Abstr., 1894, i, 588). The other product is oxyphosphoazobenzeneanilide, melting at 320--325O, and not at 357' as stated by Michaelis and Silberstein (Abstr., 1896, i, 344).I f six molecular proportions of a benzene solution of aniline be treated with one of phosphorus oxychloride, the trianilide of ortho- phosphoric acid, PO(PhNH),, is obtained ; its molecular weight in boiling alcohol is 358-359, the calculated value being 323.OItGANIC CHEMISTRY. 03 The action of phosphorus oxychloride on phenol yields the compound POCl,* OPh, which gives the normal molecular weight in boiling benzene, a little of the chloride POCl(OPh),, triphenyl phosphate, which in boiling benzene has the normal molecular weight, and a little diphenylphosphinic acid. Salicylanilinoacetic Acid [o-Carboxyphenylglycollic Acid Monanilide] and its Derivatives.By GEORG COHN (J. pr. Chem., 1899, [ ii], 60,404-406).-The monoanilide of o-curboxyphenglglycollic acid, NHPh*CO*C,H,* O*CH,* CO,H, prepared by the action of chloro- acetic acid on salicylaniline, separates from alcohol, in which it is readily soluble, in white needles melting at 159'. The corresponding phelzetidide crystallises from me thy1 alcohol, in which it is sparingly soluble, in rhombic leaflets melting a t The anisidine compound, OMe*C,H,* NH*CO*C,H,* O*CH,* CO,H, crystallises from methyl alcohol in bundles of long needles and melts indefinitely a t 174'. A. L. Diphenylamine Derivatives, especially Sulphonic Acids. By ROBERT GNEHM and H. WEBDEKBERG (Zeit. angew. Chern., 1899, 1027-1030, 1051-1055, and 1128. Compare Merz and Weith, this Journ., 1873, 74).-Sulphuric acid of 66" B6.does not react with diphenylamine in the cold, and even on warming a t 100-150" the chief sulphonation product is the disulphonic acid, although a con- siderable quantity of the base remains unaltered ; the chief and, in some cases, the only product formed when concentrated sulphuric acid is employed, a t temperatures between 105' and 140', is the disulphonic acid. Fuming sulphuric acid of different strengths at 50' yields a mixture of mono- and di-sulphonic acids which i t is impossible to separate. I n all the experiments made, the unaltered diphenylamine was found to contain a substance soluble in ether and melting a t Diphenylaminesulphonic acid is most readily obtained by sulphon- ating acetyldiphenyIamine with fuming sulphuric acid (10-25 per cent.anhydride) and subsequently hydrolysing. I n the sulphonation, it is advisable to add phosphoric oxide in order to hinder hydrolysis by the water formed. Bariuni acetyldiphenylamine sui'phonute, C,,H2,?,N,8,Ba, is ex- tremely hygroscopic, and could not be obtained in a crystalline condition, For the preparation of diphenylaminesulphonic acid, it is not necessary to isolate the pure acetyl derivative ; the crude sulphonic mixture may be boiled with water for some 3 hours and then treated with barium carbonate. Barium clil3l~enylaminssuZphon~te, C,,H,,O,N,S,Ba, is very sparingly soluble in cold water, and crystal- lises in snow-white, anhydrous, glistening plates which do not decom- pose at 170". The copper salt, with 2H?O, and the sodium salt were also prepared.Diphenylaininesulphonlc acid condenses with form- aldehyde in a.queous acid solution, *yielding triccrnilinotri~~~en~llmetlzccne- sulphonic acid, C19H3109NSSS, which dissolves in water or alcohol, readily undergoes oxidation in solution, and turns pale blue on exposure to the air. T. H. P. 175-1 78'. 246-248'.98 ABSTRACTS OF CHEMICAL PAPERS. Diphenylaminesulphonic acid is best prepared from the copper salt ; it crystallises in colourless plates, is readily soluble in alcohol or water, and condenses with diazonium solutions, yielding acid dyes. Sodium p-sulphobenxeneaxodipheny Zcminesulphonate, C18H1306N3S2Na2, crystallises from hot water in violet plates and dyes silk or wool orange- y ello w. hydyox yd initvo benxeneccixodipheny laminesu I- phonate, Cl,H120,N,SNa, forms glistening, brown plates.Diphenyl- aminesulphonic acid (2 mols.) forms a salt with picramic acid (1 mol.), Acetyldi-p-nitrodiphenylamine, NAc( C,H,* NO,),, obtained when acetyldiphenylamine is treated with a mixture of sulphuric and nitric acids at 8--15O, crystallises from hot alcohol in pale yellow, glistening plates melting a t 164" and readily soluble in most organic solvents ; when warmed with concentrated hydrochloric acid, it yields di-pnitrodi phen ylamine. When barium acetyldiphenylaminesulphonate is nitrated with a mixture of fuming sulphuric (5 per cent. anhydride) and fuming nitric acids, first a t 15" and then a t 30-35", a nitro-derivative is formed the barium salt of which could not be obtained in acrystalline condition, but when hydrolysed with sulphuric acid (37 per cent.), rtitrodiphen~lamiesulphonic acid was obtained, the bccrium salt of which is readily soluble in water and forms dark red crystals.The acid has not been obtained in a pure form and is probably a mixture of ortho- and para-nitro-compounds. Barium diphenylaminesulphonate is much more readily nitrated than its acetyl derivative, the most suitable reagent being a mixture of concentrated nitric and sulphuric acids at 0'. The product is a mononits.o.derivative. Barium diphenyZaminedisuZphonate separates from water in crystal- line masses containing 2H,O ; the potassium salt contains 1iH20 and the copper salt 4H,O; the acid is readily soluble in water or alcohol, and bas only been obtained in the form of a syrup.When the barium salt is nitrated with a mixture of nitric acid of sp. gr. 1.4 and concentrated sulphuric acid, the product is a mononitro-derivative, the bccs.ium salt of which, C,,H,O,N,S,Ba + 2H,O, forms indefinite, orange-red crystals readily soluble in warm water ; the potassium salt contains l+H,O. When reduced by Claisen's method (Ber.,' 1879, 12, 1946), aminodi- phenyZaminedisulphonic acid is obtained, the burium salt of which, C,,H,,O,N,S,Ba, forms a reddish-coloured mass, readily soluble in water, but insoluble in alcohol. Sodium J. J. 8. Characterisation of Weak Acids and Pseudo-acids. By ARTHUR HANTZSCH (Be?.., 1899, 32, 3066-3088. Compare Abstr., 1899, i, 399)-It is well known that the molecular conductivity, p, of the sodium salt of a comparatively strong acid increases with the dilution,and that the increase consequent on a doubling of the dilution has a diminishing value, tending towards 0 ; further, that the in- crease consequent upon a change of dilution from 32 to 1024 litres per gram-mol.(A1026-32) has a value of 10-12 ; also, the sodium salts of such acids are neutral to litmus (or to a solution of potassium iodide and iodate), and are not hydrolysed appreciably in aqueous sol u-ORGANIC CHEMISTRY. 95 tion. Strong acids, moreover, combine with dry ammonia, both directly and when dissolved in non-dissociating media, such as benzene. I n the case of very weak acids, the sodium salts are more or less hydro- lysed; a certain amount of sodium hydroxide is present in the aqueous solution, which then has an alkaline reaction to litmus, and exhibits an increasing, instead of a decreasing, rate of increase of conductivity with dilution, and a resulting abnormally high value of Alo,4-32 (regard must be had to the fact that the alkalinity may be due, as in the case of diazotates, to a little alkali from which it is practicably impossible to free the salt).These regularities mere in- vestigated in the case of some weak, or very weak, acids, and the results are tabulated below: K is the value of the dissociation constant of the acid; and the percentage of the sodium salt hydro- lysed in an aqueous solution containing 1 gram-mol. in 32 litres (V32) was determined approximately by measuring the hydrolysing effect upon methyl acetats (compare Shields, Abstr., 1893, ii, 448) : Sodinm salt.Per cent. hydro- K at 25". 4 o a 4 - 32' lysed ( &2)' Phenol .................... 5 10-7 28.0 6 2 : 4-Dichlorophenol ...... 31 7, 11.9 0.52 ........... 11.7 0.52 - 0.37 2 : 4 : 6-Trichlorophenol .. . 1000 ,, It is noticeable that, although nitrophenol, OH*C,H,*NO,, is 10 times as weak an acid as trichlorophenol, yet its sodium salt IS less hydrolysed; this salt must therefore be derived from an acid stronger than trichlorophenol, such as O:C,H,:NO*OH, and nitrophenol must be regarded in consequence as a pseudo-acid. The following rules are given for use in the diagnosis of pseudo-acids. I. The substance is neutwd. (1) The salt is neutral (therefore not hydrolysed, and so the salt of a strong acid) : the substance is a pseudo-acid ; for instance, phenylnitromethane, CH,Ph*N02 4 CHPh:NO*ONa. (2) The salt is alkaline: if A1024-32 is not greater than 12-13 (or if the hydrolysis is small) : the substance is a pseudo- acid ; for instance, quinonehydrazone, NHPh *N:CGH,:O - NPh:N*C,H,* ONa, and isonitrosoacetone, NOH:CH*CMeO 4 NO*CH:CMe*ONa(?).11. The su6stance i s feebly, or very feebly acid. (1) The salt is neutral : the substance is a pseudo-acid ; for instance, nitrophenylnitrosnmine, o-Chlorophenol ............ - 16.7 2.1 p-Cyanophenol 61 9 7 p-Nitrophenol .............. 96 ,> 11.9 0.28 - - NO,* C,H,*NH*NO - NO,. C,H,*N:N*ONa(anti), ethylnitrolic acid, NO - C M e < Z G > O , and dinitro- ethane, NO,*CHMe*NO, -+ NO,*CMe:NO*O~Na. ' (2) The salt is alkaline: if Alo2z-32 is but slightly greater than the normal value, the substance is a pseudo-acid ; for instance, p-bromophenylnitros- amine, C,H,Br*NH*NO -, C,H,Br*N:N*ONa ; if Ah,,,,-,, is de- cidedly greater than the normal value, the percentage of hydrolysis must be determined: if this is much less than that of sodium96 ABSTRACTS OF CHEMICAL PAPERS.phenoxide, the substance is a pseudo-acid; in the opposite case, nothing can be predicated, and other properties must be taken into account. 111. The substance is a pronounced acid with a dissociation constant readily susceptible of measurement ; the salt is not perceptibly hydrolysed: the substance, at any rate the ionised part of it, has the same constitution as the ionised s a l t ; it is possible that the undissocinted substance may have a different constitution, when the case would be one of ' ionisation isomerism.' C.F. B. Bromophenols Insoluble in Alkalis. By KARL AUWERS (Ber., 1899, 32, 2978--2987. Compare Abstr., 1898, i, 70 and 646).-A further discussion of the formuls of these bromophenols. At mesent. i t is imDossible to decide whether a comDound insoluble in ilkalis of this tip., for example, C7H70Br, is repGesenhed by the CH:CH>~~, or formula CBr *CH,* O*CH, CH,Br* CH<CH: CH \ ,CH:CH \ / R. H. P. Bromophenols from as-o-Xylenol and as-m-Xylenol. Eg KARL AUWERS (Be?-., 1899,32, 2987-3005).-A comparison of the properties of the compounds described in the following three abstracts. R. H. P. Pentabromide from [Pentabromo-derivative of ] as-nz-Xylenol. By KARL AUWERS and W.HAMPE (Ber., 1899, 32, 3005-3016. Compare Abstr., 1896, i, 424, and 1897, i, 33).-The acetyl deriva- tive of ww : 2 : 5 : 6-pentabromo-1 : 3 : 4-xylenol, C6Br,(CH,Br),~OAc (Zincke, Abstr., 1898, i, 70), forms colourless needles melting at 180', and is easily reduced t o the acetyl derivative of tribromo-1 : 3 : 4- xylenol, which crystallises from glacial acetic acid in lustrous prisms melting at 115-116'. ~~-l)iiodot~ibrorno-l : 3 : $-xyZenot, C,Br,(CH,T),* OH, prepared from the corresponding diacetate (m, p. 172', loc. cit.) by treatment with hydrogen iodide, crystallises from glacial acetic acid in rosettes of small needles which melt at 182-183', and undergo gradual decom?osition without previous solution when treated with aqueous alkalis. The same diacetnte, on treatment with a n excess of alkali, yields an in- soluble, amorphous powder, the constitution OF which could not be determined ; on treatment with acetone, i t yields a substance which melts at 230-232O, and is probably the acetyl derivative of tribromo- 4-hydroxy-m-xylylene glycol, OH* C,Br,( CH,*OH)*CH,*OAc.The glycol, obtained by treating the dibromide with acetone and water, crystallises from benzene in slender needles melting a t 145-146', and yields a trimethyl ether melting at 95-96', which, when treated with hydrogen bromide, yields pentabronzo-l : 3 : 4-xylend methyl ether, G1,Br,(CH2Br),~OMe, melting at 165-1 68'. Pentabromo-1 : 3 : 4-xylenol, when treated with aniline in benzene solution, yields a QO dianilide, which is a yellow, crystalline powderORGANIC CHEMISTRY. 97 melting at 118-121".If the acetyl derivative of the pentabromo- compound is used, a monoucetyl derivative of the dianilide is obtained ; i t melts at 209", is soluble i n alkalis, and when boiled with acetic anhydride yields a diacetate insoluble in alkalis and melting at 116-115°. The dipiperidide, obtained in a similar manner, is a colourless, crystalline powder melting at 115-1 1 To, and yields bromanil on oxidation with nitric acid, The diacetate (m. p. 172O), when oxidised in similar manner, yields a tetmbromotoluquinone, C B r < ~ ~ ~ ~ ~ ~ > C * CH,* Br, which crystallises in yellow, lustrous leaflets melting at 258-259", and on reduction yields the corre- sponding puinol, which forms brownish needles melting at 226-227".R. H. P. Pentabromo-derivative of as-o-Xylenol. By KARL AUWERS and R. VON ERGGELET [and in part H. VAN DE ROVAART and W. WOLFF] (Bey., 1899, 32, 3016-3033).