evaporation of their aqueous solutions were unsuccessful; an oil of composition CH10S2 was formed (to this substance Masson ascribes the formula C1H2S5, ibid., 247). The author considers that this compound is derived from dithioglycocine by the displacement of both sulphydryl hydrogen-atoms by the methyl and vinyl groupings respectively, thus, SMe C2H, S.CH: CH,; and in accordance with this view it is shown that the compound takes up four atoms of bromine. Diethylene bisulphide combines readily with benzyl halogen compounds; thus with the bromide it forms a substance, C,H,S2, C,H,Br, which melts at 146°, and crystallises in the rhombic system. The corresponding iodine compound crystallises in pale yellow needles, decomposing when heated at 145°, and the chlorine compound in colourless needles melting at 143°. On heating the above bromine compound with alkalis, an oil of the composition CHS2 is produced.

V. H. V.

Disulphones. By R. ESCALES and E. BAUMANN (Ber., 19, 2814-2817).—Ethylidenediethylsulphone, CHMe (SO,Et)2, is prepared by the action of potassium permanganate on a-dithioethylpropionic acid (from pyruvic acid and mercaptan). It forms plates rather soluble in water, more soluble in alcohol and ether. It melts at 60°, and distils without decomposition. The bromo-derivative, CBrMe (SO2Et)2, crystallises in small prisms melting at 115°; it is sparingly soluble. Ethylidenediphenylsulphone, CHMe (SO,Et)2, is prepared by gradually treating a very dilute solution of potassium dithiophenylpropionate (Abstr., 1886, 878) with 1 per cent. permanganate solution. It is insoluble in water, alkalis, and acids, sparingly soluble in alcohol and ether, more readily in benzene. It melts at 101-102°. It is isomeric with Blomstrand and Ewerloeff's ethylenediphenylsulphone (Ber., 4, 716; compare also Otto and Damköhler, J. Pharm. Chem., 30, 171 and 321).

N. H. M.

Disulphones. By E. BAUMANN (Ber., 19, 2806—2814).—Diethylsulphonedimethylmethane, CMe2(SO,Et)2, is prepared by shaking dithioethyldimethylmethane with 5 per cent. permanganate solution, and occasionally adding a few drops of acetic or sulphuric acid. When no more permanganate is decolorised, the liquid is heated and filtered, and the filtrate evaporated to half its bulk. The greater part of the disulphone separates on cooling. It crystallises in thick prisms, melts at 130-131°, and boils with slight decomposition at about 300°. It is readily soluble in warm alcohol and water, rather soluble in ether, benzene and chloroform. Sulphuric acid dissolves it very readily, and decomposes it when warmed; nitric acid and bromine both dissolve it, but are without further action.

Diethylsulphonepropylmethylmethane, CMePr(SO,Et)2, crystallises from water in long needles melting at 86°; it dissolves sparingly in water, readily in alcohol, ether, and chloroform.

Ethylic B-diethylsulphonebutyrate, CMe (SO,Et), COOEt, is prepared by oxidising ethylic B-dithioethylbutyrate. It crystallises from water in slender needles more than an inch long, melts at 63°, and dissolves very sparingly in cold water, more readily in alcohol and ether.

Diethylsulphonemethane, CH,(SO,Et), is obtained by oxidising ethyl orthothioformate (Gabriel, this Journal, 1877, ii, 311) with potassium permanganate in presence of sulphuric acid. It crystallises in lustrous plates melting at 104°; and dissolves sparingly in ether, readily in benzene and alcohol. When the aqueous solution is treated with bromine-water, the dibromo-derivative, CBr2(SO2Et)2, is formed. This crystallises from boiling water in lustrous needles melting at 131°.

The disulphone is probably formed by the oxidation of the sulphide CH,(SET), present in the thio-ether. N. H. M.

Reagent for the Hydroxyl-group. By H. A. LANDWEHR (Ber., 19, 2726).—The substance to be tested is added in excess to 10 to 20 c.c. of a solution of ferric chloride (prepared by adding two drops of a 10 per cent. solution of ferric chloride to 60 c.c. of water) contained in a white dish. The production of a sulphur colour denotes the presence of hydroxyl. All hydroxy-acids and all alcohols and carbohydrates which dissolve in water give the reaction. Ether, alkyl salts, formic, propionic, butyric, oxalic, fumaric, and malonic acids give negative results. N. H. M.

