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Dextrorotatory Hexyl Alcohol from Essence of Chamomile. By P. v. ROMBURGH (Rec. Trav. Chim., 5, 219-227).-By frequent fractional distillation of essence of Roman chamomile, a dextrorotatory alcohol (methethopropyl alcohol), CHMeEt-CH, CH, OH, is obtained, boiling at 154°; sp. gr. 0.829 at 15°; [a] = 8.2 at 17°. On oxidation with chromic mixture, the alcohol yields a dextrorotatory caproic acid (methethopropionic acid), CHMeEt CH, COOH, boiling at 196198°; sp. gr 0.930 at 15°; [x]D = 8.92. Its calcium and silver salts crystallise in needles, and its amide in long needles melting at 124°, soluble in water. A hexyl caproate is formed as a subsidiary product of oxidation. This boils at 233-234° with slight decomposition; sp. gr. 0.867 at 15°; [a]D = 12.86 at 19°. As both the alcohol, and also the acid obtained therefrom, are optically active substances, according to the hypothesis of Van't Hoff and Le Bel they must contain an asymmetrical carbon-atom. Of the three possible hexyl alcohols satisfying this condition, two have been identified by Lieben and by Zeisel and Silva. The alcohol now described must therefore have the remaining formula, that ascribed to it above. V. H. V.

Thiodiglycol-compounds. By V. MEYER (Ber., 19, 3259-3266). -Thiodiglycol is obtained by treating a concentrated aqueous solution of potassium sulphide with glycol chlorhydrin. The product is evaporated on a water-bath and extracted with alcohol. It is a syrup almost without odour.

Thiodiglycol chloride, S(CH, CH,CI)2, is formed by gradually mixing phosphorus chloride with thiodiglycol (kept cool), and pouring the product into water. It is an oil having a slight, sweet, ethereal odour. When cooled in ice-water, it solidifies to long prisms. It boils at 217o, and is almost insoluble in water. It has very poisonous properties: a rabbit exposed to air previously passed over filter-paper saturated with the substance died in three days.

When ethylene bromide is heated to boiling for a long time with aqueous potassium sulphide, an amorphous, insoluble product is obtained, differing from the polymerised diethylene disulphide (formed by adding ethylene bromide gradually to a solution of potassium sulphide in alcohol). It remains unchanged when boiled for days with phenol. The polymeride, which is decomposed by boiling with phenol, can also be prepared by adding ethylene bromide to the sodium salt, CH(SNA)2, covered with a little alcohol; if 50 times the weight of alcohol is used, the whole well cooled, and the bromide gradually added, diethylene disulphide is obtained.

The author is making experiments with a view to synthesise the ethyl vinyl ether of thioglycol, SEt C2H, S.CH:CH2, in order to compare it with the product obtained by the reduction of diethylene disulphide ethyl iodide (Mansfeld, this vol., p. 122). N. H. M.

Preparation of Derivatives of Carbohydrates. By E. BAUMANN (Ber., 19, 3218-3222).-Tetrabenzoyl dextrose, CAH,OBZ, is prepared by mixing a solution of 5 grams of grape-sugar in 15 c.c. of water with 210 c.c. of a 10 per cent. soda solution, adding 30 c.c. of benzoic chloride, and shaking until the odour of the chloride disappears. It

is insoluble in water, readily soluble in ether, alcohol, and benzene; it melts at 60-64°. It is only slowly decomposed by boiling acids or alkalis. 0.001 or 0·002 gram of grape-sugar dissolved in 100 c.c. of water can be detected by shaking with 2 c.c. of benzoic chloride and the corresponding amount of soda solution; the benzoyl-derivative separates as a flaky precipitate.

Hexabenzoyl saccharose, C12H1sOnBze, is obtained in a manner similar to the above compound.