--0-0 : 3 : 5 : 6-Pentabronzo- 1 : 2 : 4-xylenol, C,Br,(CH,Br),*OH, obtained by heating tribromo-1 : 2 : 4- xylenol with a n excess of bromine in a sealed tube at 130°, crystallises from glacial acetic acid in lustrous needles melting at 149-150°, and is insoluble in alkalis. The acetyl derivative melts at 127-128", and is only slowly decomposed by boiling alkalis ; on reduction, i t yields the acetyl derivative of tribromo-1 : 2 : 4-xylenol (m. p. 111--212°). : 3 : 5 : 6-Tetrab~onao-1 : 2 : 4-xylenol-o-methyl ether, OH* C6Br3(CH2Br)*CH2* OMe, formed when the pentabromo-compound is boiled with methyl alcohol, melts a t 132-133') and is soluble in caustic soda solution.The monoacetyl derivative melts indefinitely between 80" and 90' and, if treated with sodium acetate and acetic anhy- dride, yields the diacetate, OAc*C,Br,(CH,* OAc)* CH,* OMe, melting at 101-102". The corresponding ethyl ether forms sharp-angled prisms melting at 124-125", and yields a similar diucetate melting at 105-107". OH* C,Br,(CH,Br)* CH2* OH, prepared by treating the pentabromo-compound with acetone and water, crystallises from benzene in needles melting at 166-167", and is soluble in alkalis. A poor yield of the corresponding glycol melt- ing at 185" is obtained after further treatment with acetone. Its dimethyl ether, OH* C,Br,( CH,. OMe),, is a colourless, crystalline powder melting at 157".The diethyl etliev, obtained by treating the mono- ethyl ether of the tetrabromo-xylenol with alcohol, crystallises in the form of compact prisms and cubes melting at 94". The triethgl ether is a thick oil, which, on treatment with hydrogen bromide, yields penlabyorno-1 : 2 : 4-xylenol ethyl ether, C,Br,(CH,kh.')2*OEt, in the form of needles melting at 108-1 14'. The pentabromo-compound, on treatment with sodium acetate and acetic acid, yields the monoacetyl derivative, OH* C6Br,(CH2Br)* CH,* O h , which crystallises in needles melting at 154-155", forms a phenylurethans melting at 193", and when boiled with alcohol yields an ethyl ether, OH* C,Brs(CH2Br)* CH,* OEt, melting at 124-125'. The diacetyll derivative of t h e tetrabromo- compound forms small needles melting at 116", and on treatment with w : 2 : 5 : 6-F&c~bromo-L : 2 : 4-xylenol,98 ABSTRACTS OF CHEMICAL PAPERS, acetic anhydride yields the t~iacetyl derivative, OAce C,Br,(CH,* OAc),, melting at 133-1 34".On treatment with o-toluidine, the pentabromo-compound is converted into the di-o-toluidicle which melts at 153' and forms an ethyl ether melting at 121-123'. The tetrabromo-compound, when treated with aniline in benzene solution, yields the compound OH* C6Br3(CH2* OH). CH,*NHPh, which melts at 171" and forms a triacetyl derivative melting and decompos- ing at 179-181". ww-Diiodotribromo-1 : 2 : 4-xylenoZ, prepared by treating the tetra- bromo-compound previously described with hydrogen iodide, forms yellowish, compact crystals melting at 165-166*, and yields a monoacetgl derivative melting at 142'.On treatment with acetone, this diiodo-compound forms a monoiodo-derivative melting at 193", the diet?t,yZ ether of which melts at 110-11 1". The diiodo-compound, when treated with. glacial acetic acid and sodium acetate, yields the nzonoacetgZ derivative of the monoiodo-compound which melts at 185-1 90". On reduction, the tetrabromo-xylenol yields the alcohol, OH* CH,*C,MeBr,* OH { = 1 : 2 : 41. This crystallises from benzene as silky needles melting a t 170-180°, and yields a diacetate melting at 135-1 37". The monoucetyl derivative, OH- C,&IeBr,* CH,O Ac, melts at 140-142". On oxidation of the alcohol with nitric acid, tribromo- toluquinone is obtained in the form of yellowish leaflets melting at 23 3-2 35".R. H. P. Heptabromo-derivative of as-o-Xylenol. By KARL AUWERS and HARRY BURROWS [and in part H. VAN DE ROVAART] (Bey., 1899, 32, 3034--3045).-wowo : 3 : 4 : 6-1re;l)tabrorno-1 : 2 : 4.xglenol, OH- CoBr,(CHBr2)2, prepared by heating tribromo-1 : 2 : 4-xylenol in a sealed tube at 190" with an excess of bromine, forms light, silver-grey crystals melting at 199", and is insoluble in alkalis. The acetyll deriva- tive melts at 193", and is easily reduced to acetyltribromo-1 : 2 : 4- xylenol. On boiling the heptabromo-derivative with methyl alcohol, the clirrzethylucetul, CH(OMe)2*C,Er,(CHBr2)*OH [ = 1 : 2 : 41, melting at 116-1 1 8 O , is formed. The corresponding diethyl acetccl melts at 143". The corresponding diacetate, formed by treating the heptabromo- xylenol with glacial acetic acid and sodium acetate, crystallises in colourless plates melting at 155", and when boiled with acetic anhy- dride yields the triacetyl compound, OAc* C,Br,(CHBr,)*CH(OAc),, melting at 132-133'.Wher, the acetals just described are warmed with glacial acetic acid, w o : 3 : 4 : 6-pentabromo-5-hydroxy-o-toluabdehyde is obtained ; it crystallises in small needles melting at 168", is soluble in alkalis, and forms an acetyl derivative melting a t 150'. On oxida- tion with nitric acid, it yields pentabyonaotoluqucirtone, CHBr,* CBr,?,, which crystallises from glacial acetic acid in yellow prisms melting at 160". 3 : 4 : 6-T~*ib~~omo-5-hydroxy-o-tolualdehyde, obtained by the reduction of the pentabromo-compound, forms small needles melting at lS7--!8So, and yields a benxoyl derivative melting at 167-168" and a n oxime melting at 207"; on oxidation, it yields tribomotolu- quinone melting a t 234". Attempts were made to synthesise this aldehyde by brominating p-hydroxy-o-tolualdehyde, In this way,OR(3ANLC CHEMISTRY, 99 4 : 6-dibromo-3-hyd~~oxy-o-to~uuldehyds is obtained ; it forms small needles melting at 161-162', yields an oxime melting at 197', and is oxidised to 4 : 6-dibromo-3-hydroxy-o-toluic acid, which forms small, white needles melting at 232'.On further treatment with bromine, this aldehyde is converted into tetrabromo-m-cresol. This can also be prepared by the direct bromination of m-cresol or of us-0- xylenol ; it forms long, thin needles melting at 194O, is easily soluble in alkalis, and forms a n acetyl derivative melting at 165-166", and a benxoyl derivative melting at 15S-154O ; when treated with nitric acid, it yields tribrornotoluquinone and an unstable mononitro-derivative melting at 88'.~?.ibromo-p-hydroxy~~~~~~uZuZdeiLyde, OH* C,Br,( COH),, prepared by treating pentabromohydroxytolualdehyde with lime water, crystal- lises from dilute alcohol in the form of colourless needles and prisms melting at 202', and yields a n acetyl derivative melting at 205-209'. An isomeric substance melting at 245-247", and forming an acetyl derivative melting at 218-220°, is obtained in small quantity in the By CHARLES MOUREU (Ann. Chint. Phys., 1899, [ vii], 18, 76--139).-An account of work already published. (Compare Abstr., 1896, i, 215, 426, 477, 646; 1897, i, 336, 403; 1898, i, 411, 518, 644, 660; 1899, i, 30, 125, 433, 494, 679, 700.) preparation of this hydroxyphthalaldehyde.R. H. r. Catechol Derivatives. G. T. &I. Hydrogenised Derivatives of Diphenylmethane and By DANIEL VORL~NDER (Annnlen, 1899, 309, Triphenylmethane. 348-355).-An introductory paper (see following abstracts). 31. 0. F. Formaldehyde Derivative of Dihydroresorcinol. By DANTEL VORL~NDER and FRITZ KALKOW (Aiznalen, 1899, 309, 356-374. Compare Merling, Abstr., 1894, i, 177, and Vorliinder and Kalkow, Abstr., 1897, i, 513). - The sodium derivative of methylenebisd-ihydroresorcinol crystallises in prisms and contains 2H,O. The anhydride (octohydroxantheizedionej forms the oxime, C,3H,y0,N3, which is microcrystalline, and melts at about 300'.Alcoholic ammonia converts methylenebisdihydroresorcinol into deca- hydroacridinedione, which has been described already. Nitrous acid transforms this substance into octol~yd.l.oacridinedio?~e, ~H,-CO-~:CH*~*CO~qH, CH,*CH,.C:N-C*CH,* CH,) which crystallises in white needles melting at 140--142", and yields acridine when distilled with zinc dust ; the oxime becomes brown above 200°, and melts and decomposes at 250". A similar ketonic base, C,,H,,O,N, obtained by distilling decahydroacridinedione, crystallises in flat needies and melts at 144'; the hydrociilo~~ide crystallises from water in colourless needles, and the oxinze melts and decomposes at about 2 8 0 O . The ketonic acid, CI3Hl8O5, obtained from methylenebisdi- hydroresorcinol and caustic alkali, forms anhydrous bccrizcm, silver, and100 ACSTRACTS OF CHIEMICAL PAPERS.lead salts ; the oxime and sernicarbaxone melt a t 159' and 218' respec- tively, and the diethyl ester boils at 235-240'under 24 mm. pressure. Methylenebismethyldihydroresorcinol, C,,H,,O,, and methylenebisdi- methylaihyldroresorcinol, C17H2,0,, melt at 152' and 187-188' respectively ; the latter yields tetyanzethyloctohydyoxanthenedione, C17H2203, which melts at 171' and, with alcoholic ammonia, forms tetramethyldecah ydroucridinedione. Met~ylenebis~~henyldiJLydroresorcinoZ, C,,H,,O,, melts at 2 12' ; diphenyloctohydroxanthenedione, C25H220S, melts at 225-226'. Pentarnethyloctohydroxunthenedione, C,,H,,O,, from dimethyldi- hydroresorcinol and acetaldehyde, melts at 174'. Etlqltetramethylocto- hydrorcanthenedione, C,,H,,O,, melts at 139'.Wexamethyloctohydyo- xanthenedione, C,,H,,O,, melts at 245'. Compounds of Dihydroresorcinol with Aromatic Aldehydes. By DANIEL TORLANDER and 0. STRAUSS (Annalen, 1899, 309, 37~-383).-Benxylidene6isdiJ~ydro~esorcinol, C,,H,,O,, prepared from dihydroresorcinol and benzaldehyde, melts and decomposes at 208' , phenyloctohydyoxanthenedione, C,,H,,O,, melts a t 255', and the p-nitro-derivative, obtained fiom p-nitrobenzaldehyde, dihydroresor- cinol, and glacial acetic acid, melts at 246'. Phenyldecahydro- acridinedione, C1,Hl9O,N, produced on heating phenylhydroxanthene- dione with alcoholic ammonia, does not melt below 310°, and fosms, i n alcohol, a colourless solution which exhibits blue fluorescence ; distillation with zinc dust gives acridine.Benxy I idene bisdime t Ji y ldihydroresorcino I , C23H28041 obtained from dimethyldihydroresorcinol and benzaldehyde, melts at 193'; phenyltetva- methyloctohydvoxcanthenedio~ae, C2.7H2G03, melts at 200'. Cuminylidene- bisdimethyldiJnjdyoresorcinol, C26H3203, melts at 173'. Benxylidenebispheny ZdiJL ydroresorcinol, C31H2S04, me1 t s at 1 2 5', water being eliminated ; triphenyloctohydroxanthenedione, C,, K2603, is identical with '' benzylidenephenyldihydroresorcinol " (Vorlander and Erig, Abstr., 1897, i, 275), and melts at 230'. Triphenyldecahydro- acridinedione, C,,H270,N, forms red solutions having green fluorescence. By LEO MARCHLEWSKI (L pr. Chem., 1899, [ii], 60, 407-408. Compare Abstr., 1896, i, 96 and 235).- When isatin reacts with o-phenylenediamine acetate in acid solution, a mixture of indophenazine and o-aminophenimesatine is formed ; as the imesatine cannot be converted into the indophenazine under the conditions employed, i t is clear that the isatin acts as a mixture of lactam and lactim.Acids, such as acetic acid, appear t o be able t o cause the con- version of the lactim into lactam, as isatin when condensed with o-phenglenediamine in 50 per cent. acetic acid solution gives only a trace of imesatine, whilst the latter changes only excessively slowly into indophenasine when bailed with acetic acid of t h a t btrength. A . L. Optically Active truns-Hexahydrophthalic Acids. By ALFR~D WEIIKEH. and H. E. CONRAD (Bey., 1899, 32, 3046-3055)- k.ans-HexahSdrophthalic acid is a racemic compoupd apd is resolved M.0. F. M. 0. F. Tautomerism of Isatin.OltCANIC CHERIISTRY. 101 into its optically active components by fractional c r y s t a h a tion of its quinine salts in alcoholic solutions ; the neutral salt of the dextro- rotatory acid separates first, whilst the acid salt of the laxorotatory acid remains dissolved. The anhydrides of the optically active acids, prepared by heating these compounds with acetic chloride, crystallise in broad plates, whilst the corresponding racemic compound separates in needles. The dimethyl esters were produced by heating the acids with methyl alcohol containing hydrogen chloride ; the monomethyl esters were obtained by warming the anhydrides with methyl alcohol. The rnonoumide of the racemic acid was prepared by passing dry ammonia into an acetone solution of the inactive anhydride ; it melts a t 196".Active traiuhexahyd ro- phtlialiG acids and derivatives. d-truns-Acid ......... I- ,, ......... &Anhydride ......... L ,, ......... d-Dimethyl ester ... I- ... d-Monomet hyl ester. I- ,) 9 , 9 , E U l D . - 76.7 75.8 ] - 29-6 26.5 - 24.8 } M. p. of racemic M.p. compound. 17 8 -1 83" 215" 164" 140 below 0' 33 39" 96 cis-Hexahydrophthalic acid is not resolved into active components by the aid of quinine, cinchonine, o r coniine; this acid differs from its trans-isomeride in forming the ucid potussium salt, CyH,,04K c 3H20. Constitution of Santonic and Metasantonic Acids and of Metasantonin. By LUIGI FRANUESCONI (Gaxxstta, 1 S99, 29, ii, 181-257. Compare Abstr., 1898, i, 267).-A detailed account is given of the various transformations of santonic and metasantonic acids and of metasantonin.Xuntonic ucid dioxime, C,5H2204N2, is a white, friable substance which melts and decomposes a t 120-125" ; it dissolves readily in dilute halogen hydracids, alcohol, or ether. Its specific rotatory power is [a]. - 102.4". With excess of phenylhydrazine, santonic acid gives the phenyl- hydraxone of santonic acid phenylhydraxide, C27H3202N4, which is an orange-yellow powder melting and decomposing a t 95" ; it is readily soluble in alcohol, ether, or acetic acid. G. T. M. I t gives a barium salt, (C,,H,,O,N,),Ba. yO*~Me*QH-CO*~*OH Tviketosantonic acid, CMe. cH, c. CHMe. CO,H, obtained by the action of bromine on santonic acid, forms glistening, straw- yellow needles melting and decomposing at 234" ; it is readily soluble in ethyl acetate, alcohol, or water, the aqueous solution having an intense yellow colour, I t s specific rotatory power in alcohol is [ u ] ~ - 458.7'. The barium salt, C,,H120,Ba t 2H20, is a golden- yellow substance.The ethyl ester, C,,H,,0,*C02Et, forms glistening, pale yellow needles which melt a t 157-158" and dissolve readily in102 ABSTRACTS OF CHEMICAL PAPERS. ethyl acetate or alcohol; the specific rotation i n alcohol is [.ID - 394.1'. The dioxinze, C15H,,0,(NOH),, is a hard, friable substance of a straw-yellow colour and is readily soluble i n ether, alcohol, or w:rtter. The anhydride of the dioxime, C15H405<Z>0, is a hard, friable, orange-coloured mass which softens at about 1 30°, melts and decomposes at 140°, and dissolves in the ordinary solvents.