Non-acid Constituents of Beeswax. By F. SCHWALB (Annalen, 235, 106-149).-Repeated boiling with alcohol extracts about 5 per cent. of cerotic acid from beeswax. The residue is saponified with alcoholic soda, and after the alcohol has been removed by distillation and by boiling with water, the soap is separated by the addition of common salt. To remove any free alkali, the soap is pressed in a cloth, redissolved in hot water, and again salted out. This operation is repeated several times. The soap is thoroughly dried at 110-120°, and the non-acid constituents are separated by fractional solution in, and recrystallisation from, light petroleum. The most soluble portion of the extract, melting between 55° and 65°, contains two hydrocarbons; one melting at 60.5° appears to be identical with Krafft's normal heptacosane, C7H56 (Abstr., 1882, 1273), and the other which melts at 67°, is probably identical with normal hentriacontane, C3H61. It is probable that other hydrocarbons are also contained in the wax.

The myricyl alcohol is less soluble in light petroleum than the hydrocarbons. It appears to have the formula CHO, and is not identical with the alcohol C30 H2O, contained in carnauba wax (Abstr., 1884, 1281). It melts at 85-85.5°, and resolidifies at 84°. When heated with soda lime, it is converted into the salt of an acid, C3H2O2. This acid is sparingly soluble in the usual solvents at the ordinary temperature, but it dissolves in hot light petroleum, and is deposited from the solution in white needle-shaped crystals, which melt at 88.5-89°. The lead salt melts at 115-116°, and dissolves freely in acetic acid and in boiling toluene. The silver salt is amorphous. It melts at 180°, with decomposition. The copper and magnesium salts are also amorphous. They dissolve in boiling benzene. The methyl and ethyl salts crystallise in needles. They dissolve freely in warm

ether and warm alcohol. The methyl salt melts at 71-71.5°, and the ethyl salt at 69.5-70°. Heated under the ordinary atmospheric pressure, the ethyl salt decomposes before boiling into ethylene and the free acid.

Beeswax also contains two lower alcohols, namely, ceryl alcohol, CHO or C2H5O, and an alcohol of the formula, C2H5O or C23H32O. W. C. W.

50

Conversion of Starch into Glucose by means of Hydrochloric Acid. By S. HARVEY (Analyst, 11, 221–223).—In reference to the process used by Heisch, heating in a boiling water-bath is as good as heating over a naked flame. In the author's experiments, whenever the conversion of starch was complete, the results obtained were too low, owing to destruction of the glucose; in fact, it appears impossible to limit the time of heating, so as to prevent the glucose being attacked.

D. A. L.

Carbohydrates. By M. HÖNIG and S. SCHUBERT (Monatsh. Chem., 7, 455-484).-In a former paper (Abstr., 1886, 44), the authors have shown that by the action of sulphuric acid on cellulose and starch, a series of sulphuric acid-derivatives are formed of the general composition CenHonOn-r(SO). These are decomposed in alcoholic solution with production of sparingly soluble compounds, containing a smaller proportion of sulphuric acid, which in their turn are decomposed at a higher temperature with formation of various dextrins. The different phases of these changes in the case of cellulose, starch, and grape-sugar are worked out more fully in this paper. From cellulose, a series of derivatives is obtained from a form of soluble cellulose to dextrose, according to the temperature (5-33°) at which the change is effected; these increase in specific rotatory power and solubility, the lower members of the series giving a blue coloration with iodine, the intermediate a red, and the end products no coloration, corresponding with the formation of an achroodextrin. These substances also differ from one another as regards their conversion by diastase; the end members are unaltered, whilst the others are converted into dextrins.

From starch, a similar series of compounds was obtained; although in this case the specific rotatory power diminishes from that of starch to that of a dextrin similar to the final product from cellulose, but differing from it in possessing a slight cupric oxide reducing power.

With grape-sugar also, similar results were obtained.

In conclusion, the question is discussed whether the starch molecule is compounded of other less complex units, differing among themselves, a view represented by the formula 15(C12H20O10), assigned by Brown and Heron, or whether it is decomposed into these less complex molecules by a chemical change rather than by a process of disintegration. V. H. V.

Identity of Cadaverine with Pentamethylenediamine. By A. LADENBURG (Ber., 19, 2585-2586).-Cadaverine and pentamethylenediamine show the same boiling point, solubility and odour,

VOL. LII.

k

and agree in their general reactions. The mercuriochloride of pentamethylenediamine has the formula CH1N2,2HCl,3HgCl2, whilst, according to Brieger, that of cadaverine mercuriochloride is

C&H1N2,2HC1,4HgCl2.

The imine obtained from cadaverine is identical in its properties with piperidine, which the author has previously shown to be the imine of pentamethylenediamine (Abstr., 1886, 139, 269).

W. P. W.

Compounds of Aldehydes and Ketones with Mercaptan. By E. BAUMANN (Ber., 19, 2803-2806).-When furfuraldehyde and mercaptan are treated with dry hydrogen chloride, the reaction is accompanied by considerable development of heat, which causes a further decomposition. Fatty aldehydes and ketones and aromatic aldehydes also react with mercaptan with development of heat; with fatty aromatic ketones, the mixture must be warmed, whilst in the case of benzophenone the reaction only takes place in presence of zinc chloride.