Tetrabenzoyl glucosamine, CH,NO,Bz, is prepared by shaking a solution of 5 grams of glucosamine in 20 c.c. of water with 140 cc. of 10 per cent. soda solution and 20 c.c. of benzoic chloride. It is readily soluble in chloroform, insoluble in water, sparingly soluble in alcohol, from which it separates in long needles melting at 197-198°. It is completely decomposed by boiling with alkali.

Glycerol dibenzoate, C2H2O2Bz2 ÓH, crystallises from light petroleum in long, colourless needles melting at 70°; it is very readily soluble in alcohol, ether, and chloroform, insoluble in water.

N. H. M.

Formation and Composition of Humous Substances. By M. CONRAD and M. GUTHZEIT (Ber., 19, 2844-2850).-In their previous papers (Abstr., 1885, 745; 1886, 138; this vol., p. 25), the authors have shown that when cane-sugar is inverted by dilute acids, the lævulose is more quickly and completely decomposed, and yields more humous substances than the dextrose. Ulmin is the chief product from lævalose, whilst from dextrose ulmic acid entirely soluble in aqueous potash is obtained. If a more concentrated acid is employed, the humous substances from dextrose are less soluble, and concentrated hydrochloric acid yields a product practically insoluble in cold aqueous potash. The authors draw the following conclusions from their experiments :


(1.) That when saccharoses and glucoses are decomposed by dilute acids, the yield of humous substances stands in no direct relation to that of formic and acetopropionic acids. (2.) Saccharoses by the action of dilute acids first suffer hydrolysis, and the resulting glucoses, by the elimination of the elements of water, yield on the one hand formic and acetopropionic acids, and on the other humous substances. (3.) Saccharoses and glucoses, with the exception of lævulose, yield more humous substances by boiling with dilute (7-10 per cent.) hydrochloric acid than with sulphuric acid. (4.) The more concentrated the acid, the greater is the yield of humous substances. (5.) With dilute acids, lævulose yields more humous substances than dextrose. (6.) The percentage composition of the humous substances varies between 62.3-66·5 C and 3·7-46 H; those obtained by the action of concentrated acids containing the highest percentage of carbon.

The authors have confirmed Sestini's observation that air-dried humous substances when heated above 110° give off a vapour of acid reaction, and capable of reducing silver from solutions of its salts.

W. P. W.

Arabinose. By H. KILIANI (Ber., 19, 3029-3036).—Arabinose is prepared by heating cherry gum (1 part) with 8 litres of 2 per cent. sulphuric acid for 18 hours in a water-bath, neutralising with hot,

saturated, aqueous baryta, and evaporating the solution (without filtering) to a small bulk; it is then shaken with much 96 per cent. alcohol. The clear solution is decanted, most of the alcohol distilled off, and the residue evaporated down; it is again shaken with alcohol, and the solution concentrated by distillation. On cooling, crystals separate; these are washed with alcohol and recrystallised from six or seven times their weight of alcohol (sp. gr. 0-825); the product is

then pure.

Arabonic acid (Bauer, Abstr., 1885, 501) is prepared by shaking a solution of 20 grams of the sugar in 100 c.c. of water with 40 grams of bromine for an hour; the bromine is then removed by warming and the hydrobromic acid by means of silver oxide. Analytical results show that it is a tetrahydroxyvaleric acid, C5H10O6, and not an acid of the formula CH12O, (Bauer, loc, cit.). The calcium salt, (CsH9O6)2Ca + 5H2O, and the barium salt which forms microscopic plates were analysed. The acid could only be obtained as a syrup.

Arabinosecarboxylamide, C,H1O,N, separates as a fine, white, crystalline powder, when a clear solution of arabinose (1 part) in water (1 part) is mixed with 60 to 70 per cent. hydrocyanic acid, and kept for eight days in a closed vessel. It dissolves readily in water, but is insoluble in strong alcohol and ether; when heated, it becomes yellow at 130°, and decomposes completely at 160°, with evolution of gas. Boiling water and hot alkali solutions decompose it with evolution of ammonia.