~ribromo-a-santonin, C15H1503Br3, obtained by the action of bromine on santonic acid! melts a t 187-18S0 and dissolves in ethyl acetate and to a less extent in ether, but is insoluble in solutions of alkali car- bona tes. T. H. P. Action of Sodium Methoxide on Dibrornides of Propenyl Gompounds and of Unsaturated Ketones. By F. J. POND, 0. P. MAXWELL, and G. M. NORMAN (J. Amer. Chern. Xoc., 1899,21, 955-967. Compare Pond and Beers, Abstr,, 1898, i, 645).-When isoapiole dibromide (Ciamician and Silber, Abstr., 2890, 1294) is treated with sodium methoxide according t o the method previously described, a ketone, COEt* C6H(OBle),:0,:CHq is obtained which crystallises from alcohol in colourless prisms melting at 95.5' ; its oxime cryatallises from methyl alcohol in colourless needles melting at 124", and is readily reconverted into the ketone when heated with dilute sulphuric acid on the water-bath.The constitution of the ketone follows from the fact that it yields propionic acid when heated at 250" with concentrated sulphuric acid. Eugenol propyl ether, OYr* C,H,(OMe)*CH,* CH:CH,, is a colourless oil boiling a t 270.5'and having a sp. gr. 1.0032. Cahours (this Journ., 1877, i, 461) gives its boiling point as 263-265'; when boiled with alcoholic potash, it is converted into isoeugerml propyl ether, CHhlIe:CH* C,H,( OMe)*OPr, which distils at 280-281' and forms large, colourless prisms melting at 53-54'; it may also be obtained by the action of propyl bromide on the potassium salt of isoeugenol.I t s dibmmide melts at 53-54", is readily soluble in alcohol or ether, but cannot be recrystallised without decomposing ; when treated with sodium methoxide, it yields t h e ketone, COEt- C,H,(OMe)*OPr, which, after distillation under reduced pressure, crystallises from methyl alcohol in large prisms melting at 63-64', and boiling with slight decomposition at 284-287' under atmospheric pressure. The oxinze, Cl,Hl,O,N, forms large crystals melting at 114'. Benzylideneacetophenone (Claisen and Clapardde, Abstr., 1882,5 12) yields a dibwmide crystallising in small prisms and melting at 156O; this dibromide is converted by the action of sodium metboxide into dibenzoylmethane (Baeyer and Perkin, Abstr., 1884, 64 ; Claisen, ibid., 1887, 575).An unstable oil, probably the unsaturated ether OMe* CPh:CHBz, has been isolated as a n intermediate product; on treatment with dilute acids, it yields dibenzoylmethane. Anisylideneacetop~enone crystallises in fine, yellow needles melting at 77-7Soj its dibromide cryatallises in white prisms melting a t 140-141', and on treatment with sodium methoxide yields anisoyLORGANIC CHEMISTRPI 103 befixoylmethacne, ClsH1403, crystallising in plates and melting at 131-132'. Bromine converts the diketone into a bromine derivative melting at 127-128'. By R. C. FARNER and ARTHUR HANTZSCH (Ber., 1899, 32, 3101-3109)- The criteria enumerated in this vol., i, 95, are applied to the cases in question. Isonitrosoacetone, NOH:CH* CMeO, is neutral to litmus, is not appreciably dissociated, and does not form a compound with dry ammonia.But the sodium salt exhibits on dilution a n increase of conductivity, A1024;321 only a little greater than in the case of salts of strong acids, and it IS only slightly hydrolysed in aqueous solution. Consequently, isonitrosoacetone is a pseudo-acid, and its sodium salt has a different constitution, either NO*CH:CMe*ONa, CMe<ti>N*OEa, J. J, S. a-Oxirninoketones and Quinoneoximes as Pseudo-acids. or ONa CMe<$i>N. Quinonemonoxime, NOH:CGH,:O, does not unite with ammonia in benzene, and very slowly in ethereal, soIutions ; but its sodium salt exhibits the normal increase of conductivity on dilution, Alo24-32 ; it must therefore be the salt of a comparatively strong acid, and hence quinoneoxime is a pseudo-acid.Quinoneoxime, in aqueous solu- tion, has a decided acid reaction and a moderately large dissociation constant, and its very dilute solution has the same (greenish-yellow) colour as equivalent solutions of the red sodium (with 2&H20) and green potassium salts (with 1H,O) ; hence the oxime 'itself undergoes a partial transformation in aqueous solution and the case is one of ' ionisation isomerism.' Quinonedioxime, on the other hand, has no appreciable conductivity, and i t s sodium salt is a true oxime salt, for it is largely hydrolysed in aqueous solution, as the abnormally large increase in conductivity on dilution, A1024-32, shows ; indeed, the solution gradually deposits a n anhychicle, (CGH4<s>O) , a bright- red, amorphous, very stable substance. o-Toluquinoneoxinie resembles its lower homologue, and '' nitroso-orcinol " forms a very strongly acid solution.C. E. B. Space Isomerism of the Ethers of Toluquinoneoxime. By W. CONGER MORGAN (Amel.. Chem. J., 1899, 22, 402--407).-The benzoyl derivative of toluquinone-m-oxime melting at 139' (Bridge and Morgan, Abstr., 1899, i, 130) is completely converted into the stereoisomeride melting at 193' by heating with alcohol in a sealed tube for 3 hours at 120' ; the latter, under similar conditions, is not changed, but on raising the temperature t o 150°, is completely decom- posed. Caustic alkalis hydrolyse the compound of lower melting point to the corresponding oxime, which, however, on treatment with benzoyl chloride, yields ,the modification of higher melting point exclusively ; the latter appears from these experiments t o be the more stable form, The phenomena described by Bridge and Morgan have been repro- duced completely in the ethers formed by the interaction of acid chlorides with the sodium salt of the oxime prepared by the action of amyl nitrite on the sodium salt of o-cresol; since there is no104 AUSTRSCTS OF CHEMICAL PAPERS. possibility of a hitro-compound being formed under these conditiods, although this is not precluded in the action of nitrous acid on the cresols, the lower melting stereoisomerides cannot be considered as merely the higher melting compounds rendered impure by such ad- mixture.The benzoate, C,,H,,O,NBr, of bromotoluquinone-o-oxime, prepared by boiling the corresponding dibromide, Cl4HI1O3NBr2 (Bridge and Morgan, Zoc.cit.), with 75 per cent. alcohol, forms yellow crystals and melts a t 184". The dichloride, C,,H,,O,NCI,, of toluquinone-o-oxime benzoabe crystallises from glacial acetic acid in short, thick, colourless prisms and melts a t 149'; when boiled with dilute alcohol, it loses hydrogen chloride and yields cldorotoluquinone-o-oxime benzoate, C,,H,,O,NC1, which forms yellow crystals and melts and decomposes a t 185-133'. All these compounds appear t o exist in one form only. W. A. D. Isomerism in the Menthol Series. By IWAN L. KONDAKOFF and EUGEN LUTSCHININ (J. pr. Chem., 1899, [ii], 60, 257-279).- Menthyl iodide, prepared by the action of hydriodic acid on either menthol or menthomenthene, boils a t 124-126' under a pressure of 18 mm., and has a sp.gr. 1.3836 at 0' and 1,3155 at 16.5'. It acts very rapidly on moist silver oxide, yielding tertiary menthomenthol ; the passage from secondary menthol to tertiary menthomenthol is closely analogous to that from methylisopropylcarbinol to dimethyl- ethylcarbinol. Dihydrocarvone, prepared by oxidising the dihydrocarveol from I-carvone, boils a t 221-224', has a sp. gr. 0.9308 a t 16', a refrac- tive index n, 1.47243, the molecular refraction being 45.78; its specific rotation is [.ID + 17' 27.5'. The constants obtained for the product from d-carvone were as follows : boiling point, 221-222'; sp. gr. 0.9269 a t 22', refractive index nD =1*46998, molecular refraction 45.80, and specific rotatory power [a], - 19' 35'.This dihydrocarvone is readily reduced by sodium and alcohol to pure dihydrocarvol boiling at 224-225', and is readily converted into carvenone by Kondakoff and Gorbunoff's method (Abstr., 1898, i, 145); the latter substance boils for the most part a t 231-233' under 763 mm., and at 101-103° under 10 mm. pressure, but invariably leaves a residue which boils a t 233-240'. Klages' observation that carvenone may be obtained by treating dihydrocnrvone with formic acid (Abstr., 1899, i, 624) is the natural outcome of the work of Kondakoff and Gorbunoff ; it is not necessary, however, to use anhydrous formic acid or to prolong the action; the product obtained by this method boils a t 232' under 759 mm. pressure, and not a t 232-235" as stated by Klages. Carvomenthol, obtained by reducing carvenone by Wallach's pro- cess (Abstr., 1894, i, 44), boils at 220-221' under 762 mm.pressure, but contains a fraction boiling a t 240' ; i t has a sp. gr. 0.9070 at 20.2" ; its refractive index is nD 1,4672, its molecular refraction being 47.49. The foregoing carvomenthol was purified by conversion into tetra- hydrocarvone as recommended by Wallach, but much loss is ex- perienced in this process. The substance now boiled at 222", had aORGANIC CHEMISTRY. 105 ~ p . gr. 0.9010 at 23', a refractive index n, 1.4696, and a molecular refraction 47.58. Carvomenthol, prepared from specimens of active carone, varies considerably in opticzl activity, as do the derivatives prepared from it. Carvonzenthyl acetate, C,,H,,OAc, boils at 235-238' under 76 1 mm.pressure, and a t 105-107° under 11 mm.; it is a colourless, fairly mobile liquid having a faint odour of cherries; it has a sp. gr. 0.9250 at 22'/4', a refractive index n, 1.45079, a molecular refraction 57.42, its specific rotation being [ u ] D + 4'7'. Carvomenthyl chloride, C,,H,,CI, is colourless and has an odour resembling menthyl chloride; it boils at 90-95' under 15 mm. pressure, and at 82-55' under 11 mm., is optically inactive, has a sp. gr. 0.9450 a t 21°/4', and refractive index VZ, 1.46534 a t 21°, the molecular refraction being 50.48. The bi*omide, CloH19Br, is colour- less, boils a t 95-99' under 10 mm. pressure, has a sp. gr. 1,1870 at 21°, a refractive index nD 1.49060 a t 21"/21', and a molecular refrac- tion 53.39.Carvomenthene, prepared by heating carvomenthyl chloride or bromide with alcoholic potash, is divisible in two portions by fractional distillation, about 90 per cent. of the whole distilling a t 172-1745", and the rest a t 174°5-1780. It is a colourless, mobile liquid having an odour of menthene, is altered by exposure to air, and reacts readily with permanganate and with bromine. The portion of the carvomenthene of lower boiling point has a sp. gr. 0.8230 a t 16.5"/4', a refractive index n, 1,45979, molecular refraction 45.68, and a specific rotation [a], - 2'4'. The fraction of higher boiling point had a sp. gr. of 1.8230 a t 19'/4', a refractive index n, 1.46105, a molecular refraction 45.89, and a specific rotatory power [a], - 1'28. Carvc?;nlenthene hydrochloride boils at 90-98" under 18 mm., and a t 89-95' under 16 mm.pressure ; it has a sp. gr. 0.9390 at 19"/4', a re- fractive index ~YL, 1.464941, the molecular refraction being50-95, whilst its specific rotatory power is [ a ] , - 1'22'. I t s properties are thus identical with those of carvomenthyl chloride, with the exception of the rotatory power. Baeyer has shown (Abstr., 1893, i, 722) that carvomenthene combines with hydrogen bromide or iodide in the cold, yielding tertiary halogen derivatives, convertible through the intermediary of the corresponding acetates into a mixture of carvomenthene and tertiary carvomenthol. The authors have prepared the bromo-compound by heating the hydro- carbon with strong hydrobromic acid a t 160-170° ; it boils at 92-98' under 10 mm.pressure, has a sp. gr, 1.1620 at 20*5"/4', a refractive in- dex n, 1.48822 at 20*5", and a molecular refraction 54.27 ; it is opti- cally inactive. Its properties are almost identical with those of carvo- menthyl bromide, but it is highly probable that it consists of a mix- ture of the secondary and tertiary bromo-compounds, derived from two isomeric carvomenthenes in the parent hydrocarbon. The carvo- menthene regenerated from the hydrobromide boiled at 172-1 75', had a sp. gr. 0'8230 at 20'/4', a refractive index VZ, 1.45959, a mole- cular refraction 45.69, and a specific rotatory power [a], - 0'83'. Carvomenthyl chloride or bromide, on treatment with moist silver VOL. LXXVIII. i. 2106 dBSTRACTS OF CHEMICAL PAPERS. oxide, affords tertiary carvomenthol and a small auantitv of a sub- stance, C10H2203, whYich crystallises in slender neekes anh melts a t 1 0 1-1 0 2 O .It is not improbable that the behaviour of menthomenthol and carvomenthol illustrates a general law whereby hydro-aromatic alcohols containing the group *CHR*CH(OH)* are converted by halogen hydrides into tertiary halogen derivatives. The behaviour of fenchyl alcohol in this respect is being investigated. Solubility of Camphor in Hydrochloric Acid. By AL. J. ZAHARIA (Chem. Centr., 1899, ii, 308; from Bul. SOC. Sci. Bucuresci, 1899, 8, 53-61).