180-185°/5 mm., was obtained from both isomerides, in 64% yield. When treated with hydrochloric acid, this product afforded the imide CH, COCO,H-CH,CMe 2 CH, CO NH, m. p. 155-156°, which was hydrolysed by aqueous sodium hydroxide to the butanetricarboxylic acid, m. p. 165-169°, previously obtained by Thorpe and Wood from the additive product of the "labile” B-methylglutaconic ester. The addition of methyl cyanoacetate to glutaconic esters thus appears to be the normal addition to an aß-unsaturated ester, and it is concluded that the additive reactions of glutaconic acids cannot be properly used to support the view that the "normal" forms of these acids cannot be represented by conventional formula. F. G. WILLSON. Condensation products of ethyl acetoacetate. I. New compound of glyoxal and ethyl acetoacetate, ethyl formylmethylenebisacetoacetate. E. S. WEST (J. Amer. Chem. Soc., 1925, 47, 27802789). Glyoxal (1 mol.) reacts with ethyl acetoacetate (2 mols.) in aqueous solution (neutral to litmus), the mixture depositing, in the course of a few days at the ordinary temperature, a crystalline product and an oil. The former is ethyl formylmethylenebisacetoacetate, CHO•CH[CH(CO•Me)•CO,Et], m. p. 109-110°. It is rapidly resinified when treated with alkali, one carboxyl group being eliminated (cf. Knoevenagel, A., 1895, i, 48). It reduces Fehling's solution, but is inert to Schiff's reagent. Its solution in very dilute alkali gives a series of characteristic colour reactions with various reagents, the colours not being developed if treatment with alkali is omitted. Treatment with hydroxylamine yields the aldoxime of ethyl 5-formyl-3-methyl-A2-cyclohexen-1one-4: 5-dicarboxylate, m. p. 94-95° (decomp.) after becoming brown at 90-92°, which, when kept in a vacuum over sulphuric acid, is converted into a substance, m. p. 140° (decomp.) after becoming brown at 126°. The oil accompanying the formylmethylene derivative contains the furan derivatives differences observed in all the methylated gluconic acids. By-Dimethylglucose was oxidised by bromine to By-dimethylgluconolactone, [x] +58.5°; the sodium salt had [a] +44-1° and the free acid [a] +22·5°. yet-Trimethylgluconolactone had [a] +44.1°; the sodium salt had [a] +24.0° and the free acid [a] -6.3°. Bye-Trimethylgluconolactone had [a] +90-8°; the sodium salt [a] +64.4° and the free acid [a] +19.3°. Tetramethylgluconolactone had [a] +106·1°; sodium salt [x] +76-4°, free acid [a] +43°. Pentamethylgluconic acid had [a] +22-5° and its sodium salt [x] +53·7°. C. R. HARINGTON. Mucic and allomucic acids. R. HAC and B. HODINA (Bull. Soc. chim., 1925, [iv], 37, 1242-1245). -Sodium mucate and allomucate are without influence on the titration of borax with alkali, using phenolphthalein as indicator, an observation which is difficult to reconcile with the similar spatial formulæ assigned to these acids and to saccharic acid, in the presence of the sodium salt of which two equivalents of alkali are required by borax for neutrality (cf. Böeseken, A., 1921, i, 843). It is suggested that in saccharic acid, the hydroxyl adjacent to the carboxyl of the latter group, and that mucic and allomucic occupies the cis-position with respect to the hydroxyl acids have the corresponding trans-configuration, e.g., COH, OH.C неон н-фон The isomerisation of mucic to allomucic acid under the conditions described by Fischer (A., 1891, 1193) is complete only in the presence of copper or copper salts. In a silver vessel, no change occurs and in the presence of nickel only 8% of allomucic acid is Khotinska and produced. The observation of Epifanova (A., 1925, i, 783) that appreciably less than the theoretical amount of alkali is required for the titration of mucic acid is confirmed. Allomucic acid behaves similarly. The m. p. of mucic acid after warming to 130°. Allomucic acid does not varies from 208°, when freshly prepared, to 225° show similar variations. R. BRIGHTMAN. Bromosulphoacetic acid. H. J. BACKER (Rec. trav. chim., 1925, 44, 1056-1063; cf. A., 1925, i, 359). The yellow syrup obtained by addition of sulphur trioxide to bromoacetic acid is probably a mixed anhydride of bromoacetic and sulphuric b. p. 130-140°/0.5-0.8 mm. (slight decomp.), d acids. When heated at 80° it is rapidly converted 1.1488 (cf. Polonowski, A., 1888, 1067). F. G. WILLSON. Optical rotation of methylated gluconic acids. P. A. LEVENE and G. M. MEYER (J. Biol. Chem., 1925, 65, 535-544).