The lactone of arabinosecarboxylic acid, C,H12O7, is prepared by dissolving the amide in the corresponding amount of hot barytawater, evaporating until the odour of ammonia has disappeared, and precipitating the barium exactly with sulphuric acid. The filtrate is made clear by the addition of a few drops of hydrochloric acid, and evaporated. It crystallises from water in very lustrous prisms (probably rhombic), melting at 145-150°; it is very sparingly soluble in alcohol. It has nearly the same rotatory power as the lactone of dextrosecarboxylic acid; [a]D = 54-8. The calcium and barium salts are amorphous.

The mother-liquor from the preparation of arabinosecarboxylamide contained chiefly ammonium arabinosecarboxylate, N. H. M.

Decomposition by Heat of the Nitrates of the Paraffinoïd Amines. By P. v. ROMBURGH (Rec. Trav. Chem., 5, 246-251).The decomposition of ammonium nitrate may be explained on the supposition that the nitrite is at first formed, on which the oxygen liberated acts to form an unstable combination, NH2OH,NO-OH, which in its turn is decomposed into water and nitrous oxide. If this were the interpretation of the reaction, the nitrates of the paraffinoïd amines should yield a nitrosamine as a product of their decomposition, thus: NMe2H,OH NO2 == NMe2H,OH NO + 0 = NMe2 NO + H20 + 0 ; the liberated oxygen would partly oxidise either the salt or the nitrosamime formed.

Dimethylamine nitrate decomposes at 150°, with evolution of nitrogen and carbonic anydride; and from the residue dimethylnitrosamine is obtained, the yield of which is 50-54 per cent. of that

required by the above theory. Similarly also diethylamine nitrate is decomposed when heated at 170°, and the reaction becomes violent with rise of temperature; carbonic anhydride and nitrogen together with an inflammable gas are evolved, and from the residue diethylnitrosamine may be obtained.

Experiments on the decomposition of methylamine, ethylamine, and tetrethylammonium nitrate were not so successful.


V. H. V.

Action of Hydrogen Chloride on Mixtures of Aldehyde with Alcohols and Phenols respectively. By A. CLAUS and E. TRAINER (Ber., 19, 3004-3011).-When a mixture of aldehyde and methyl alcohol (1 vol. 2 vols.) is treated with hydrogen chloride at a temperature below 0°, dried, and treated with sodium isobutoxide, the chief product is dimethylacetal; methylisobutylacetal (from chlorether contained in the original product) is also formed; it boils at 124-128°. When equal mols. of aldehyde and methyl alcohol are used, dimethylacetal, methyl-isobutylacetal, and di-isobutylacetal are obtained; the last compound would be formed from a-dichloro-ether in the original product.

Ethyl alcohol and aldehyde give a good yield of a-chlor-ether together with diethylacetal and a-dichlor-ether (compare Wurtz and Frapolli, Annalen, 108, 226).

Isoamyl alcohol and aldehyde (equal mols.) yielded a-chlorethyl isoamyl ether; when 2 mols. of the alcohol are used, di-isoamylacetal, C,H,O2(CH)2, alone is formed. It boils at 209-211° (uncorr.). Isobutyl alcohol (1 mol.) gave a better yield of monochlorether than amyl alcohol, and in the reaction with 2 mols. of alcohol a small amount of a-chlorethylisobutylacetal (boiling at 155-160°) could be isolated.

Ethylidene diphenyl, CHMe(C,H,OH)2, is obtained by passing hydrogen chloride through a mixture of aldehyde (1 mol.) with phenol (2 mols.). It is readily soluble in alcohol, ether, chloroform, &c., insoluble in water, benzene, and light petroleum; it could not be obtained in the crystalline state. It softens at 100°, and becomes viscous at 125°. Aqueous alkali dissolves it readily.

Ethylidene-di-a-naphthol is formed in a similar manner, and is completely analogous in its properties to the diphenyl-derivative.