--CTamphor is rather soluble in water and the aqueous solution becomes turbid on addition of sodium carbonate or sodium chloride solution. Camphor is very soluble in concentrated hydrochloric acid, and the more concentrated the acid and the lower the temperature the greater the quantity dissolved.On account of the volatility of camphor, the amount dissolved could not be determined. A saturated solution containing 35.74 per cent. of hydrochloric acid has a sp. gr. 1.1405. The acid solution of pure camphor is orange- yellow, and of impure camphor reddish-yellow, changing gradually to deep-red. Any excess of camphor is coloured light brown and may be dissolved with the exception of a small resinous residue by adding more hydrochloric acid. When a few drops of nitric acid are added t o the hydrochloric acid solution, an oil separates which, when distilled or treated with water, again forms camphor. By electrolysing the hydrochloric acid solution, hydrogen is liberated a t the cathode and a liquid is quickly formed a t the anode, which by exposure to the air or treatment with water regenerates camphor.The amount of camphor in solution could not be determined polarimetrically, for the rotatory power depends on the quantity of hydrochloric acid present. When chlorine is passed into a hydrochloric acid solution of camphor, an oil is very slowly formed. Camphor appears t o behave towards hydriodic acid in a similar way. E. W. W. Nitroso-derivatives of Caryophyllene and Cadinene and their bearing on the Characterisation and Classification of the Besquiterpenes. By OSWALD SCHREIR'ER and EDWARD KREMERS (Pharrn. Archives, 1899, 2, 273-300. Compare Abstr., 1899, i, 619). -A pure specimen of caryophyllene, boiled at 136-137" under 20 mm.pressure, had a sp. gr. 0.90301 at 20°/20", index of refrac- tion N~ 1.49976 a t 20°, and specific rotatory power [a], .- 8.959 a t 20°. The nitrosite is not polymerised, but has the simple formula C15H2403N2, as shown by cryoscopic determinations in benzene solu- tion ; it has a specific rotatory power [a],, of about + 103 in 1.6 per cent, benzene solution, and, with benzylarnine, it yields a product which melts a t 167'. When exposed t o sunlight in absolute alcoholic solution, it is transformed into a colourless (a) isomeride with the same mole- cular weight ; this melts a t 113-114', is soluble in alcohol and benzene, and has no appreciable optical activity. When the nitrosite is exposed to sunlight in benzene solution, another colourless (/I) substance is formed, which melts at 146-148', ,and is insoluble in benzene or A.L.0 R G AN I C C H E bl ISTR T, 10'9 alcohol j the yellow-orange rays are most active in effecting this change. The nitrosochloride can be obtained crystalline by mixing caryophyl- lene, alcohol, ethyl acetate, and ethyl nitrite, cooling in a freezing mixture, adding saturated alcoholic hydrogen chloride, leaving the whole in the cold for an hour, and then exposing it to sunlight ; it melts and decomposes a t 1 5 8 O , and has the bimolecular formula (C,,H,,ONCl), ; with benzylamine, i t forms two derivatives, u and /3, melting a t 167' and 12s' respectively ; the former is the less soluble in alcohol. The nitrosate is also bimolecular; with benzylamine, i t yields a product, melting a t 12S0, identical with the P-product obtained from the nitrosochloride. The hydrochloride of caryophyllene can be obtained crystalline by saturating an ethereal solution of the sesqui- terpene with hydrogen chloride, and exposing the solution to intense cold ; it melts a t 69-70'.When cadinene is mixed with glacial acetic acid, cooled with a freezing mixture, ethyl nitrate added, the mixture treated with strong nitric and glacial acetic acids, and diluted with alcohol, cadinene nityosate, melting and decomposing a t 105-1 lo", is precipit- ated. When a saturated solution of hydrogen chloride in glacial acetic acid is added, instead of the nitric and acetic acids, a nitrosocldoyide, melting and decomposing a t 93-94', is obtained. C. F. B. Oil and Terpenes from Aralia Nudicaulis.B~WILLIAM C. ALPERS (Chem. Centr., 1899, ii, 623 ; from Amer. P?m~nz., 71, 370-378).- The fresh root of Aralia nudiccculis contains 40-60 per cent. of water, and the dry drug yields on a n average 5.53 per cent, of ash, which contains about 1-38 per cent. of sodium and potassium chlorides and sulphates, The dark red, fatty oil, obtained by extraction, has a sp. gr. 0.921 a t 20', is soluble in light petroleum, benzene, ether, o r chloroform, slightly so in absolute alcohol, and insoluble in water ; i t solidifies at 3', has acid number 7.3, saponification number 192, iodine number 106, and molecular weight of about 900 ; it consists chiefly of triolein. About 0.12 per cent, of an oil is obtained by distilling finely powdered aralia with steam ; it has a pleasant, aromatic odour, and is composed mainly of a sesquiterpene, wwliene, CI5Hl4, which boils at 270", has a sp.gr. 0.9086 at 20', a specific rotatory power [aID - 7 to - So, and a refractive index nD 1.49936. It combines with bydrogen chloride t o form an oily hydrochloride, but does not yield a solid bromide by the action of bromine. With a solution of hydro- gen chloride in glacial acetic acid, it forms a bluish compound. The ethereal oil also contains a small quantity of a sesquiterpene alcohol, and a little azulin, U,,H,,O, which boils a t about 300". E. W. W. Liquorice Oil. By HEINRICH HAENBEL (Chenz. Centr., 1899, ii, 624 ; from Pharm. Centr.-H., 40, 533).--Sy distilling Spanish liquorice root (Glycyryhizu glubrcc), 0.03 per cent. of an ethereal oil is obtained ; the Russian roots yield 0.035 per cent.These oils have a feeble acid reaction, which is possibly due to glycyrrhizic acid, but their composition is not identical, for whilst the Russian oil is dextrorotatory, the Spanish is laevorotatory. E. W. W, i 2108 ABSTRACTS OQ CHEMICAL PAPERS. Ethereal Oil of Poplar Buds. By FRITZ FIcmxR and E. KATZ (Ber., 1899, 32, 3183-3285).--'lhe principal fraction obtained by distilling oil of poplar buds under diminished pressure is a terpene boiling a t 132-137' under 13 mm. pressure, and a t 263-269' under ordinary pressure; it has a sp, gr. 0.8926 a t 15O/4', and a specific rotatory power 10'48' at 22'; its vapour density corresponds with that of a sesquitierpene, C,,H,,. The nitrosochloride, C,,H,;KOCl, obtained from the sesquiterpene and amyl or ethyl nitrite, and hydrochloric acid, separates as a crys- talline powder from its solution in benzene or chloroform on the addition of methyl alcohol; it melts indefinitely, the range of tem- perature being 164-1 70".The nitrolpiperidine from the preceding compound and piperidine crystallises from alcohol and melts at 151-152" ; the nityolbenzyl- amine crystallises from alcohol in needlesand melts a t 132-133' ; the chlorides of these substances have the composition C,,H,,ON* C,NH,,, + HCl and C,,H,,ON*NH* CH,Ph -I- HCl respectively. The nitroso- or iso~itroso-sesp.2c~~rpene, C15H2,:NOH, is obtained as an oil on treating the nitrosochloride with sodium ethoxide ; on re- duction, this substance yields an aminosesquiterpene.The nitrosite, produced by the action of nitrous acid on the sesqui- terpene, separates a t first in blue needles melting at 127'; after crystallisation from alcohol, it becomes colourless and melts at 172'. The nitrosate from the sesquiterpene, amyl nitrite, and nitric acid, crystallises from benzene and melts at 162-163'. The sesquiterpene does not yield crystalline additive compounds with bromine, hydrogen bromide, or hydrogsn chloride, neither does it combine with elements of water (Wallach, A bstr., 1893, 101). The properties of the sesqui- terpene of poplar buds and its derivatives resemble those of t,he humulene in oil of hops (Chapman, Trans., 1895, 67, 57 and 780). On the other hand, the sesquiterpene, although it may contain humu- lene, cannot consist wholly of this hydrocarbon, for the former is optically active whilst the latter is inactive.The higher fractions of poplar oil coxltain a mixture of paraflins, stearoptenes," consisting of the hydrocarbon C,,H,, and its higher homologues ; the total amount of paraffin in the oil is only h per cent. G. T. M. Glucosides and Enzymes contained in the Root of some Spirmas. By MARTINUS W. BEYERINCK (Chenz. Centr., 1899, ii, 259 ; from C'entr. Bakt. Parusitenk., [ ii], 5, 425--429).-The roots, rhizomes, and lower portions of X p m m ulrnayia, X.3Jipendula, and 8. palrnata contain a glucoside, gaultherin, and an enzyme, gaultherase, and by the interaction of these compounds methyl salicylate is formed. The elder portions of the roots and rhizomes of 3.kamschatica also contain a second glucoside, spirzin, which is decomposed by gaultherase, forming salicylaldehyde. Gaultherin is prepared from the root nodules of X.$Zipendula by treating with boiling alcohol or boiling water, which dissolves the glucoside, but decomposes the enzyme. The glucoside could not be obtained in a crystalline form. Gaultherase, prepared from the same root by allowing the enzyme toORGANIC CHEMISTRY. 109 act on the glucoside and then extracting with alcohol, is soluble in water. It is not identical with emulsin, since it does not act on salicin or amygdalin, and gaultherin is not attacked by emulsin. By distilling the decomposition products formed in the production of gaultherase in steam, gaultheria oil is obtained. Hydrocyanic acid could not be detected in the products of the decomposition of gaultherin or of spirzein.The presence of even 0.1 per cent. of gaultheria oil prevents the growth of mould. The odoriferous substances contained in plants may serve to protect them from insects. The merest traces of Capuchin oil are sufficient to prevent the growth of Sacchammyces mycodevma, but this oil has very much less effect on the lactic acid ferment or on acetic acid bacteria. This preventive action may be due to the presence of a hydroxybenzylthiocarbimide. E. W. W. Derride and Pachyrhizide : Indian Fish Poisons. By H. E. TH. VAN SILLEVOLDT (Chem. Centr., 1899, ii, 588-589 ; from Ned. Tijd. Pharm., 11, 246-256; and Arch. Pharm., 1899, 237, 595).-The stupefying fish poisons occur mainly in plants of the family of Papilionucece.Derride, C3,H3,01,, prepared from the root of Dewis elliptptica, Benth., by treatiag with water, extracting with alcohol, evaporating, and treating the residue with ether, is a pale yellow substance,melts a t 73", and is easily soluble in the usual organic solvents, slightly so in light petroleum, and insoluble in water. The alcoholic solution has a faintly acid reaction. Derride is dis- solved by sulphuric acid, forming a brownish-violet solution, from which it is reprecipitated by water, and it appears to combine with phenylhydrazine. By boiling with an alcoholic solution of hydrogen chloride, it forms an anhydro-derivative, C33H2809, wh:ch is also present in crude derride, and is nct dissolved by ether. This com- pound forms small needles, melts a t 214O, and when treated with hydriodic acid forms a compound, ~,oH190,(OH)3, which melts a t 2 4 0 O .The preparation of pachyrhizide, C,,H,,Olo, from the seeds of Pachy~hizzcs angulatus, Rich., is similar to that of derride. Pachy- rhizide melts at 81°, and closely resembles derride. A compound, C2,H2,09, which is insoluble in ether and melts a t 196" is also con- tained in the seeds. The anhydro-derivative of pachyrhizide, C,,H,,O,, obtained by warming it with an alcoholic solution of hydrogen chloride, is a crystalline substance, melts at 182O, combines with phenylhydrazine, and contains two methoxy-groups. Derride and pachyrhizide appear to belong to the same homologous series as Pfaff's timboin (Abstr., 1191, 938), for which the formula C,,H,,O,, may be calculated from his analyses.E. W. W. Chlorophyll. By G. BODE (J. p. Chem., 1899, [ii], 60, 385-3136). -A reply to lSlarchlewski (Abstr., 1899, i, 381). Phylloxanthin. By G. BODE (Chem. C'sntv., 1899, ii, 529; from Bot. Centr., 20, 227--239).-A continuation of the controversy with Marchlewski (Abstr., 1899, i, 381). The alcoholic plant extract which contains chlorophyll combined with a lecithin is named crude110 ABSTlElACTS OF CHEMICAL PAPERS. chlorophyll solution, By the action of weak acids, this compound undergoes an intramolecular change, being converted into the crystal- line, olive-green chlorophyllan, and by the action of alkalis or of strong acids is decomposed into the lecithin constituents and alkali or acid compounds of chlorophyll ; the latter (Marchlewski’s alkachlorophyll and phyllocyanin) are decomposed by water.The chlorophyll com- pounds have different colours, according to the nature of the solvent and the concentration, which determine whether the compound remains undecomposed or is resolved into ions (compare Ostwald and J. Wagner; Deussen). Marchlewski’s phylloxanthin is impure chlorophyllan and, like phyllotaonin, not really a chlorophyll derivative, whilst phyllo- porphyrin is a product formed from chlorophyll by an intramolecular change. E. W. W. Furfuraldehyde from Beetroot and Molasses. By KARL ANDRL~K (Chem. Cent?.., 1899, ii, 460 ; from Zeit. 2uck.-Ind. Bdhm., 23, 55 1-559).--The colour of the furf uraldehyde-phloroglucide obtained from molasses is not the same as that of the pure compound.I n an experiment in which large quantities were employed, about 7 per cent. of a substance which appeared to be methylfurfuraldehyde was found in the portion which distilled a t 162-168’. Constitution of Arginine. By ERNST SCHULZE and ERNST WINTER- STEIN (Ber., 1899, 32, 3191-3194. Compare Abstr., 1898, i, 281 ; 1899, i, 107).-The formula previously proposed by the authors for arginine is confirmed by the fact that this substance is formed when ornithine is treated in the cold with cyanamide. Ornithine itself is probably as-diaminovaleric acid, since the distillation of its hydro- chloride yields a small amount of a substance which gives the re- actions of pyrrolidine, but has not yet been analysed. By D. LAWROFF (Zeit, physiol. Chem., 1899, 28, 585--586).