-In all cases examined the specific rotation of the methylated gluconic acids was less than that of their sodium salts; the effect of methylation on the rotation varies with the position in which the substituting group is introduced; the theory previously advanced (A., 1924, i, 615) that the reason for the similarity in rotatory power between the Be-anhydro-derivatives of gluconic and mannonic acids and their salts was due to the rigidity of the structure of these acids is supported by the E into bromosulphoacetic acid, CHBr(SO2H) CO2H,H2O, very hygroscopic crystals, m. p. 119.5°. The acid is also obtained in good yield by heating sulphoacetic acid with bromine in aqueous hydrobromic acid solution at 80° in presence of a little iodine. The following salts are described: sodium (+1H2O), ammonium, silver (+H2O), thallium, barium (+1·5H2O, whereas Kohler, A., 1899, i, 488, gives 2H2O). The acid, when heated above its m. p., gives a mixture of sulphoacetic acid with dibromomethanesulphonic acid (barium salt +H,O), identical with that obtained by bromination of sulphoacetic acid in a sealed tube at 150° (cf. Andreasch, A., 1886, 786). Bromosulphoacetic acid, heated at 200° in aqueous solution, yields bromomethanesulphonic acid (barium salt +H2O). On the other hand, when the barium or ammonium salt is heated at 160-190° with excess of base it suffers a profound decomposition. The potassium salt is quantitatively reduced in cold aqueous solution by potassium sulphite to give sulphoacetic acid. G. M. BENNETT. 18 2015 21:5 which is the primary reaction, the use of a platinumiron catalyst causes quantitative reduction of the carbonyl group to a secondary alcoholic group, whilst with a pure platinum catalyst it is reduced to a methylene group, followed by deep-seated reduction in the benzene nucleus. Reduction of a methoxygroup attached to the nucleus also occurs in this Reduction of aldehydes and ketones in the case, but only in accordance with the scheme R⚫OMe → RH+Me OH, the benzene nucleus being always presence of platinum-black. M. FAILLEBIN (Ann. Chim., 1925, [x], 4, 156-182).-The effect of imsimultaneously reduced to a cyclohexane ring. The purities present in the catalyst on the products differential effect of the various catalysts is also observed in the reduction of aldehydes, but is less obtained by the catalytic reduction of aldehydes and ketones with platinum-black have been studied by sharply defined, the platinum-iron catalyst giving a quantitative yield of the secondary alcohol, whilst the preparation of a pure platinum catalyst to which known amounts of iron, aluminium, and silica were pure platinum causes incomplete reduction to the hydrocarbon, the action of the two catalysts being added. The catalyst was prepared by the method more similar with aromatic aldehydes. A summary of Loew (A., 1890, 453), the metallic impurity being introduced before the reduction of the chloroplatinic of the reductions effected, usually in acetic acid or acid. The essential factors for the preparation of ethyl acetate solution, is as follows: o-methoxystyryl an active catalyst are that the reduction should methyl ketone on reduction with a fatigued catalyst proceed slowly, and be carried out at a low temperature (the action being very rapid) yields B-0-methoxyby the slow addition of the alkali, and the precipitated phenylethyl methyl ketone, b. p. 147°/10 mm., 81°/ 0.16 mm., ns 1.5215, d1s 1.050, which on reduction platinum well washed and aërated. In the reduction of aliphatic ketones without a solvent, the use of a with a platinum-iron catalyst yields 8-0-methoxypure platinum catalyst favours the reduction of the phenylbutan-3-ol, b. p. 144°/13 mm., 90–91°/0-5 mm., carbonyl group to a methylene group, the hydro-2 1-5245, d 1.044 (benzoate, b. p. 212°/19 mm., 163°/0.3 mm.), whilst a pure platinum catalyst carbon being the main or sole product. Thus acetone yields propane, methyl ethyl ketone yields butane yields 8-cyclohexylbutan-3-ol (main product), 8-2and sec.