in a current of ammonia gas, it loses water, but no compound richer in ammonia is formed.

When zinc cyanide is dissolved to saturation in alcohol, treated with a current of ammonia gas, and the liquid allowed to evaporate spontaneously, the compound ZnCy2,2NH, is obtained in transparent crystals, which lose ammonia rapidly when exposed to the air and become opaque, and are very soluble in aqueous or alcoholic ammonia. The same compound is obtained by passing ammonia gas over gently heated zinc cyanide. Zinc cyanide forms only one compound with ammonia, and not a series of compounds like the chloride and bromide. C. H. B.

Methyl Mercaptan and some of its Derivatives. By J. OBERMEYER (Ber., 20, 2918-2928).-Methyl thioacetate is prepared by the action of lead methyl mercaptide on a slight excess of cooled acetic chloride; it boils at 95-96° (not 62-68°, Cahours, Compt. rend., 80, 1317, and 81, 1163). The substance described by Cahours (loc. cit.) is probably a mixture of the ether with methyl iodide, acetic acid, and hydrobromic acid.

Methyl thiopropionate, C,H,SO, prepared from propionic chloride, is a colourless liquid of repulsive odour, boiling at 119-120°.

Methyl thiobutyrate, CHOSO, is a light oil having an odour resembling that of butyric acid; it boils at 140-144°.

Methyl a-thiobenzoate, CH,SO, boils at 231-232°.

Methylisopropyl sulphide, SMePr, is prepared by dissolving sodium in isopropyl mercaptan diluted with absolute ether, and the mixture, contained in a reflux apparatus, is treated with methyl iodide in small portions; it is then heated for 15 minutes in a water-bath and filtered. The heavy oil which separates from the solution when kept over night, is removed, and the ethereal solution evaporated and fractionally distilled. It boils at 93-95°.

Methyl amyl sulphide, SMe C5H1, is prepared by the action of methyl iodide on amyl mercaptide; it boils at 136-138°. Isoamyl disulphide is also formed.

Methyl allyl sulphide, SMe CзH, is formed when 25 grams of lead methyl mercaptide is heated with allyl bromide and ether at 100°. It is a clear liquid of a very penetrating odour, boiling at 91-93°.

When allyl tribromide is heated with an excess of lead methyl mercaptide and ether at 100°, a compound, probably of the formula SMe-C,H,Br, is obtained. It could not be purified, as it decomposes at 120-130°.

Methyl benzyl sulphide, SMe-C,H,, is obtained by heating lead methyl mercaptide, and benzyl chloride at 100°. It is a clear liquid of an odour resembling horse-radish, and boils at 195-198°.

Methyl phenyl sulphide, SMe-Ph, prepared from lead thiophenol and methyl iodide, forms a clear liquid boiling at 187-188°.

Dimethyl thioresorcinol, C.H.(SMe)2, is an oily liquid of a disagreeable odour boiling at 278°.

Methyl diphenyl sulphide, SMe C12H9, is obtained from lead thiodiphenyl; it crystallises from alcohol in flakes of very slender needles, melting at 107-108°.

Dimethyl diphenyl disulphide, CH4S2, is prepared by heating the lead mercaptide of diphenylthiohydrate with methyl iodide. It crystallises from alcohol in lustrous bright-yellow plates melting at 185-186°. N. H. M.

Brandy from a Wine from Charente Inférieure. By E. C. MORIN (Compt. rend., 105, 1019-1022).-The composition of the brandy in 100 litres is as follows:-Aldehyde, traces; ethyl alcohol, 50837 grams; normal propyl alcohol, 27-17; isobutyl alcohol, 6·52; amyl alcohol, 190-21; furfuraldehyde and bases, 2-19; fragrant oil, 7.61; acetic and butyric acids, traces; isobutylenic glycol, 219; glycerol, 4:38. There is no normal butyl alcohol, and amyl alcohol constitutes five-sixths of the higher alcohols. The fragrant oil is one of the constituents to which the wine owes its bouquet. (Compare Abstr., 1887, 714 and 746.) C. H. B.

Production of Normal Amyl Alcohol by the Fermentation of Glycerol by Bacillus Butylicus. By E. C. MORIN (Compt. rend., 105, 816-818).-When glycerol undergoes fermentation by Bacillus butylicus under the conditions determined by Fitz, 4 per cent. of the alcohols formed is normal amyl alcohol, boiling at 137-138°; refractive index at 13.5° for D : 1.414.

It is worthy of note that all the alcohols produced by B. butylicus are normal. C. H. B.

Action of Zinc Methyl on Valeraldehyde. By J. KUVSINOFF (Chem. Centr., 1887, 987-988, from J. Russ. Chem. Soc., 1887, 204). Methyl isobutyl carbinol is produced when zinc methyl is added to well-cooled valeraldehyde, and the product of the action decomposed with ice-water. It is a light, mobile liquid, boiling at 130°, sp. gr. 0.8271 at 0°; its acetate boils at 147°, sp. gr. = 0·8805 at 0°; its ketone boils at 116-116.5°, and on oxidation yields isopropylacetic, isobutyric, acetic, and formic acids, and is therefore identical with methyl isobutyl ketone. V. H. V.