-A method is described of isolating the hexon bases by the use of benzoyl chloride and subse- quent extraction with various solvents such as light petroleum. E.W. W. A. H. Benzoyl Compounds of Hexon Bases. W. D. H. An Alkaloid contained in the Bark of the Pomegranate. By ANTONIO PTCCININI (Gaxxettcc, 1899, 29, ii, 311-318).--From the light petroleum mother liquors obtained in the preparation of methyl- granatonine from the pomegranate root, an oily substance may be separated from which the author has isolated a buse of the composition C,HIFON. On decomposing the picrate by means of potassium carbon- ate, it is obtained as a colourless oil which has a very faint basic odour and boils at 114-117O under 26 mm. pressure. It is soluble in water in all proportions, giving a strongly alkaline solution.The picrate, C1,H,,O,N,, forms a crystalline powder melting at 152-153’ and soluble in boiling alcohol. The aurichZoi*ide, C,H170N,HAuCI,, separates from dilute hydrochloric acid in orange-yellow rosettes and melts at 115-1 17”. The hydrochloride is a viscous mass soluble in water. ‘J.’he base forms a semicap6cczone, C10H200N4, which separates fromORGANIC CHEMISTRY, 111 water in large, colourless, lustrous crystals which melt a t 169' and dissolve in alcohol, but are insoluble in ether. The hydrochloride, C,,H2,0N,,HCl, crystallises from dilute alcohol in slender, colour. less needles which melt with decomposition and evolution of gas a t 208' and are very soluble in water but insoluble in absolute alcohol ; the aqueous solution of the hydrochloride gives a yellow, oily precipi- tate with a solution of gold chloride.T. H. I?. By GOTTFRIED FENNER and JULIUS TAFEL (Bey., 1899, 32, 3220-3228. Compare Abstr.i 1898, i, 446)-The normal aurichloride of piperidine is always formed when auric chloride acts on piperidine hydrochloride in aqueous solution, and is also produced by the action of water on the abnormal salt. The latter is formed when piperidine hydrochloride and auric chloride are brought together in alcoholic solution, or when the normal salt is treated in alcoholic solution with hydrogen chloride or piperidine hydrochloride. It appears to dissociate when heated, either alone or in alcoholic solution, into the normal salt and piperidine hydrochloride, Abnormal isopropglamine aurichloride, ( C,H,oN),AuCl,, is prepared in a similar manner to the piperidine compound, and is a golden-yellow, microcrystalline powder melting a t 159' ; water decomposes it with formation of the normal salt.Abnormal 1-methyl piperidine auricldoride, (C,H,,N),AuCl,, melts between SO and 88' and yields the normal salt when treated with water. I n aqueous solution, 2 : 5-dimethylpyrrolidine yields an oily normal aurichloride, but in alcoholic solution a n abnormal aurichloride, which crystallises in yellow plates melting at 102-104°. Abnormal guinoline uurichloride melts a t 180' and decomposes a t 260'. Methylamine, coniine, aniline, and pyridine do not appear to yield abnormal salts. A. H, Synthesis of Glutaric and Trimethylene Derivatives.By ICILIO GUARESCHI and ERNESTO GRANDE (Chem. Centr., 1899, ii, 439-440; from Atti. Real. Accad. T o r h o , 34. Compare ibid., Abnormal Aurichlorides of Organic Bases. 33)-3 ; 5-Dicyano-4methg 2-4-eth?/Ztrimet~~Z~nedicccrbonimide- (dicyano- homocaronimide), NH<Co.C(CN, co*F(C")>CMeEt, prepared from the di- bromide, N H < ~ ~ , " ~ ~ l ~ ~ { > C M e E t , by heating at 110' for a \ I short time, crystallises in hard, lustrous, rhombic prisms, melts a t 210°, and is slightly soluble in water. When heated with sodium hydroxide, the imide loses 1 mol. of ammonia, and the SOlUtiOR, after acidifying with acetic acid, forms a silver salt when treated with silver nitrate ; by the action of hydrogen sulphide on this salt, an acid is obtained which is soluble in water and melts a t lS4'.Unlike dicyano- 2 : 6-dioxy-4-methyl-4-ethylpiperidine, the dicarbonimide does not evolve ethane from neutral aqueous solutions, and even when heated to 240-245' gives only small quantities of carbon monoxide, methane, and ethane. The ammonium derivative of 3 : 5-dicyano-2 : 6-dioxy- 4-dimethy@iperidirte, prepared by the action of acetone on ethyl cyanoacetate in presence of alcoholic ammonia, forms a white, crystalline, easily soluble mass ; its aqueous solution does not evolve gas even if112 ABSTRACTS OF CHEMICAL PAPERS. in lustrous, colourless leaflets, melts a t 216-217', and is slightly soluble in cold water, more so in alcohol or acetic acid. With potass- ium nitrite and sulphuric acid, it gives a characteristic, yellow colora- tion, and when heated at 310-320' evolves methane. The silver derivative, C,H,O,N,Ag, forms a white, crystalline precipitate. The dibromo-derivative, C,H102N,Br2, melts a t 190-1 95", and when heated for a long time with a 40 per cent.solution of acetic acid yields 3 : 5-dicyano-4-dimethyZtrimethyZenedicnrbonimide, CgH70,N,, which crystallises in small, hard, lustrous, colourless prisms, melts and decom- poses at 242', is soluble in water, alcohol, or acetic acid, and forms a silver salt. 3 : 5-Dicyano-2 : 6-dioxy-4- methyl-4-lzexylp~eridine, pre- pared by the action of methyl hexyl ketone on ethyl cyanoacetate in presence of alcoholic ammonia, crystallises in broad, colourless leaflets, melts a t 156-157", is very slightly soluble in water, and decomposes i n aqueous solutions, forming hexane and dicyanomethylglutaconimide, C,H,02N3.The dibvomo-derivative, C,,H,70,N,Br2, forms small, lustrous crystals, melts at 135O, loses its bromine when heated for several hours with a 50 per cent. solution of acetic acid, forming 3 : 5-dicyccno-4-methyl-4-hex~~tvimet~~~~ened~cavboni~ide, C, 4H, 70,N3 ; this compound crystallises in nacreous leaflets, melts a t 154-155', and is very slightly soluble in water. Pinacoline does not react with ethyl cyanoacetate and ammonia. The following conclusions are drawn : (1) By the action of ethyl cyanoacetate and ammonia on ketones of the type CH,* CO*C,H2,+1, the glutarimides o r piperidine derivatives, \ I are formed. These compounds may also be regarded as derivatives of aa-dicyanoglutaric acids, CnHan+l* CMe[CH(CN)*CO,Et],.(2) These new saturated eompounds form dibromo-derivatives from which tri- CO*C(CN) methylene derivatives, NH<Co, b,C-,)>CMe(CnHZn+l), may be pre- pared, Unlike the compounds of the p;-eceding class, these substances, and the dibromo-derivatives from which they are prepared, do not give a yellow coloration with potassium nitrite and sulphuric acid. E. W. W. Action of Heat on Hydrogenised Compounds. By ICILIO GUARESCHI and ERNESTO GRANDE (Chem. Centr., 1899, ii, 440; from Atti Real. Accad. Y'ovino, 34. Compare this vol., i, 52).-(1) Cyano- trimethyldihydropyridone, C,H,,ON,, decomposes at 320-330°, forming mainly methane and cyanodimethylpyridone, which melts a t 288-289'. (2) Cyanotetramethyldihydropyridone, C,,H1,ON,, which melts at 142--143*5O, decomposes at 320-330°, forming methane and cyano-1 : (?)-dimethylpyridone, CgH,,0N2; the latter melts a t 203-204O.3 : 5-Dicyano-2 : 6-dioxy-4-dimethylpiperidine, and other compounds which contain the group *CH,*CMeEt* or the group *CH,*CMe,*, under similar conditions, y.ield methane or ethane. (3) Ethyl 2 : 4 : 6- trimethyldihydropyridinedicarboxylate, C,,H,,O,N, decomposes0 1tG A N I C C H EM I STR Y . 113 340-350°,forming carbon dioxide, carbon monoxide, methane, ethylene, and alcohol, together with ethyl 2 : 6-dimethylpyridine-5-carboxylate, C,,H1302N, and ethyl 2 : 6-dimethylpyridinedicarboxylate. Of these two esters, the former (compare Weiss, Abstr., 1886, '719) is a colour- less base and boils at 255--257", and the latter crystallises in long, colourless needles, melts a t 7 3 O , and boils a t 300-305°. (4) Ethyl phenyldimethyldihydropyridinedicarboxylate, C,,H,,O,N, prepared by the action of benzaldehyde on ethyl acetoacetate in presence of alcoholic ammonia, forms crystaIs and melts a t 157'.On dry distillation, it decomposes into carbon dioxide, ethylene, hydrogen, and ethyl phenyl- dimethylpyridinecarboxylate, Cl6HI7O2N, which boils a t 315--320'. Alcohol, benzene, carbon monoxide, and ethyl trimethylpyridinedi- carboxylate are also formed by secondary reactions. ( 5 ) Ethyl dimethyldihydropyridinedicarboxylate, C1,Hl,O,N, prepared by the action of formaldehyde on ethyl acetoacetate in presence of aIcoholic ammonia, crystallises in fluorescent needles, melts at 183', and, on dry distillation under the ordinary pressure yields carbon monoxide, carbon dioxide, ethylene, ethane (?), ethyl dimethylpyridinecarboxylate, and ethyl dimethylpyridinedicarboxylate. The last compound melts at 73", and is the principal product of the decomposition.The results of these experiments shorn that the esters of dihydro- acids decompose on distillation, liberating 1 mol. of hydrogen, which often takes part in secondary reducing actions, and that the carboxy- ethyl group of the original compound, or of the est,er derived from it, also decomposes, forming carbon dioxide and ethylene, E. W. W. Pseudo-ammonium Bases. By ARTHUR HANTZSCH and M. KALB (Bey., 1899, 32, 3109-3131. Compare Abstr., 1899, i, 400).- Pseudo-bases are neutral substances isomeric with true ammonium hydroxide bases, aod correspond with the pseudo-acids previously described (Abstr., 1899, i, 399 ; this vol., i, 94, 103).Their existence may be discovered (1) by the phenomenon of gradual neutralisation, when the conductivity of a mixture of the ammonium chloride with sodium hydroxide gradually decreases to that of the sodium chloride produced, as the true base changes to the pseudo-base; (2) by 'abnormal neutralisation phenomena,' even where the velocity of change in (1) is too great t o be observed, the neutral ammonium chloride giving a neutral solution with a n equivalent of alkali, and the neutral pseudo- base giving a neutral salt when mixed with an equivalent of acid; (3) by the reluctance of the dry pseudo-base to combine with a dry acid or anhydride (CO,,HCN); (4) by the formation of abnormal anhydrides and ethers.The ammonium cyanides resemble the hydroxides, and frequently pass into pseudo-salts which are insoluble in water, soluble i n organic solvents, undissociated, and stable towards acids. Methylpyridinium hydroxide, C,NH,Me(OH), gave p32 = 21 3 and p25s=219 at 25'; i t is almost completely dissociated a t moderate dilution and shows no tendency to pass into a pseudo-base. 1-Methylquinolinium 1-hydroxide, C,NH,Me*OH, gave pZ2 = 20'7.5,114 ABSTRACTS OF CHEMICAL PAPERS. but is much less stable than the pyridine base, and passes into 1-methyl-1 : 2-dihydroquinoline oxide, O(CyNH7Me)2, th'e anhydride of the pseudo-base ; this separates in minute, white needles. Methylisoquinolinium hydroxide gave pZa = 206.9, and, like the preceding base, rapidly undergoes change.Phenylmethylacridinium hydroxide, CPh' 'NMe* OH, gave pzs6= 117.5 a t Oo, falling to 57.4 in 10 minutes, 14.1 in 1 hour, and becoming zero in about 15 hours. For the chloride, pIz8 = 45.6 a t Oo, and pm is calculated to be 50.0; whence p a for the base=127.2, showing that it is as highly dissociated as the caustic alkalis. A t 25", the isomeric change proceeds very rapidly, especially during the first few seconds, and is complete within 6 hours. Phenylmethylacridol, OH* CPh<CGH4>NMe, C H the pseudo-base, is completely insoluble in water, to which it imparts not the slightest conductivity, and does not combine with carbon dioxide or hydrogen cyanide, although with strong acids i t gives true acridinium salts; it is stable towards oxidising and reducing agents, and cannot therefore be represented by the formula CHPh<E:%>NMe:O.C6H4 \c,H,/ 6 4 When liberated from ;he= iodide by sodium hydroxide, dimethyl- /C,H*\ acridinium hydroxide, CMe' 'NMeeOH, is completely converted into the pseudo-base in 3 hours a t 0' in N/512 solution and methyl- acridinium hydroxide within 20 minutes in N/256 solution. At 25", ' gradual neutralisation ' can no longer be observed, but ' abnormal neutralisation ' occurs, the neutral iodides giving a neutral solution on adding an equivalent of caustic soda, whilst the pseudo-base is precipitated immediately, a separation which only takes place very slowly in the case of the phenylmethylacridinium base.Phenglmethylacridine ctjanide, NMe<C6H4>CPh*CN, CH separates gradually from a mixture of potassium cyanide and phenylmethyl- acridinium iodide as a white, crystalline substance, which melts a t 176". dissolves in organic solvents but not in water. and \C,H,/ 6 4 is not attacked by a d s . The first product is the true cianide, CPh /c"4\NiNe*CN, --___ which is stable at Oo, but is gradually con- \(?,HA/ verted [nt; the ' pseudo-salt ' a t 25O, the conductivity reaching a minimum within 16 hours. The pseudo-base does not combine with hydrogen cyanide. The azonium bases are regarded as pseudo-bases and shorn ' abnormal neutralisation ' lshenomena : thus the neutral salt I N-C H f;lph,$i>NPhC1 a t once gives a neutral solution with anORGANIC CHEMISTRY.11s equivalent of caustic soda and is converted into the pseudo-base y*C,H,.rYh - CPh-CPh,OK, which is quite insoluble in water, but dissolves in organic solvents. Aqueous solutions of cotarnine give evidence of the presence of a pseudo-base in the high temperature coefficient of the dissociation- constant and the formula C , H , O , < ~ ~ ~ . ~ ~ ~ > H M e is suggested for pseudocotai*nine. By the action.of hydrogen cyanide on co tarnine, or of potassium cyanide on the hydrochloride, a cyanide is produced which is regarded as pseudocotarmhe c p n i d e , C , H , O , < ~ ~ ~ ~ ~ ~ Y Y ; i t melts a t 86O, dissolves readily in organic solvents but only slightly in cold water, crystallises unchanged from water, and, unlike the true cyanides, is neutral, undissociated, indifferent to hydrochloric acid, and gives no precipitate with silver nitrate, By RUDOLF CAM Ps (Be?., 1899, 32, 3228-3234).