-butyl alcohol, and methyl propyl ketone methoxycyclohexylbutan-ß-ol, b. p. 73°/0.16 mm., yields pentane. In aqueous solution, acetone also n05 1.4625, d20 0.970 (acetate, b. p. 133·5-134° / yields only the hydrocarbon when a platinum-silica 9 mm., n 1.4540, das 0-972), 8-cyclohexyl-n-butane, catalyst is used. In all cases, the use of a platinum- 8-0-methoxyphenylbutan-3-ol, and possibly 8-2-methiron catalyst (iron 5-10%) causes almost quantitative oxycyclohexyl-n-butane; p-methoxystyryl methyl reduction to the secondary alcohol, no hydrocarbon ketone yields 3-p-methoxyphenylethyl methyl ketone, being produced. In the reduction of ethyl acetowhich with a platinum-iron catalyst yields 8-p-methacetate, either without solvent or in ether or n-hexane oxyphenylbutan-3-ol, b. p. 107°/0-5 mm., ns 1-5249, solution, a pure platinum catalyst yields only ethyl 1-042 (acetate, b. p. 160°/14 mm., 104°/0-25 mm., butyrate, whilst with a platinum-iron catalyst 1.4956, da 1-0322; benzoate, b. p. 1720/0-3 mm., quantitative reduction to ethyl B-hydroxybutyraten 1-5427, d 1·080), whilst with a pure platinum occurs. A platinum-aluminium catalyst gave similar catalyst it yields, in addition, 8-cyclohexyl-n-butane, results, only a trace of ethyl butyrate being obtained, 8-4-methoxycyclohexyl-n-butane, b. p. 47°/0.25 mm., but a platinum-silica catalyst yielded both reduction 1-4645, d 0-907, (?)p-methoxyphenyl-n-butane, products, its action being intermediate between that 8-cyclohexylbutan-B-ol, 8-4-methoxycyclohexylbutanof the pure platinum and the platinum-iron catalysts. B-ol, b. p. 84°/0.25 mm., n 1-4635, d 0-956 (benzoate, In alcoholic solution, however, with a pure platinum b. p. 207°/9 mm., 150°/0-25 mm., n 1-5101, dis catalyst comparable yields of the two reduction 1-052). Reduction with platinum-aluminium products were obtained, this solvent favouring the catalyst yields 8-p-methoxyphenylbutan-3-ol (60%) production of the hydroxymethylene rather than together with the products obtained when platinum the methylene group. Ethyl 3-hydroxybutyrate is is employed, and, in addition, the hydrocarbon not an intermediate in the reduction of ethyl aceto8-p-methoxyphenyl-n-butane. Reduction of the acetate to ethyl butyrate, since it is not reduced by 8-p-methoxyphenylbutan-3-ol yields only the correthe platinum catalyst in ether or ethyl acetate solu- sponding 8-cyclohexyl and 8-4-methoxycyclohexyl alcohols, and this compound cannot, therefore, be an intermediate product in the reduction of the original ketone with a pure platinum catalyst. Reduction of 4-hydroxy-3-methoxystyryl methyl ketone yields B-4-hydroxy-3-methoxyphenylethyl methyl ketone (zingerone), which on reduction with a platinum-iron catalyst gives 8-4-hydroxy-3-methoxyphenylbutan-3-ol, b. p. 192°/15 mm., 138°/0-25 mm., n 1-5431, di 1-135 (diacetate, m. p. 46°, b. p. 143°/ 0.25 mm., n 1.5000, d 1.121; benzoyl-derivative, m. p. 84°; b. p. 198°/0.25 mm.); 3: 4-dimethoxystyryl methyl ketone on reduction yields ẞ-3: 4-dimethoxyphenylethyl methyl ketone, which, reduced tions. J. W. BAKER. Hydrogenation of aldehydes and ketones in the presence of platinum-black. Hydroxysubstituted styryl methyl ketones. M. FAILLEBIN (Ann Chim., 1925, [x], 4, 410-496).-The use of pure platinum-black and of platinum-black containing iron, aluminium, or silica (cf. preceding abstract) has been extended to the catalytic reduction of a large number of ketones and aldehydes of the type R.CH.CH.CO.CH, and R.CHO, where R is a substituted phenyl group. In general, subsequent to the reduction to the corresponding saturated ketone d n a 21-5 with a platinum-iron catalyst, yields 8-3: 4-dimethoxyphenylbutan-p-ol, b. p. 125°/0-2 mm., n 1-5316, dis 1-095 (acetate, b. p. 132°/0.3 mm., ns 1.509, dis 1.086). Reduction of piperonal ketone (cf. Vavon and Faillebin, A., 1919, i, 447) with a platinum-iron