Action of Zinc Isoamyl and Zinc Isobutyl on Aldehyde. By E. SOKOLOFF (Chem. Centr., 1887, 988, from J. Russ. Chem. Soc., 1887, 197-204). When zinc isoamyl is added to aldehyde, kept cool, and the resultant product decomposed with ice-water and distilled, methyl isoamyl carbinol is obtained besides isopropylethylene, and ethyl and isoamyl alcohols. The first yields an acetate boiling at 166-168°, and a ketone boiling at 143-145°, which yields on oxidation isopropylacetic acid. Zinc isobutyl when treated in like manner yields isobutyl and ethyl alcohols. V. H. V.

Methyl Isopropenyl Carbinol. By J. KONDAKOFF (Chem. Centr., 1887, 981, from J. Russ. Chem. Soc., 1887, 336).-When treated with a 6 per cent. hydrochloric acid solution, methyl isopropenyl carbinol is converted into the isomeric trimethylethylene glycol. The readiness with which this change is effected is dependent on the

atomic arrangement; this has also been observed in the case of unsaturated acids. V. H. V.

Iodide of Starch. By H. B. STOCKS (Chem. News, 56, 212213). The author takes exception to the four points set forth by F. Mylius (Abstr., 1887, 568), and makes the following remarks on each point. (1.) He states that iodide of starch is producd by the action of solutions of pure iodine, or of the vapour of iodine, on moist starch. (2.) That a limited amount of chlorine produces the blue colour in mixtures of hydriodic acid, or of an iodide, with starch; but that excess of chlorine destroys the colour, probably by the formation of a colourless chlorine compound of starch and iodine chloride. (3.) Silver nitrate does decolorise the iodide by removing the iodine as silver iodide, the colour being reproduced on the addition of either iodine or hydriodic acid; the action in the latter case may, however, be assumed to be due to iodine set free by the nitric acid liberated from the silver nitrate. (4.) Aqueous solutions of iodine do produce

the blue colour with starch.

Water is necessary for the production of iodide of starch; therefore solutions of iodine in absolute alcohol do not colour dry starch blue. The blue iodide is destroyed by heat, the iodine being, in open vessels, partially volatilised, partially converted into hydriodic acid; in closed vessels, on the other hand, it is entirely converted into hydriodic acid. This decomposition is quick or slow according as the quantity of iodine is smaller or greater. By adding iodine to a solution decolorised in this manner, the blue colour is again formed, and this decolorisation and recolorisation may be frequently repeated with the same starch. Exposure to sunlight also decolorises iodide of starch. Iodide of starch is not affected by alcohol, ether, benzene, or carbon bisulphide; in fact, iodine may be removed from its solutions in the last two solvents by means of starch-paste.

Iodide of starch dissolves to a certain extent in water, and is precipitated from the solution by absolute alcohol, by dilute hydrochloric, sulphuric, and nitric acids, by strong hydrochloric acid, and by salts which do not react with it, such as sodium chloride. Strong nitric and strong sulphuric acid decompose it. Starch solutions are not precipitated by dilute acids like the solution of the iodide.

D. A. L. Constituents of Rice-starch. By L. SOSTEGNI (Chem. Centr., 1887, 896, from Stud. di Chim. Agr. di Pisa, 6, 48-68).—The results quoted of the amount of dextrose obtained by the saccharification of starch accord with those of Salamon. In the course of the preparation of starch cellulose by Schulze's method, a fat melting at 47— 48° was extracted; the crude fatty acids obtained therefrom melt at 50-51°; the proportion of fat found was 15 to 20 per cent. of the cellulose. The portion of residue, insoluble in ether, obtained in the saccharification of starch, differs from cellulose by its solubility in a 2 per cent. solution of potash, and its partial decomposition when warmed. From its solution, acetic acid precipitates an amorphous substance, turning brown in the air, soluble in Schweizer's reagent when moist, but not when dry; it is decomposed when boiled with

hydrochloric acid. The author regards starch cellulose as a mixture of cellulose with the derivatives of the latter substance or a modification of granulose. V. H. V.