-o-Acetaminoacetophenone is readily converted by aqueous soda into a mixture of 2-hydroxy-4-methyl- quinoline and 4-hydroxy-2-me thylquinoline, the elements of water being eliminated.A similar reaction is given by other acylaminoacetophenones, 2- or 4-hydroxy-derivatives, or a mixture of these, being formed, ac- cording to the constitution of the acid residu-es. In addition to the two hydroxymethylquinolines, o-acetamino- acetophenone yields a small amount of o-aminoacetophenone and of o-flavaniline and its acetgl derivative. T. M. L. Synthesis of 2- and 4-Hydroxyquinolines. o-Flavaniline, which has already been obtained in t e r i smdl amount by Bischler (Abstr., 1893, i, 531), crystallises in yellow needles melting a t 83-84' ; the clcetyl derivative melts at 13s'.I n the preparation of o-aminoacetophenone by the reduction of the corresponding nitro-compound, an oil boiling at 127-128" under 16 mm. pressure is obtained, which yields indigo when heated in the air, I t s constitution has not yet been ascertained. A. H. Carbamide and Thiocarbamide Derivatives of Diacetone- amine. By WILHELM TRAUBE and H. W. F. LORENZ (Bey., 1899,32, 3156-3163. Compare Abstr., 1894, i, 170).-Anhydrodiacetone- phenylthiocarbamide may be represented by one or other of the follow- ing formuh : CH<Eg'f>C-NHPh or CHqCafelN CMe*NPh>C.sH. in accordance with the former, it should, as a derivative of penthi- azoline, have a basic character, mhereas it reacts as a feeble acid forming metallic derivatives, the silver compound, C,,H,,N,SAg, being described ; the chemical behaviour of the substance is therefore more closely indicated by the second formula.The basic character of the pyrimidine ring is rendered manifest when the compound is alkylated, the methyl derivative being a stropg base.116 AlPSTltACTS OF CHEMICAL PAPERS. The oxime, C, 3H,0N,S, of diace t on ep hen yl t h iocar bamide, obtained by treating this compound with alcoholic hydroxylamine, melts at 152-1 5 3 O ; the corresponding phenylhydraxone, C,,H,,N,S, separates from alcohol in colourless crystals and melts at 169". hydriodide, C,,H,,N,S,HI, produced by mixing together alcoholic solutions of anhydrothiodiacetonephenyl thiocarbamide and methyl iodide, separates from water in lustrous crystals.Diacetoneullylthiocal.bamide, C,,H,,ON,S, crystallises from alcohol and melts at 138' ; its phenylhydraxone melts at 122O. The anhydro- compound is obtained either by heating the thiocarbamide above its melting point, or by treating i t with warm dilute sulphuric acid ; it crys- tallises from alcohol and melts at 130" ; its silver derivative is produced by treating the substance with a n alcoholic solution of ammonia and silver nitrate. ~-Methothiogl-p~~enyl-4 : 4 : 6-trimethyldihydropyrimidine 2-Methothio-d : 4 : 6-trimet?~yFl-aZlyZdihydrop~~imi~irne, CMe*N (C,H,)>c SMe, CHqCBze,- N obtained as a n oily base by treating anhydrodiacetoneallylthiocarb- amidewith an alcoholic solution of methyl iodide and sodium meth- oxide, boils at 159' under a pressure of 580 mm.; its platinichloride, (C1~I3~,N2S),, HgPtCIG, forms orange-yellow crystals. Anhydrodiacetonecarbamide (Abstr., Zoc. cit.) resembles the pre- ceding anhydrothiocarbamides, and by analogy its formula should CMe-NH>co be CH%Me2*NH ~rinitroccnh?/drodiucetonecccr6anzide, C7H,0N2(N0,),, cry stallises from methyl alcohol in colourless, silky needles which, when heated, take fire like guncotton. The substance is a dibasic acid dissolving in alkalis and ammonia to form dark yellow solutions. The barium salt, C7H7N2(N0,),Ba + 3H,O, crystalliees in reddish-yellow needles ; when heated, it explodes violently, and is decomposed by prolonged boiling with water. The silver salt, obtained i n brown needles, is even more explosive.The free acid, when boiled for some time with water, is converted into the compozsnd CGH,O,N,; this substance, which is obtained by concentrating the solution under diminished pressure, crystallises i n obliquely truncated prisms and melts at 214'; it is a monobasic acid, and is not explosive ; its bayium salt, (C,H,O,N,),Ba + 2H20, is sparingly soluble in water. G. T. M. Action of Amidines on Mesityl Oxide and Phorone. By WILHELM TRAUBE and RUDOLF SCHWARZ (Bey., 3163-31 74. Compare Abstr., 1887, 932; 1894, i, 170; 1898, i, 121 ; and preceding ab- s trac t >.- 2 -Anzino-4 ; 4 : 6-trimeth yldihydropyrimidine, CMe=N>cj .NH,, CH,<CMe, * N prepared by heating a mixture of guanidine and mesityl oxide on the water-bath, crystallises from hot water in white, rhombic plates, melts at 145O, boils a t 210' under a pressure of 10 mm., and sublimes in a vacuum, forming fern-like aggregates of slender needles.ItORGANIC CHEMISTRY. 117 dissolves in Tvater, alcohol, or benzene, and rapidly absorbs carbon dioxide from the a i r ; it is a strong monoacidic base, its salts being decomposed by caustic alkalis but not by ammonia. The hydrochloride is very hygroscopic, the oxdate forms colourless crystals and melts at 238', the picrate crystallises i n needles and melts a t 246', and the platinichloyide, (C,H,,N,),,H,FtCI,, and mercuricldoride melt at 176-177' and 184' respectively. The base takes up six atoms of bromine when treated with this reagent in glacial acetic acid solution ; the product, when crpstallised from warm water, forms reddish-purple, four-sided prisms which sinter together a t 108' and melt at 113'; when separating from boiling solutions, i t appears as yellow needles, these sinter together a t 108' but only melt a t 137' ; the purple prisms appear t o be a n impure form (containing free bromine) of the yellow compound, C7H1,N,Br6 ; the latter compound is decomposed on pro- longed boiling with water.When aminotrimethyldihydropyrimidine is heated with acetic anhydride, it yields an oily acet3Z derivative which has basic characters ; its platinicldovide, (C,H,,ON,),,H,PtCl,, crystallises in yellow leaflets and melts a t lSl-182'. Diacetoneguccnidine, NH:C( NH,)*NH* CMe,* CH,Ac, prepared by heating a mixture of guanidine thiocyanate, mesityl oxide, and sodium ethoxide at 120°, crystallises from hot water in needles melting at 163' ; it was only obtained crystalline in one experiment, the product at other times being amorphous.The acet?yl derivative, C,H,702.N,, produced by heating the crude base with acetic anhydride, crystallises from hot water in long needles and melts at 157'. 2-Phenyl-4 : 4 : 6-trinzet~yZdil~ydyo~yri~idine (anhydrodiacetonebenz- amidine), CH2<CMei. N>CPh, obtained by heating benzamide and mesityl oxide on the water-bath, separates from methyl alcohol in colourless, acicular prisms and melts a t 91'; i t is readily soluble in the ordinary organic solvents. The Iydrr-ocldoride, C,,H,,N2,HC1+ 2H20, crystallises from alcohol in well-defined cubes and melts a t 74' ; the platinichboride, ( C13H,6N,)2,H,PtC16 + 2H,O, crystallises in aggre- gates of rhombic plates and melts at 193'; the mercurichloride, C,,Hl6N2,HHgC1, + 2H20, crystallises in flattened needles melting at 179'; the oxalate crystallises in rosettes of leaflets and melts a t 210-21 1'.Anhydrotriacetonediguccnidine, C,,H,,N,, result,s from the condensation of guanidine (2 mols.) with phorone (1 mol.), the reaction being assisted by heating on the water-bath ; the product, a diacidic base, crystallises from water in long needles melting a t 1'74-175'. The hydrochloride, C,,H,,N6,ZHC1, crystallises in lustrous, rhombic plates and melts at 269' ; the plcctinichloride, C,lH,,N,,H,PtC1, + H,O, crystallises in yellow leaflets and decomposes a t 246'.Tricccetonedi- benxcLmid ine, CO( CH, CMe,*NH* CPh N H),, obtained by heat in g together phorone and benzamidine and extracting the product with cold alcohol, crystallises from the alcoholic solution on the addition of light petroleum; it melts a t 160'. The nitvate crystallises in prisms or six-sided plates ; when separated slowly from warm water, it melts a t 134', but when repeatedly crystallised from rapidly cooled solutions, it meltsat 218'. Theplc~tinicl~loi.ide, C,,H,,ON,,H,PtCl, + H20 CMe * N118 ABSTRACTS OF CHEMICAL PAPERS. crystallises from hot water in four-sided leaflets and decomposes at 263-265' ; the mercurichloride melts a t 269'. L formed as a bge-product in the preceding condensation, is obtained in larger quantity when the reaction is carried out at 160-110°, or when tha preceding base is heated to the same temperature ; it crystal- lises from alcohol in four-sided, acicular prisms, and melts a t 212", sintering at 201'.The hydvocldoride, C,,H,7N,0,HC1 + H,O, crystal- lises from hot water in six-sided prisms, sinters a t 150°, and melts a t 165'. G. T. M. Carbamide and Guanidine Delaivatives of Diacetoneamine. By WILHELM TRAUBE and MAX. SCHALL (Ber., 1899, 32, 3174-3176. Compare preceding abstracts).-The cyclic anhydrodiacetonephenyl- thiocarbamide does not exchange its sulphur for oxygen, but the open chain diacetonephenylthiocarbarnide, when boiled with yellow mercuric oxide and alcohol, yields an oil which is probably diacetonephenyl- carbamide, for on further treatment with acetic acid 2-hydroxy-l- phenyl-4 : 4 : 6-trimetJt?/ldiJqdropyrimidine (anhydrodiacetonephenyl- carbamide), CH<CMez-N>C*OH, CMe-NPh is produced ; this substance crystaliises from dilute alcohol in lizstrous leaflets, melts a t 161°, and dissolves in concentrated, but not in dilute, acids.results when the removal of sulphur is effected by mercuric oxide in alcoholic ammonia; it melts at 161' and is a strong base, but its salts are ill- defined ; the platiniclhloride, however, is crystalline. Diucetonetolylthiocurbamide melts a t 168' ; when treated in succession with mercuric oxide and acetic acid, i t yields 2-hylroxy-l-tolyl-4 : 4 : 6- trz'rnethyldihydro~yrin~i~ine, which crystallises from dilute alcohol in needles melting a t 151'. Similar compounds are obtained with xylylcarbimide.Additive Products of the Carbodiirnides. By WILHELM TRAUBE and A. EYNE (Ber., 1899, 32, 3176-3178. Compare Abstr., 1898, i, 241, and 1899, i, 192).--The carbodiimides readily combine with ethyl malonate, ethyl acetoacetate, and similar substances in the presence of a trace of sodium ethoxide, yielding additive products having the general formula NR : C: NHRoCHXY. NPh:C(NHPh)*CH(CO,Et),, produced from carbodiphenylimide and ethyl malonate, crystallises in colourless needles and melts a t 16'7'. The corresponding ditolyl com- pound from carboditolylimide melts a t 135'. G. T. M. Ethyl diphenyletJ~enyZ~c~idinedic~?.bonate, Ethyl acetyZdipl~emyZetJ~engZarnidi?zecarbonate, NPh: C(NHPh) CHAc* CO,Et, from ethyl acetoacetate and carbodiphenylimide, melts at logo; the ditolyl compound melts at 97'.ORGBNIC CHEMISTRY, 2i9 biacetyldiphen ylethen y lamidine, NP h : C( NH P h) CH A c2, from ace t yl- acetone and carbodiphenylimide, melts a t 150' ; the ditolyl compound meltsat 149'.The combination does not take place unless sodium ethoxide is present ; all the compounds produced are readily soluble in the ordinary organic solvents. Preparation of Phenylindoxyl. By MARTIN HENZE (Ber., 1899, 32, 3055-3060. Compare Abstr., 1895, i, 371, and 1896, i, 696).-The following compounds were prepared in attempting to synthesise phenylindoxyl. Phen yliminodi~henykacetic acid, NPh (C HPh. C0,H) 2, produced either by melting together ethyl anilinophenylacetate and zmc chloride o r by warming a mixture of anilinophenylacetic an6 bromophenylacetic acids at looo, is a white, amorphous powder sintering a t 90" and melting a t 105-1 10'.G. T. 11. v TetraphenyZ-P6-diket opiper axine, CHP h < ~ ~ , ~ ~ ~ > C H P h , obtained by heating a solution of anilinophenylacetic acid in acetic anhydride a t 155', is a white powder decomposing at 260'; this reaction is reversed when the condensation product is boiled with sodium amyloxide. Ethyl CLnthrunilrphenylacetate, prepared by boiling an alcoholic solution of anthranilic acid, ethyl bromophenylacetate, and sodium acetate, crystallises in white needles and melts a t 175-176", the acid, CO,H*CGH,*NH.CHPh*CO,H, melts at 227". Neither this acid nor benzylanthranilic acid is affected by fusion with caust,ic alkalis at 2 0 9-300'. G. T.AT. Orthoquinonoid Structure of Saffranine, Oxazine, and Thiazine Colouring Matters. By ARTHUR G. GREEN (Bey., 1899, 32, 3155-3156. Compare Kehrmann, this vol., i , 62).-With reference t o Kehrmann's formulation of the azonium, oxazine, and thiazine colours as orthoquinonoid bases, it is pointed out t h a t the author had previously expressed similar views (Proc., 1892, 195, and 1896, 226), and had also given reasons for believing that oxygen and sulphur ar0 quadrivalent in the latter compounds. The following are suggested as alternative formula, C,H4< NR>C,H4 and NCl y c1 C,H4<$C,H,. These formuh differ from those proposed by Kehrmann, C,H,<T>C,H,, in containing the acidic radicle (chlorine in this case) attached t o nitrogen and not to oxygen (or sulphur); this seems more probable in view of the more basic character of the nitrogen atom.Another constitution for these substances is possible, namely, that in which both aromatic nuclei are represented as being quinonoid, In certain azonium compounds, it is found that both nuclei appear to be quinonoid, and react with amines; these formuh offer a simple explanation of this behaviour, it being otherwise necessary to assume a migrationof the CsH4gN NC1 R>C,H4 and C,H,<~!?