catalyst yields 8-3: 4-methylenedioxyphenylbutan-B-ol, b. p. 168/10 mm., 120°/0-3 mm., ng 1.5340, da 1.146 (acetate, b. p. 125°/0.5 mm., n 1-5104, do 1.134; benzoate, b. p. 245°/13 mm., n5 1.5550, d215 1.170), but with a pure platinum catalyst reduction is difficult, less than 1 mol. of hydrogen being taken up, and no definite products could be isolated. By comparative reduction experiments on the white and yellow forms of piperonal ketone (cf. Haber, A., 1891, 704) the author's view that the yellow form is merely piperonal ketone contaminated with dipiperonal ketone (cf. Vavon and Faillebin, loc. cit.) is confirmed. In exception to the general behaviour, the reduction of acetophenone with a platinum-iron catalyst yields a large amount of the hydrocarbon, ethylbenzene, whilst p-benzoquinone is reduced to quinol. isoValeraldehyde and heptaldehyde with a platinum catalyst yield, respectively, n-pentane and isoamyl alcohol, and n-heptane and n-heptyl alcohol, but with a platinum-iron catalyst only the alcohol is obtained. Reduction of acetaldehyde is slow, ethyl alcohol being the only product. Benzaldehyde yields toluene, methylcyclohexane, and benzyl alcohol when a platinum catalyst is employed, and a quantitative yield of the alcohol when iron, aluminium, or iridium is present in the catalyst. Reduction of the enolic forms of ethyl acetoacetate, ethyl oxalacetate, and acetylacetone were studied, the products obtained being the same as those produced from the ketonic modifications. In the case of acetylacetone, reduction with a platinum-iron catalyst yields mainly the dihydroglycol, no acetylacetonate of ferrous iron being formed, but with a platinum-aluminium catalyst the same products are obtained as with a pure platinum catalyst (mainly n-pentane), the aluminium being removed as its acetylacetonate. Two alternative theories to explain the differential action of the catalysts are discussed. J. W. BAKER. Acetone-isoacetone equilibrium. W. L. EVANS and W. D. NICOLL (J. Amer. Chem. Soc., 1925, 47, 2789-2792). When freshly precipitated mercuric oxide is treated with acetone in presence of potassium hydroxide, it is converted into the compound (Me CO:CH2),Hg,2HgO, the formation of which was used to investigate the enolisation of acetone to isoacetone in presence of alkali (cf. Evans and Looker, A., 1922, i, 102). The results obtained indicate that the enolisation of acetone is entirely analogous to that of ethyl acetoacetate and similar compounds. In presence of 0.0369M-alkali, 26-5% of the acetone is present as the enolic form. Further increase in alkali concentration does not increase the enolisation, for which a logarithmic relationship holds from the above concentration of alkali down to 0.0021 M. F. G. WILLSON. Partial hydrolysis of sucrosephosphoric acid to d-lævulose and dextrosephosphoric acid. J. HATANO (Biochem. Z., 1925, 159, 175-178).Sucrosemonophosphoric acid is warmed with dilute sulphuric acid until the first traces of free phosphoric acid appear. Dextrosemonophosphoric acid is isolated as the barium salt and lævulose demonstrated in the residue. E. C. SMITH. Preparation of raffinose from cotton-seed meal. D. T. ENGLIS, R. T. DECKER, and A. B. ADAMS (J. Amer. Chem. Soc., 1925, 47, 2724-2726). -See B., 1925, 1004. Sugars. VI. H. KILIANI (Ber., 1925, 58, [B], 2344-2362; cf. A., 1923, i, 1059).-Although the sodium salt of d-saccharolactone crystallises very readily when pure and is sparingly soluble in cold water, it is not suitable for the isolation of d-saccharic acid from the products obtained by the action of nitric acid on dextrose or starch, since its separation is readily inhibited by the presence of foreign matter. It is remarkable that the sodium salt readily separates when a solution of d-saccharolactone in water is treated with crystalline sodium acetate, but not when it is neutralised by sodium hydroxide. The sodium salt is not reduced by aluminium or sodium amalgam to glycuronic acid; the free lactone is, however, reduced in acid solution to glycuronolactone (yield 30%). For the preparation of d-saccharic acid (cf. Kiliani, loc. cit.), rice starch is allowed to remain in contact with nitric acid (20%) in proportion of 1 g. to 3-4 c.c. for 12 hrs., after which the temperature is gradually raised in a manner depending on the weight of starch taken. The product is finally heated for several hrs. at 100°, after which the oxalic acid is removed by calcium carbonate. The residual acid solution is neutralised completely with potassium hydroxide, concentrated at 50°, and treated with so much acetic acid that potassium hydrogen d-saccharate is formed. The latter is crystallised if necessary from water and transformed successively into the normal potassium and calcium salt from which d-saccharomonolactone is obtained by the aid of oxalic acid. The lactone does not readily pass into d-saccharic acid in aqueous solution at 20.7°. The following method is very suitable for the preNeuberg and Hirschberg, A., 1910, i, 653). The paration of l-arabonic acid from cherry gum (cf. gum is hydrolysed by 2% hydrochloric acid at 100° and the filtered solution is oxidised with bromine. After neutralisation of the acid with freshly slaked lime, the solution is immediately evaporated until a solid skin is formed. Calcium l-arabonate separates very slowly from the cold solution, crystallisation The crude salt is very easily recrystallised from usually requiring several weeks for completion. after treatment with oxalic acid. Brucine l-arabonate water, and the pure salt readily gives l-arabonolactone has 4H2O (cf. Nef, A., 1908, i, 5). For the preparation of l-mannonic and l-gluconic acids (cf. Kiliani, A., 1922, i, 223), a mixture of l-arabinose and hydrocyanic acid is added to a very concentrated barium hydroxide solution contained in a dish immersed in briskly boiling water. The product is evaporated as rapidly as possible on the water-bath to a thick syrup, and is subsequently well stirred with a spatula until ammonia almost ceases to be evolved. The barium is removed with the necessary amount of sulphuric acid, after which the solution is evaporated to a syrup and worked up for l-mannonolactone and brucine l-gluconate as previously described. The latter salt is more readily crystallised from a very little water than from 85% alcohol. Contrary to previous observations (loc. cit.), it contains an appreciable proportion of brucine l-mannonate. Separation of the acids is completely effected by transforming the brucine into the barium salts, since barium l-gluconate crystallises readily, whereas barium l-mannonate does not. Pure brucine l-gluconate has m. p. 167-168°. The sparing solubility of normal sodium mucate in water (cf. Khotinska and Epifanova, A., 1925, i, 783) has been observed previously by the author; the statement that the anhydrous salt is insoluble in boiling water is incorrect. Calcium mucate and calcium galactonate form a crystalline double salt, [CH-OH](CO2)2 Ca(CH1107)2,8H2O. The probability The probability that Kiliani's oxygluconic acid" is identical with B-ketogluconic acid obtained by the action of barium hypobromite on dextrose and fermented to d-arabinose has been suggested by Hönig and Tempus (A., 1924, i, 712). The calcium salt of Kiliani's acid does not yield arabinose when fermented with pure yeast (cf. van Niel and Visser 't Hooft, A., 1925, i, 1237). The preparation of B-glucoheptonolactone is greatly simplified if the mother-liquor from which the a-compound has separated is treated with only 2-2.5 parts of water and the solution is saturated with brucine at 35°. The brucine salt is converted into the barium salt, and thence into 3-glucoheptonolactone, which crystallises readily. Acetyl-d-galactonic acid, CH110,Ac, m. p. 160° after softening, is obtained readily by the action of glacial acetic acid and nitric acid (55%) on d-galactonic acid at 21°; hydrochloric may replace nitric acid but with less advantage. d-Gluconolactone and a-glucoheptonolactone are not acetylated under these conditions. 