Lichenin. By M. HöNIG and S. SCHUBERT (Monatsh., 8, 452— 465). As there was considerable doubt whether the carbohydrate from Iceland moss (Cetraria islandica) was a single substance or a mixture of two or more, the authors have reinvestigated it. The dried and sorted moss was treated repeatedly with a 1 to 2 per cent. solution of K,CO3. A pale-green mass quite free from the original bitter

taste was thus obtained. This was then boiled for some time with

water and filtered through linen. The filtrate on cooling deposited a gelatinous precipitate, which separated better when the solution was frozen. The liquid still contained some of this gelatinous substance, together with an easily soluble starch. The gelatinous precipitate, for which the authors propose to utilise the name lichenin, previously used for the whole extract, is very sparingly soluble in cold water, but dissolves in boiling water to an opalescent solution, which is at once cleared by the addition of a little potash. The greater part is precipitated from its solutions on cooling, or on the addition of alcohol. It is not coloured by iodine. When heated with dilute sulphuric acid, it very readily yields a crystalline dextrose, which gives a rotation [a]; = +55 52°, and closely resembles, if it is not identical with, ordinary dextrose. The intermediate dextrin-compounds are tasteless and nonrotatory. The above-mentioned soluble carbohydrate, for which the authors propose the name lichen-starch, could not be obtained free from lichenin. It is strongly rotating, the rotation increasing the freer the starch is from lichenin. It is easily soluble in water, but is thrown down as a flocculent precipitate by alcohol. The highest rotation obtained was [a]; = +102·82°. It is coloured blue by iodine. Diastase converts it readily into a dextrin showing rotation [a]; = 162·44°. Lichenin is not affected by diastase. Lichen-starch, therefore, appears to be a soluble, unorganised modification of ordinary starch. L. T. T.

Reactions of Chloral. By O. REBUFFAT (Gazzetta, 17, 406-409). -Chloral and sodium acetate, in presence of acetic anhydride, do not react in accordance with Perkin's reaction; the change is for the most part more profound, leading to the destruction of the molecule of chloral. Sodium acetate at a low temperature combines directly in equimolecular proportions with sodium acetate to form a compound, C2C12HO,C2H2O,Na, which is white and minutely crystalline; it is decomposed by water and by alcohol to form chloral alcoholate. Experiments were also made with the anhydrides of other fatty acids, but without success. V. H. V.

Trithioacetaldehydes. By W. MARCKWALD (Ber., 20, 28172818; compare Abstr., 1886, 864).--Trithioacetaldehyde, when mixed with four times its weight of ethyl iodide and allowed to remain in a closed vessel for some weeks, suddenly undergoes conversion into a crystalline mass of the B-derivative. This change is not due to

the presence of free iodine in the ethyl iodide, since the change does not take place when an ethereal solution of the y-aldehyde containing a small quantity of iodine is similarly treated. W. P. W.

Metallic Derivatives of Acetylacetone. By A. COMBES (Compt. rend., 105, 868-871).-The author has previously shown that acetylacetone has the constitution CH,AC COMe, and that the hydrogen of the CH2-group is readily displaced by chlorine or by sodium.

The

Acetylacetone and its homologues act on metallic salts like true acids, and yield a new series of crystalline compounds of the general formula M(C,H,O2)n, in which M is a metal with a valency n. sodium and potassium derivatives form white, hexagonal prisms belonging to the rhombic system, and are most readily obtained by adding the required quantity of sodium or potassium ethoxide to an alcobolic solution of acetylacetone. They are somewhat soluble in absolute alcohol, but are insoluble in ether.

The magnesium salt is obtained by mixing acetylacetone with an excess of magnesium carbonate. There is rapid effervescence, and the filtered liquid when evaporated in a vacuum, deposits transparent, colourless, hexagonal prisms belonging to the rhombic system, which are anhydrous when dried at 125°. The aluminium compound is formed in the preparation of acetylacetone, and is also obtained by the action of the latter compound on a slightly acid solution of aluminium chloride. It is insoluble in water, somewhat soluble in alcohol, but less soluble in ether. When the solution is concentrated, it deposits nacreous crystals of the same form as the preceding compound, but they are readily decomposed by heat.

The copper salt is obtained in pale blue needles of the same form, when a somewhat concentrated solution of cupric acetate is mixed with a warm saturated aqueous solution of acetylacetone. The compound is insoluble in water, and in moderately dilute solutions the precipitation of the copper is complete. Larger crystals are formed when a dilute solution of cupric chloride is added to a boiling solution of acetylacetone. The crystals are anhydrous when dried at 125°.

Ferric chloride and acetylacetone yield a dark-red solution, the formation of which may be used as a test for the ketone, and when this is extracted with ether the red compound is dissolved. When the ether evaporates, the iron salt is deposited in bright-red crystals, similar in form to those of the ammonium salt.

The lead salt is formed by the action of lead carbonate on the ketone, is soluble in water, and resembles the magnesium compound in its crystalline form.

Acetylacetone behaves in fact like a monobasic acid. The sodium and potassium salts are, however, decomposed by hot water, with formation of acetone and an alkaline acetate, and the aluminum and iron compounds are not decomposed by ammonia in alcoholic solution. The sodium salt and methyl iodide yield a new derivative, methylacetylacetone, boiling at 165°, which has acid properties similar to those of the original compound. It seems, in fact, that the group CO-CH, CO has the properties which characterise the group COOн,