>C,H,.120 ABSTRACTS OF CI-IEMICAL PAPERS. quinone linkings (Kehrmann, Abstr., 1898, i, 439). Moreover, the formulae suggested for the azonium bases render it possible to repre- sent saff ranones, rosindones, and similar anhydrides as p-anhgdro- their constitution being more probable than that based on Kehrmann's / 1.p- formula, which represents them as m-anhydrides, $JiNB>c6H, I C.T. M. Constitution of &Methyluric Acid, By ROBERT BEHREND and EMIL DIETRICH (Annalen, 1899, 309, 260--281).-Although uric acid contains only four replaceable atoms of hydrogen, five mekhyluric acids have been described (compare E. Fischer, Ber., 1899, 32, 461). Of these compounds, &methyluric acid, which certainly contains the methyl raaicle in the alloxan group, is regarded by Fischer as 4-methyl- acid, CO ."&.C .NH >CO, along with a-methyluric acid (Hill) YH-CO $*NH and c-methyluric acid (Fischer and Ach, this vol., i, 63). The authors' experiments, however, lead them to the conclusion that &methyluric ri\ile*CO*E*NH acid is 6-methyluric acid, c(, , NH, .NH>CO.If this is actually the case, it would become necessary to reconsider the accepted formultx of several purine derivatives. The results which have led to this con- clusion are as follows. Besides acetylcarbamide and oxalic acid, methyluracil yields oxaluric and acetic acids when oxidised with potassium permanganate. I n the same circumstances, P-dimethyl- uracil gives rise t o acetylmethylcarbamide, and acetic, oxalic, and methyloxaluric acids ; from a-dimethyluraci1,rnethyloxaluric acid only is obtained, showing that the isomerides, so far as concerns the position of the methyl group, have the constitution NMe<gE::g>CMe. Nitric acid converts a-dimethyluracil into nitromethyluracilcarboxylic acid, NMe<CO-N&>C*C02H, CO*C(NO ) which loses carbon dioxide, yield- ing methylnitrouracil ; the same methylnitrouracil is produced by methylating nitrouracil; it is the same substance from which von Loeben first prepared &methyluric acid.P-DirnethyluraciZ, NMe<CO CO*CH ,NH>CMe, occurring in the mother liquor of a-dimethyluracil (m. p. 219-220°), is produced when methyl- uracil, dissolved i n alcoholic potash, is heated with methyl iodide, a-dimethyluracil and trimethyluracil being formed at the same time ; it crystallises in serrated leaflets or long needles before precipitation, the purified substance forming lustrous prisms which melt at 260'. Methyloxaluric acid, NH,. CO *NMe*CO*CO,H, prepared by oxidising a-dimethyluracil, crystallises from water in prisms, and melts and decomposes at 1S0-l9O0, according to the rate a t which the tempera-ORGANIC CHEMISTRY.121 ture rises ; the potassium salt forms a gelatinous mass which becomes crystalline. Nitronzethyluracilcarbo~~lic acid, obtained hy the action of nitric and sulphuric acids on a-dimethyluracil, crystallises from water in needles or prisms containing the solvent, which is removed a t l05', the anhydrous substance melting at 255-256' ; the potctssium salt contains 1H,O, and forms a potussium nityate double salt. Isodialuric acid is readily converted into dialuric acid under certain conditions, and if the analogous change took place when methyliso- dialuric acid is condensed with carbamide, 3-methyluric acid would be produced ; the authors find, however, that dialuric acid itself yields no trace of uric acid, but merely undergoes, in part, oxidation to nlloxan.M. 0. F. Deoxytheobromine. By JULIUS TAFEL (Bey., 1899, 32, 3194-3206. Compare the following abstract).-When a solution of theobromine in 50 Der cent. sulDhuric acid is submitted t o electro- lytic reduction, deo&theobromini (5-0x9-1 : 4-dimetlql-6 : 7-dihydro- NH* CH,*#*NMe purine), &O.NMe.C-N>CH, is formed ; it crystallises from water in thin prisms containing 2K,O, which are sparingly soluble in cold, but very readily in boiling water ; the anhydrous base melts a t 215'. The hydrochloride forms large, very soluble prisms, the platinichlwide is a granular precipitate, the picrate decomposes at 205O, and the meycurichloride is a crystalline precipitate. Bromine in chloroform solution converts the base into a n unstable monobromo-compound, C7H90,NBr, which readily passes into the isomeric 5-oxy-1 : 4-dimethyl- purine hydrobromide.Deoxytheobromine is converted by oxidation with silver acetate. bromine, and acetic acid, or lead peroxide and F=CH-g-NMe acetic acid into 5-oxy-1 : 4-dirmethplpurie, CO *NMe*C--NaCHP which crystallises, with 2H,O, in colourless prisms, and melts, when anhydrous, at 256-257'. This compound is also formed by the methylation of 5-oxy-l-methylpurine, its constitution and that of deoxytheobromine being thus determined. The hydrochloride, hydro- bromide, hydrogen sdphute, picyate, and platinichloride 81-0 all crystal- line salts. A. H. Deoxycaffeine. By THOMAS B. BAILLIE and JULIUS TAFEL (Be?.., 1899, 32, 3306-3220.Compare Abstr., 1899, i, 268, and the pre- ceding abstract).-In addition to the salts of deoxycaffeine which have ahead y been described, the sulphate, nitrate, cupochZm*ide, and rnethiodide have been prepared. When boiled with baryta water, the base yields carbon dioxide, formic acid, a n amino-acid of unknown composition, ammonia (1 mol.), and methylamine (2 mols.). Bromine in absence of water converts deoxgcaffeine into a monobromo-corn- pound which is probably 5-oxy-1 -:Cdimethylpurine 6-methobromide, NMeBr:CH* C *NMe &-,-NMe-E-B>CH, whilst a yellow perbromide is formed when a n excess of bromine is employed. Oxidation with lead peroxide and VOL. LXXVIII. i. I;122 AUS’I’11ACTS OF CHEMICAL 1’AI’X:BS. acetic acid converts the base into oxydirnetlLylpwine suetlbocccetate, TMeAc: CH- C*NMe CO-NAfe-z-N>CH, which is converted by alkalis into 5-0x9- this decomposes and melts a t 160°, is stable in the air, and does not; absorb carbon dioxide, whilst the solution is strongly alkaline and behaves in every way like that of a strong ammonium base.It is therefore probable that the constitution of the dry salt is reDresented rMe*CH* (OH)*fi*Nlne by the formula CO--NMe &CH, and that of the basein solution by the alternative formula just given. The ciiboride, bromide, picrate, pldinichlovide, and aurichlode have all been prepared. The same base is formed when 5-oxy-1 : 4-dimethylpurine rnethiodide is converted into the acetate, and the latter decomposed by alkali. From this it follows that the methohydroxide has the constitution assigned to it above, whilst deoxycaffeine is 5-oxy-1 : 4 : 6-trimethyl- 6 : ’7-dihydropurine, O-NMe-c-N, >CH.When the metho- hydroxide is heated at 170-lSOc, caffeine and deoxycaffeine are formed along with decomposition products of the latter. Constitution of the so-called Oxyazo-compounds. By 3%. C. FAUMER and ARTHUR HANTZSCH (Bey., 1899,32, 3089-3101).- The criteria enumerated in this vol., i, 95, are applied to the case in question. Free quinonehydraxone (“ hydroxyazobenzene ”) is neutral to indicators, is not an electrolyte, and does not form a compound with ammonia in benzene solution ; its constitution is probably NHPh*N:C,H,:O (and that of its hydrochloride, NH2PhCl*N:C,H,:O). But it is a pseudo-acid, for its sodium salt, with 3H,O, is only hydro- lysed t o the extent of about 0.3 per cent.at dilution VS2, and therefore must be derived from a comparatively strong acid, probably having the formula NPh:N*C,H4*ONa ; moreover, the quinone- hydrazone dissolves in aqueous ammonia, probably having undergone a molecular transformation into the hydroxyazo-compound, which then united with ammonia, pQuinonephenylhydrazone forms alkali salts most easily ; the oquinonephenylhydrazones (from o-toluquinone and from pseudocumoquinone) do so less readily and the products are less stable ; the meta-isomeride could not be obtained. P-Naphthalene- 0-quinonephenylhydrazone will only form a salt when treated with the alkoxide ; the p-chloro- and p-nitro-phenylhydrazones form salts with concentrated aqueous potash, but the salts are decomposed by water.The abnormal hydrates, NHPh*N:C,H,(OH)2 (Hewitt, Abstr., 1895, 353), occupy a position intermediate bet ween the quinonehydrazones and hydroxyazo-compounds ; they are best prepared by treating the hydrochlorides of the quinonehydrazones with water or aqueoua sodium carbonate or acetate, and they contain 1, or more often +, H,O; a number were prepared, although not all for the first time. Some benzoates and acetates were prepared from the qninone- rHMe*CH,*fi *NMe A. H.ORGAKIC CHEMISTRY. 123 hydrazones or their hydrates, and methyl derivatives (azoanisolcs, NR:N*C6H,*OMe) were prepared from the sodium or silver salts, and also from the nitrosohydrocarbon and the anisidine ; in no case was a nitrogen-ether obtained.No hydrazone could be obtained from quinone and phenylhydrazine ; quinol, and an oxidation product of phenylhydrazine, diphenyltetrazone, being obtained instead. Derivatives of ( p - ) cluinone : m-chlorophenylhydrazone, the methyl derivative is yellow and melts at 53"; o-tolylhydrazone, the acetate melts a t 65", and the methyl derivative is brown and melts at 59" ; pseudocumenehydrazone, the hgdrocldoride melts at 162", and the methyl derivative is brown and melt,s at 89'. Derivatives of o-chloroquinone : the phenylhydrazone is yellow and melts a t 8 8 O , the hydrochloride melts at 150°, the hydrate, which is brick-red below 50" and yellow above, melts at 73"; o-tolylb ydrazone, the hydrochloyide melts a t 148". Derivatives of o-toluquinone : m-chlorophenylhydraxone is yellow and melts a t 104", the hydmte is red, melts a t 76", does not Iose water readily, and is not dissociated in benzene solution, as cryoscopic experiments show, the benzoate is pale yellow and melts at 101"; o-tolylhydrazone, t h e hydvocldoride melts at 157", another Aydyate is brick-red, effloresces readily, and melts a t 83".The following compounds are, perhaps, new. 0. F. B. Constitution of the Hydroxyazo-compounds. By WILLIAM MCPHERSON (Amer. Chem. S., 1899, 22, 364--383).-The early por- tion of this paper contains details of work already published in brief (Abstr., 1896, i, 27) ; that thep-hydroxyazo-compounds have the con- stitution denoted by their names, and are not, quinone derivatives of the type O:R:N*NHPh, is held to be established by the following facts. (1) p-Hydroxyazobenzene by direct acylation or alkylation, yields derivatives unquestionably of the type NPh:N.C,H,* OR (R = acyl o r alkyl), although o-hydroxyazo-compounds give by acyla- tion derivatives as unquestionably of the form O:R:N*NPhAc (Golclschmidt and others).(2) The free p-hydroxyazo-compounds do not interact with phenylhydrazine at loo", although all p-quinone- benzoylphenylhydrazones react explosively with this substance. (3) All p-hydroxyazo-compounds are readily soluble in dilute caustic alkalis, whilst the o-hydroxyazo-compounds derived from naphthalene, which are undoubtedly quinonephenylhydrazones, are insoluble. (4) The results obtained in the aryoscopic researches of Auwers and Orton (Abstr., 1897, i, 40, and ii, 11 2).The hydrazones described were prepared by the interaction of the quinones with salts of the respective hydrazines. QuipionencetyZpheny Zhp?raxone, 0: C,H4*N *N P h Ac, crystallises f rorn a mixture of benzene and light petroleum in flat, yellow needles, melts at 11 So, and i s not identical with p-acetoxyazobenzene, NPh:N*C,H,*OAc (Wallach and Kiepenhener, Ber., 1881, 14, 2617), which melts at S9*5', not 84-85'; when heated with alcoholic potash, however, i t yields p-hydroxyazobenzene. Toluquinonebenxoyl- phenylhydrcczone, O:C,H,Me: N*N Ph* COPh, cry st allises from benzene in small, square, y+ow plates, and melts at 151"; when reduced with zinc dust and acetic acid, it yields benzanilide, and is converted by124 ABSTRACTS OF CHEMICAL PAPERS.alcoholic potash into benzeneazo-0-cresol, although not identical with the benzoate of the latter (Noelting and Kohn, Abstr., 1884, 901 ; compare Goldschmidt and Pollak, Abstr., 1892, 974). Thyrnoquinone- benxoylphenylhydrcLxone, O:C,H,MePrB: N*NPh* COPh, crystallises from a mixture of benzene and light petroleum in yellow plates and melts at 132'; there is also formed a colourless, crystalline substance, Cl5HI4O2N2, melting nt 155'. The hydrazone, on reduction with zinc dust and acetic acid, yields benzeneazothymol, but is not identical with the benzoate of the latter, OBz* C6H2MePrs*N,Ph, prepared by Baumann's reaction, which crystallises from hot alcohol in reddish- yellow needles, melts at 115', and is converted by alcoholic potash into the parent substance.a Napht7~nquinonebenzoylphenyZhyd~*azone crystallises from a mixture of benzene and light petroleum in yellow, silky needles, and melts at 161.5' J i t is not identical with benzene- azo-a-naphthyl benzoate (Meldola, Trans., 1889, 55, 606). When benzoqninone and a-phenylmethylhydmzine hydrochloride are brought together in aqueous solution, nitrogen is evolved and diphenyl- dimethyltetrazone formed ; with toluquinone and thymoquinone, similar action occurs. Diphenyldibenxyltetyaxone, N2( NPh*C,H,),, ob- tained similarly from benzoquinone and a-phenylbenzylhydrazine sulphate, crystallises from a mixture of benzene and light petroleum in colourless rhombohedra, and melts and decomposes at 145'. a-Naphthaquinonephenylmetir.ylhydraxone, O:C',,H6:N*NMePh, crystal- lises in long, flat, amethyst-coloured crystals, melts at 118.5: and is not identical with 4-benzeneazo-a-naphthol-1-methyl ether, OMe*C,,H,* N2Ph (Zincke and Bindewald, Berm, 1884,17,3026).a-N'pht?