66 The suggested applicability of semicarbazide to the removal of "uronic acids "from the products of the oxidation of sugars by nitric acid (A., 1923, i, 1059) has proved illusory. Further examination shows that the "semicarbazone of l-galacturonolactone " is the semicarbazide of unoxidised d-galactonic acid. Similarly, the semicarbazone of l-mannuronolactone is proved to be the monosemicarbazide of l-mannosaccharodilactone. The identity of the products derived from a-glucoheptonolactone and isosaccharin could not be established definitely. The above discovery sensibly diminishes the prospects of obtaining uronic acids by the bromine oxidation method, which, according to the results of experiments on d-galactonic and similar acids, does not appear very suitable for the purpose. During examination of the possibility of using hydrazine and substituted hydrazines for the isolation of "uronic acids," the following observations have been made. Glucurolactone and p-nitrophenylhydrazine in cold, acetic acid solution readily yield the corresponding hydrazone, m. p. 224°. I-Mannohepturonolactone-p-bromophenylhydrazone, m. p. 165° (decomp.) after darkening at 145°, and the unstable 7-mannohepturonolactone-o-tolylhydrazone are pre Hexahexosan and trihexosan. P. CASTAN and A. PICTET (Helv. Chim. Acta, 1925, 8, 946-948; cf. A., 1924, i, 1288).-Hexahexosan is purified by fractional precipitation of its aqueous solution by alcohol. The presence of higher polymerides causes the colour produced with iodine to be violet instead of a bright red. If the iodine is added gradually, or if the mixture and iodine are heated until colourless and then cooled, the colour appears first blue, then violet, and then red, showing that the substance of higher mol. wt. forms iodine complexes of greater stability. Hexahexosan is found cryoscopically to have the formula (CH1005); it has [x] +173-2° in water. Acetyl bromide acts on it with production of hepta-acetylmaltose and only a trace of dextrose, as with starch. It is attacked by amylase and less readily by emulsin to yield maltose. Trihexosan is hydrolysed at 100° by 5% sulphuric acid to dextrose (96.3% of the theoretical yield). Amylase acts on it slowly, producing maltose. Acetyl bromide yields hepta-acetylmaltose and dextrose. G. M. BENNETT. Dihexosan and tetrahexosan. A. PICTET and R. SALZMANN (Helv. Chim. Acta, 1925, 8, 948-949; cf. A., 1924, i, 1288).-Emulsin acts on trihexosan to give dextrose and dihexosan, [x] in water +135·8°. By the action of concentrated hydrochloric acid or barley amylase it is converted into maltose. Acetylation yields B-octa-acetylmaltose, m. p. 155°. Ďihexosan is therefore an anhydride of maltose. From the products of the action of emulsin on trihexosan there has also been isolated a crystalline tetrahexosan, (C6H1005)4 m. p. 260°, [a] +162.6° in water, which is considered to be formed by polymerisation of the dihexosan under the influence of the enzyme. Amylase slowly attacks it, producing maltose. G. M. BENNETT. Thio-sugar from yeast. P. A. LEVENE and H. SOBOTKA (J. Biol. Chem., 1925, 65, 551–554).—The sugar obtained on hydrolysis of the adenine nucleoside isolated from yeast by Mandel and Dunham (A., 1912, i, 320) and Levene (A., 1924, i, 802) has proved to be identical with the sugar containing sulphur recently described by Suzuki and others (A., 1925, i, 338). The substance forms a p-bromophenylosazone even after exposure for 96 hrs. to excess of bromine; it cannot therefore be an aldose nor can OH·CH2•C(OH)·CH(SM∞)-CH(OH)·CH2 or the y- or 8-position of the substituent group being still Distribution of lignin in wood. G. J. RITTER (Ind. Eng. Chem., 1925, 17, 1194-1197).-See B., 1925, 985. Synthesis of N-methylputrescine and of putrescine. H. W. DUDLEY and W. V. THORPE (Biochem. J., 1925, 19, 845-849).—Benzoyl-8-bromoand benzoyl-8-iodo-butylamine were prepared by benzoylating the amine halides. The iodo-compound was then converted into monobenzoyl-N-methylputrescine, NHBz [CH2] NHMe, by boiling with methylamine for 2 hrs. From this compound N-methylputrescine dihydrochloride was obtained by heating at 130° for 8 hrs. with concentrated hydrochloric acid. N-Methylputrescine yields a dipicrate, m. p. 229-230-5° (corr.), chloroaurate, m. p. 192° (corr.) after softening, decomp. 