When B-naphthol and aldehyde are treated with hydrogen chloride, a crystalline compound, melting at 162-163°, is formed, having the formula C2H,O2(CH)2. It has none of the properties of a phenol, but corresponds with the acetals. The authors consider that this different behaviour of a- and B-naphthol (the one behaving like a phenol and the other like a fatty alcohol) is fresh evidence in favour of his unsymmetrical naphthalene formula. N. H. M.

Acid Propionates and Butyrates. By W. G. MIXTER (Amer. Chem. J., 8, 343-346).—The following salts are described: Acid barium propionate, (C,H,O2) Ba,C,H,O2+ 3H,O, forms tabular crystals that very slowly lose water and acid in dry air. Acid strontium propionate, (C,H,O2)2Sг,C3H6O2 + 34H,O, forms long, thin

crystals, that lose acid on exposure to the air. Acid calcium propionate, 2(C,H,O2)2Cа, C3H6O2 + 5H2O, forms long needles, that have an acid reaction and decompose on heating. Acid barium isobutyrate, (C,H,O2)2Ba,C,H,O2, was obtained by heating a solution of the normal salt with the excess of the acid at 100° until constant.

H. B.

Preparation of ß-Iodopropionic Acid. By V. MEYER (Ber., 19, 3294-3295). The author finds that ẞ-iodopropionic acid can be readily prepared from the glyceric acid obtained by the oxidation of glycerol with nitric acid, since the accompanying products neither form crystalline compounds with phosphorus iodide, nor interfere with the crystallisation of the iodo-acid. The syrup obtained by the oxidation of glycerol and subsequent removal of nitric acid, is diluted with water to a sp. gr. of 1.26, and 30 c.c. of the solution is then poured into a flask containing phosphorus iodide prepared from 50 grams of iodine and 65 grams of yellow phosphorus. A vigorous action takes place either in the cold or on gently warming, and the contents of the flask on cooling solidify owing to the separation of 3-iodopropionic acid in large, colourless laminæ, which after one crystallisation from water are quite pure. W. P. W.

Methylisopropylacetic Acid. By P. v. ROMBURGH (Rec. Trav. Chem., 5, 228-239).-Köbig concluded that the caproic acid obtained by the oxidation of the hexyl alcohol from the essence of Roman chamomile was identical with that obtained by Markownikoff from the nitrile derived from methyl isopropyl carbinol. This view is not confirmed in the present paper, in which it is shown that methylisopropylacetic acid is not identical with the caproic acid obtained from the essence of chamomile. Two methods were used for the synthetical formation of methylisopropylacetic acid, CHMePr-COOH, namely, the conversion of ethyl sodiomalonate into the isopropyl-derivative, and this into the ethereal salt of methylisopropylmalonic acid, from which the acid itself was obtained by hydrolysis; this, when heated, readily decomposed into carbonic anhydride, and the corresponding acetic acid; (ii) the conversion of ethyl acetoacetate into ethylic methylisopropylacetoacetate and the decomposition of this by alkalis into methylisopropyl acetone and methylisopropylacetic acid. Of these methods, the former is preferable.

The acid boils at 189-191°; sp. gr. = 0·928 at 15°; its silver salt crystallises in delicate needles, and its amide in micaceous scales. Methylisopropylacetone, CHMePr-COMe, boils at 135-140°, has a strong odour resembling menthol; sp. gr. = 0·815 at 20°; it does not seem to react with sodium hydrogen sulphite or with phenyl hydrazine.

Methylisopropylmalonic acid, CHMePr(COOH)2, is crystalline, melts, though not very definitely, at 124°; its silver and calcium salts are sparingly soluble; its ethyl salt is a colourless liquid boiling at 221°; sp. gr. = 0·990 at 15°; it has an agreeable odour. As a subsidiary product, isopropylmalonic acid was obtained, a substance previously described by Conrad and Bischoff. V. H. V.

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