When dithiophenyldimethylmethane, CMe2(SPh)2 (Abstr., 1885, 749), is prepared, avoiding development of heat, a solid product is obtained instead of an oil. It forms large, clear crystals, which melt at 56°, and dissolve readily in alcohol, ether, benzene, &c., and are insoluble in water. When heated at 100°, it decomposes into a mixture of several substances, which no longer solidifies. Dithioethyldimethylmethane, CMe: (SEt), (loc. cit.), was also prepared at a lower temperature, and was obtained as a mobile, strongly refractive liquid, boiling at 190-191°; it combines directly with methyl iodide, yielding a crystalline substance. N. H. M.

Linoleic Acid. By K. PETERS (Monatsh. Chem., 7, 552-555).The formula generally ascribed to linoleic acid is C16H28O2; it would thus be the isologue of palmitic acid, and convertible into it by hydrogenising agents. It is here shown that the analytical results of a sample of an acid, purified by means of its barium salt, are more in accordance with the formula C18H32O2, and when heated with phosphorus and hydriodic acid, it yields not palmitic, but stearic acid.

V. H. V.

Acetyllævulinic Acid. Constitution of -Ketonic Acids. By J. BREDT (Annalen, 236, 225-232).-Acetyllævulinic acid is formed by the action of acetic anhydride on lævulinic acid at 100°. It is deposited from an alcoholic solution in crystals, resembling those of potassium nitrate. It melts at 78-79°, and boils about 140°, under 15 mm. pressure; under the ordinary atmospheric pressure, it splits up on boiling into acetic acid and a- and B-angelica lactones.

As the compound is neither decomposed by water nor by a cold solution of sodium carbonate, the author regards it as a hydroxylactone-derivative, not as an anhydride. This is evidence in favour of the formula CH2 CO-O CH2›CMe·OH for lævulinic acid.

W. C. W.

New Reaction of Aluminium Chloride; Syntheses in the Acetic Series. By A. COMBES (Compt. rend., 103, 814-817).-When aluminium chloride is added to a solution of acetic chloride in carbon bisulphide or chloroform, there is abundant evolution of hydrogen chloride, and a white, crystalline solid of the composition CHOAI2C1, is obtained. It remains unaltered in dry air, but is immediately decomposed by water with evolution of carbonic anhydride. If the water is added carefully to the solid, or if the latter is thrown into water in small quantities at a time, a clear liquid is obtained, which, when extracted with ether, or better, chloroform, yields a colourless liquid boiling at 136-137° under a pressure of 750 mm. It has the composition CH,O2, and is lighter than water, in which it is readily soluble without undergoing any decomposition. The action of aluminium chloride on acetic chloride is represented by the equation

2

2

6C2H2OCI+A1,Cl, 4HCl + (COMe CH, CO-CH, CCl2O·),Al2C11, and the solid compound is decomposed by water with formation of aluminium hydroxide and the acid COMe CH, CO CH2COOH, which immediately loses carbonic anhydride and yields acetylacetone, C,H,O2.

Acetylacetone has the properties of a diketone, and combines, with development of heat, with a concentrated solution of sodium hydrogen sulphite. It is not affected by phosphorous chloride or acetic chloride, but is decomposed by potash or soda, with formation of acetone and an acetate. When treated with sodium amalgam, it yields isopropyl alcohol, pinacone, and sodium acetate. If slowly hydrogenised in an acid solution, it should yield symmetrical amylic isoglycol, CH(CHMeOH)2. Bromine acts energetically on acetylacetone, with formation of acetic bromide and penta- and tetra-bromacetone. Phosphoric chloride removes the oxygen, and yields a tetrachloride which immediately loses 2 mols. HCl, and yields chlorides of the composition C,H,Cl2, derived from an unknown valerylene. When the solid product of the action of aluminium chloride on acetic chloride is treated with absolute alcohol instead of water, no gas is evolved, The products will be described in a subsequent

paper.

This reaction is general, and takes place with propionic and butyric chlorides, and with chloral. C. H. B.

Gluconic Acids. By F. VOLPERT (Ber., 19, 2621-2623). – Ethylic pentacetylgluconate is a white, crystalline substance, readily soluble in alcohol and water; it melts at 103.5°. Ammonium and potassium gluconate crystallise well in plates and needles. Comparative experiments made with Hoenig's paragluconic acid (Abstr., 1881, 893) show that it is identical with gluconic acid.

N. H. M.

Action of Thiocarbamide on Ethyl Acetoacetate. By R. LIST (Annalen, 236, 1-32) — In the preparation of thiomethyluracil from thiocarbamide and ethyl acetoacetate, by the process previously described by the author (Abstr., 1886, 443), it is found that the pre