215° (corr.), chloroplatinate, decomp. 230.5° (corr.). The picrolonate, decomp. 254-265°, mercurichloride, m. p. 149° (corr.), and the dibenzoyl compound, m. p. 115.5° (corr.), were also obtained. Monobenzoylputrescine was obtained by heating benzoyl-8-iodobutylamine with ammonia and alcohol in a sealed tube. Putrescine dihydrochloride was obtained by hydrolysing mono- or di-benzoylputrescine with concentrated hydrochloric acid in a sealed tube. Di-[8-benzamidobutyl]amine hydrochloride, C22H30O2N3Cl, prisms, m. p. 233° (corr.), was obtained as a by-product in the process of preparation of monobenzoylputrescine. From this compound the monobenzoyl base and di-8-aminobutylamine hydrochloride were obtained. The tripicrate, m. p. 255° (corr. decomp.), and the chloroaurate, m. p. 209° (corr. decomp.), were prepared from the S. S. ZILVA. base. BB'B"-Triaminotriethylamine and its complex metallic compounds. F. G. MANN and (SIR) W. J. POPE (Proc. Roy. Soc., 1925, A, 109, 444-458; cf. A., 1924, i, 1049).-BB's"-Triaminotriethylamine, unlike aẞy-triaminopropane, and contrary to expectation, acts in all cases, for co-ordination purposes, as a tetrabasic amine in spite of the great diminution in the basic properties of the tertiary amino-radical, brought about by the presence of the three substituting groups. Such compounds as the following have been obtained, [Cl2PtN(CH2°CH2•NH2)3]Cl2, and [PtN(CH2 CH2 NH2)3]2. The first of these compounds (containing quadrivalent platinum) is easily represented by the Werner models of spatial configuration. The second (containing bivalent platinum) cannot be reconciled with these models so readily, for obvious. and N(C2H NH2)3,2AuCl,,4HCI, m. p. 187-189° (decomp.); mercurichloride, N(C2H1 NH2)3,5HgCl2,3HCl, m. p. 202-204° (decomp.); chlororhodiates, chlororutheniate, the platinum salts, N(C2H1 NH2) ̧,2RuCl,,4HC1,2H2O; 2N(C2H1 NH2)3,3PtCl2,6HCl,3H2O, 2N(C2H NH2),,3PtC14,6HC1,10H2O, m. p. (anhydrous) 231-232° (decomp.) after darkening at 225°; N(C2H, NH2)3,2PtC14,4HC1,10H2O, m. p. (anhydrous) 271-273° (decomp.) after darkening at 260°. The following metallic, co-ordinated derivatives of triaminotriethylamine are described [tren= N(C2H, NH2)3]: [Cl2Pt tren]Cl2, m. p. 263-266° (decomp.) after darkening at 240°; [Cl,Pt tren]I, decomp. 233-237° after darkening at 225°; [Cl2Pt tren]PtCl6,2H2O, m. p. 287-288° (decomp.) after darkening at 275°; [Cl,Pt tren]Pt(CN)4, which darkens at 225° but does not melt below 300°; [Pt tren]PtCl1, m. p. 270–275° ́ (decomp.) after shrinking at 265°; [Pt tren]I, m. p. 267-269° (decomp.) after darkening at 260°. S. BARRATT. Nitration of hexamethylenetetramine. G. C. HALE (J. Amer. Chem. Soc., 1925, 47, 2754-2763). -Hexamethylenetetramine dinitrate, m. p. 165°, is precipitated when nitric acid (d 1·42) is added, at 0°, to a solution of hexamethylenetetramine (1 part) in water (3 parts). When added to concentrated nitric acid, the dinitrate is converted into cyclotrimethylenetrinitroamine (cf. Henning, U.S.P. 104280, 1899; Herz, B., 1922, 158), best yields being obtained by the use of nitric acid of 90-95%, at 30°. Direct nitration of hexamethylenetetramine to the trinitroamine (cf. Herz, loc. cit.) gives best results when the base (1 part) is added to 92% nitric acid (11 parts) at 30°, and the solution cooled to 0° before dilution, but yields higher than 75% are not obtainable, owing to hydrolysis of the hexamethylenetetramine to formaldehyde and ammonia, and production of the above dinitrate. F. G. WILLSON. Steric series. VII. Configuration of aspartic acid. K. FREUDENBERG and A. NOË (Ber., 1925, 58, [B], 2399-2408; cf. A., 1925, i, 1275).—The configurative relationship of (+)-lactic acid to natural alanine and natural malic acid has been established, as also that of natural alanine to natural aspartic acid, so that it has been shown indirectly that the natural forms of malic and aspartic acids have the same steric arrangement. This is confirmed by direct comparison of derivatives of these acids. It is remarkable that similar behaviour is exhibited |