~apuinonepli,enyl- benzylhyclrazone, O:C,,H,:N *NPh* C,H,, cryetallises f rorn a mixture of benzene and light petroleum in yellow, dichroic, flat needles aIid melts at 136'; the benzyl ether, C,H,* 0 *C,,H6*N2Ph, prepared by the action of benzyl chloride and caustic soda on benzeneazo-a-naphthol, forms ruby-red monoclinic crystals, and melts a t 1029 The benxoyl derivative, O:C,,H,:N*NPhBz, is obtained by the action of benzoyl chloride on an alcoholic solution of P-naphthaquinone- phenylhydrazone and sodium ethoxide, and also by the interaction of P-naphthaquinone and a-benzoylphenylhydrazine sulphate ; i t forms yellow needles, melts at 19l0, and on hydrolysis with alcoholic potash or concentrated sulphurie acid, yields benzoic acid and @-naphtha- yuinonephenylhydrazone.When the latter is heated with methyl iodide and alcoholic sodium methoxide, the methyl ether of %benzene- azo-a-naphthol is formed (compare Meldola and Hanes, Trans., 1894, 65, 834; Noelting and Grandmougin, Abstr., 1891, 1076), which crystallises from alcohol in reddish-yellow plates and melts at 95O ; P - n a p ~ t h a q u i n o n e p h e n y l ~ e t ? ~ ~ Z ~ y ~ r ~ z ~ e crystallises from alcohol in yellow needles and melts a t 1345O. W. A. D. Action of Benzoyl Chloride on the Phenylhydrazones of Benzoin. By PAUL C. FREER (Amer. Chem. J., 1899,22, 396-402. Compare Smith, Abstr., 1899, i, 909).-The product of the action of benzoyl chloride on benzoin-@-phenylhydrazone dissolved in absolute ether at winter temperature," consists principally of0 RG A S 1 C C H E 31 I ST 1i Y . 125 benzanilide and benzil, together with lophine, dibenzoylaniline, hydrogen chloride, ammonium chloride, and aniline hydrochloride, but a considerable amount of resin is also formed; tm-nitrobenzoyl chloride, under similar conditions, gives rise to m-nitrobenzoylaniline, but the action of benzoyl chloride on benzoin-P-phenylhydrazone methyl ether yields only an intractable resin.The author discusses the nature of these reactions at some length, on the assumption that CPh t h e compound, NH<Nph>CPh, is initially formed ; the formation of lophine from benzoin-P-phenylhydrazone is explained by assuming that the latter first dissociates into benzaldehyde and the group :CPh*NH*NHPh, the benzaldeh yde subsequently combining with the benzil and ammonia simultaneously formed.The author reiterates his statement (Abstr., 1899, i, 357) t h a t benzoin-a-phenylhydrazone is not affected by benzoyl chloride. W. A. D. Unsymmetrical Disubstituted Hydrazones. By HANS LABHARDT and K. vox ZEMBRZUSKI (Bey., 1899, 32, 3060-3063).- The phenylhydrazones of benzaldehyde, salicylaldehyde, and their homo- Zogues are white or pale yellow; the hydrazones containing nitro- groups and their sulphonic acids are either yellow or red, the latter compounds dyeing wool and silk from acid baths. The hydrazones derived from secondary hydrazines -and aromatic aldehydes have similar properties and the following compounds of this type are described : PlLenyl-p-nitvo benx ylidenemetltylhydraxine, NMePh N: CH * C6H;N0,, obtained by mixing equivalent amounts of p-nitrobenzaldehyde and a-phenylmethylhydrazine in alcoholic solution, melts a t 132O ; the m-nitro-compound melts a t 11 2' and the o-nitro- a t 77" ; these sub- stances form red crystals readily soluble in the ordinary organic solvents; the para-compound may also be produced by methylating phen yl-p-nitrobenzylideneh ydrazine.Phenyl-o-hydroxybenxylidenemthylhydvuzine crystallises in white needles and melts a t 71' ; its solution in alcoholic potash is yellow, Plhenyl-p-nit~obenzylidenetl~ylhydruzine melts a t 13 1' and the rn-nityo-compound at 114' ; these substances are red, whilst the o-nitro- derivative, which melts a t 44', crystallises in brownish-yellow needles.Dipl~enyl-p-nitrobe~zyZiden~T~ydrazine melts a t 13 lo, the m-nitro-com- pound at 119-120'; both these substances are brownish-yellow ; the o-nitro-compound melts at 146' and is yellowish-red ; the o-hydroxy- compound crystallises i n white needles and melts at 139O. p-~olyl-a-methylhydruxine, prepared by reducing p-tolylmethylnitros- amine, is a non-crystallisable oil, readily soluble in the ordinary organic solvents ; it is decomposed by concentrated mineral acids, its hydrochloride being most conveniently obtained by passing hydrogen chloride into its ethereal solution. p-Toly I- p-nitro benxylidenemetl~ylhydrazine melts at 1 4 3', the m-mho- compound at 150*5O, and the o-nitro-compound a t 90.5' ; these nitro- derivatives are red, whilst the p-hydroxy-compound melting a t $5--86", is pale yellow. G.T. M.126 ABSTRACTS OF CHEMICAL PAPERS. Normal Diazo-compounds as ‘‘ Pseudodiazonium Compounds.’ By ARTHUR KANTZSCH (Ber., 1899, 32, 3132-3136 j.-The relation of normal diazo-compounds (metallic salts, diazo-oxides, diazo-ethers, and normal diazo-cyanides) to d iazonium salts exactly corresponds with t h a t of the pseudo-bases (see this vol., i, 113) t o the ammonium salts. The non-existence of the isomeric diazonium compounds corre- sponds with the labile or unstable natnre of the ammonium bases, their cyanides and other derivatives, the velocity of change being here too great to be observed.v The latter part of the paper is a reply to Bamberger (Ahstr., 1899, i, 750). T. M. L. Decomposition of Proteids by Acids. By THOMAS BOKORXY (Zeit. angew. Chem., 1899, 1099--1100).-The action of 4 per cent. aqueous solutions of hydrochloric, hydrobromic, sulphuric, oxalic, an& acetic acids on purified egg-albumin has been studied. The action begins soonebt with hydrochloric acid, and the others follow in t h e order given. The albumoses and peptones formed were separately precipitated after the several mixtiires had been boiled for 2 hours. Moderately large quantities of peptone were obtained from t h e hydrochloric, hydrobromic and srilphuric acid solutions, none at all from the clxalic acid, and merely a trace from the acetic acid.Com- pare Wroblewbki on peptonisation (Abstr., 1895, ii, 516). J. J. S. Amount of Tyrosine from Proteids. By FELIX REACE (Vi~chow’s Archiv, 1899, 158, 288-296).--The amount of tyrosine obtained from the decomposition of various proteids is very differently given by different observers, and also differs considerably with differ- ent proteids (from 0.25 to 5 per cent.). In the present research, the proteid material was decomposed by pancreatic digestion, but in parallel experiments with the same proteid the results vary. Thus with fibrin, the amount of tyrosine varied from 0.6 t o 3.8 ; with egg-white from 0.1 t o 0.6 ; with muscle pro- teids, from 1.06 to 1.37 per cent. The one experiment quoted with casein gave a yield of 4.5 per cent. of tyrosine. W. D. H. Nomenclature of the Mbumins of White of Egg. By ALExEr A. PANORMOFF (Chem. Centr., 1899, ii, 480; from J. Buss. Chem. Xoc., 1899, 31, 555--556).-The eggs of different birds contain different kinds of albumin, and the author proposes t o name the albumin of hen’s egg, which is easily crystallised from ammonium sulphate solution, albumin, and the more soluble albumin, albuminin (compare Abstr., 1899, i, 655). I n other cases, to the albumin which is least solubIe in ammonium sulphate solution a name is given which is formed by attaching the termination “-in ” t o the zoological name of the bird, the more soluble albumins being similarly designated by words ending in “-inin” and “-inidin” in the ordex of increasingsoluhility. Thus the amorphous albumin of pigeon’s egg is columbin and the more soluble crystalline albumin is columbinin. E. W. W.Action of Heat, Dilute Acids, and Alcohol on Albumin. By ALEXEI A. PANORMOFF (Chem. Centy., 1899, ii, 480-481 ; from J. RIMS. Chem. Soc., 1899, 31, 556-560. Compare Abstr., 1899, i, G55).- When 0*05-0*5 per cent. solutions of albumin in hydrochloric, hydro- bromic, phosphoric, pyrophosphoric or metaphosphoric acid are dialysed at the ordinary temperature, acid solutious are obtained in all cases but the last, metaphosphoric acid alone forming a precipitate, The rotatory power of these acid solutions differs from those of the original solutions and is still further increased by heating a t 100'. I n both cases, compounds of albumin with the acids are formed, and the change of rotatory power must therefore be due to polymerisation or depolymerisation. These polymeric compounds have also n diff crent solubility in water. The compounds obtained by dialysing the cold solutions, when reduced, regenerate the original albumin, but the com- pounds prepared by heating at looo yield only amorphous compounds of the same composition. The formula Alb,5HC1, in which Alb = C,,,H42,0,,N6,S,, is ascribed to the hydrochloride and Alb,3HBr to the hydrobromide. Phosphoric acid forms compounds containing 2 H,P04, 3H,P04, and 4H,P04 respectively, according to the concentra- tion of the acid, and pyrophosphoric acid compounds containing 3 H4P,07 or 7H4P,07. By heating either of the two latter compounds with a 0 3 or a 0.5 per cent. solution of pyrophosphoric acid, the compounds Alb,4H,Y04 or Alb,3H,P04 are formed respectively. The albumin obtained by evaporating dialysed albumin in a vacuum or by coagulat- ing it at 1OOOand finally drying at looo in a stream of hydrogen, has properties which differ from those of the albumin prepared by pre- cipitating with alcohol and ether and drying in a similar manner, although both have the composition given above. Solubility of Serum-Globulin in Water. By EMIL MARCUS (Zeit. physiol. Chem., 1899, 028, 559-575).-Doubt is cast on the hitherto accepted fact that serum-globulin is insoluble in water. It was prepared by several methods from serum and subjected to dialysis ; only a small quantity of the globulin was precipitated. The globulin so precipitated and that which remains in solution do not, however, differ in elementary composition, coagulation-temperature, or specific rotatory power. W. D. H. By V. ARNOLD (CILem. Centv., 1899, ii, 344; from Centr. med. Wiss., 37, 465--468).-The rose-red solu- tion of haematoporphyrin in alcohol or chloroform turns violet on adding bromine water. On adding strong hydrochloric acid, the solution becomes steel-blue. When mixed with aqueous caustic potash, a brown colour is obtained; on adding excess of bromine water, the mixture turns a dirty green, and when hydrochloric acid is added in excess a pure green is obtained. Measurements are given of the bands contained in the absorption spectra of these various solutions, E. W. W. Spectroscopy of the Blood. L. DE K. Extractives of Muscle. By MAX SIEGFRIED (Zeit. physid. Chem., 1899, 28, 524-529).-The N : P ratio in various preparations of carniferrin varies considerably according t o the method of preparation.128 ABSTRACTS OF CHEMICAL PAPERS, This is due to varying amounts of impurity, of which the principar constituent is an albumose-like substance. W. D. H. By TH. RICHARD KRUGER (Zed. physiol. Chem., 1899, 28, 530-534).-By ‘ salting-out ’ solutions of muscle nucleon by sodium chloride or magnesium sulphate, the amount of nitrogen is diminished slightly. If ammonium sulphate is used, the phosphorus is lessened also, and the N : P ratio sinks. These results show that decomposition occurs, A corresponding effect is produced by peptic and tryptic digestion. Similar experiments with milk nucleon gave t h e same results, except that peptic digestion produces no change and ammonium sulphate causes little or no precipitation. Nucleons. W. D. H. Plasmic Acid. By ALBERTO ASCOLI (Zeit. physiol. Chem., 1899, 28, 426--438).-This substance was originally prepared from yeast nuclein by Kossel (Abstr., 1893, i, 680), and differs in many of its characters from nucleic acid. It is now shown to be metaphosphoric acid. As prepared, however, it contains about 1 per cent. of iron,. although whether this is to be regarded as ‘ organic ’ or ‘ masked ’ iron is uncertain, the various colour reactions giving contradictory results. W. D. H. By CARL THORE MORNER (Zeit. physiol. Chem., 1899, 28, 471-523).-By treating gelatin in succession with water, dilute potash, dilute acetic acid, water, alcohol, and warm water, filtering, precipitating with alcohol, drying, powdering, ex- tracting with ether, &c., a product was obtained containing only from 0.25 to 0.75 per cent. of ash. It contains 0-2 per cent. of sulphur ; this is present in the gelatin, not in impurities ; the higher percentage of sulphur given by others is due to proteid admixture. With Millon’s reagent, it gives a reaction which, however, is transitory unless the reagent is considerably diluted with water. With sodium chloride, potassium ferrocyanide, and acetic acid, i t gives a precipi- tate when these reagents are present in suitable proportions. The idea that gelatinisation depends on the presence of mineral constituents was not confirmed ; neither was any support found for what Dastre calls the ‘ salt-digestion ’ of gelatin. Cystin, a Decomposition Product of Keratin. By KARL. A. H. MORNER (Zeit. physiol. Chem., 1899, 28,595-615).--Horn was treated on the water-bath with 25 per cent. hydrochloric acid for several days ; among the products of decomposition (tyrosine, &c.) separated out, most interest attaches t o the presence of cystin, 11 grams of which were obtained from 450 grams of dry keratin ;. cystein was also obtained. I n another experiment, more cystin was obtained in proportion, but no cystein. Properties of Gelatin. W. D. H. W. D. H.