acid, which yields a barium salt of the composition PO(OPr)O2Ba, anhydrous at 100°, and soluble in cold water, from which it separates on boiling, and an ethereal salt, PO(OPr)3, which is most soluble in water at 70-80°, dissolves in alcohol and ether, and cannot be distilled without decomposition, even in a vacuum. C. H. B.

Synthesis of Diethyl Methyl Carbinol. By A. REFORMATSKY (J. pr. Chem. [2], 36, 340-347).-Diethyl methyl carbinol, CMeÊt, OH, is prepared by the action of zinc on a mixture of diethyl ketone (100 grams) and methyl iodide (495 grams), and subsequent treatment with water. It is a colourless, mobile liquid, having a pleasant smell resembling trimethyl carbinol, boils at 122-123°, and has the sp. gr. 0-8237 at 20°, 0·8194 at 25°, 0-8179 at 30°, and 0.8143 35° (water at 0° 1). The acetate is a colourless liquid, boiling at 148 (corr.). The iodide boils at 140-144°, and is partly decomposed on distillation. When oxidised with chromic mixture, diethyl methyl carbinol yields acetic acid as the sole product. G. T. M.

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Bromination of Allyl Alcohol. By I. FINK (Monatsh., 8, 561562). By bromination of allyl alcohol in absence of water, a dibromhydrin is formed almost in the theoretical proportions, as observed by Markownikoff and v. Tollens. In the presence of water, there is formed in addition a monobromhydrin, CH,BrO2, boiling at 138°, at a pressure of 17 mm.; it is shown to be of this constitution by its conversion into glycerol and triacetin. V. H. V.

CH2CMe

Diisobutenyl Oxide. By S. PRZYBYTEK (Ber., 20, 3239—3246). -The methods of preparation of the following substances have already been given (this vol., p. 123). The dichlorhydrin, C,HCl(OH)2, is a thick, viscid, pale-yellow liquid, of faint odour and burning taste. CH2 Diisobutenyl oxide, ·CMe•CH2·CH2 CMe<-0is a colourless, mobile liquid, of agreeable odour and burning taste; it is heavier than water, and boils at 170-180° under 125 mm. pressure. As was to be expected from their respective constitutions, it combines with water with greater slowness and difficulty than does erythrene dioxide.

-0

Octylerythrol, C,H(OH), is a thick and very viscid liquid, of bitter taste, readily soluble in water and alcohol, but insoluble in ether. It can be formed directly from the chlorhydrin by heating with potash and a large excess of water. A. J. G.

Action of Hydrogen Chloride on Glycerol. By A. FAUCONNIER and J. SANSON (Bull. Soc. Chim., 48, 236-238).-Dry hydrogen chloride was passed into glycerol for five days, in an apparatus provided with a reflux condenser. The fraction of the product boiling below 80° contains hydrochloric acid and water, together with a small quantity of an oily substance precipitated by water; the fraction 80-120° contains the two dichlorhydrins, in quantity equal to half the weight of the glycerol; the fraction 120-150° contains glyceryl monochlorhydrin, and substances which crystallise in the receiver. The products boiling above 150° have not yet been examined.

The crystalline solid in the last fraction amounts to 0.75 per cent. of the glycerol used. It crystallises from alcohol in white needles, which have the same composition as epichlorhydrin, and melt at 109-110°. The substance is probably a polymeride of epichlorhydrin; it dissolves readily in cold benzene, ether, carbou bisulphide, and chloroform, is somewhat soluble in alcohol, especially on heating, and dissolves slowly in boiling water, from which it crystallises in very long needles. C. H. B.

Sugar-like Nature of Formose. By O. LOEW (Ber., 20, 3039— 3043).—A solution of formose (10 grams) in 1 litre of water is boiled in a reflux apparatus, and the whole extracted with chloroform; the residue obtained by evaporating the chloroform is treated with alcohol, aniline, and a little hydrochloric acid, when an intense red coloration is produced, showing the presence of furfuraldehyde. When formose is digested with 1 per cent. sulphuric acid on a water-bath, more furfuraldehyde is obtained than from other sugars.

Formose has all the following characteristics of sugar :-(1) Sweet taste; (2) strong reducing power; (3) ready decomposition by dilute alkali; (4) formation of saccharic acid by the action of lime; (5) power of combination with hydrogen and hydrogen cyanide, and formation of an osazone; (6) formation of humous substances by acids; (7) formation of furfuraldehyde by dilute acid; (8) capability of fermentation. The author concludes with a criticism of Wehmer's paper on the carbohydrate nature of formose (this vol., p. 40).

N. H. M.

Erythrene Dioxide. By S. PRZYBYTEK (Ber., 20, 3234-3239). -Erythrene dioxide, when treated with bromine in tubes immersed in cold water, is gradually converted into a citron-yellow, crystalline dibromide, which is insoluble in water, alcohol, and chloroform, and readily decomposes with evolution of hydrogen bromide.

A polymeride of the dioxide is obtained in very small quantities by heating the dioxide at 110-130° (below its boiling point = 137°), a better yield being obtained at 140-150°, but the best yield is obtained when sealed tubes containing powdered anhydrous sodium sulphate just moistened with the dioxide are heated at 110-120° for 10 days. In all cases the polymerisation is very incomplete. It is an amorphous, colourless substance, devoid of taste and odour, and insoluble in water, alcohol, ether, benzene, and chloroform. It can, although with difficulty, be converted into erythrol and its derivatives.

Dihydroxyerythrenedisulphonic acid, C.H.(OH)2(SO,H)2, is obtained when erythrene dioxide is shaken with a slight excess of concentrated aqueous hydrogen sodium sulphite, and the sodium salt formed decomposed with oxalic acid. It forms a deliquescent mass of felted needles, and is very unstable, charring when gently heated, and yielding sulphurous anhydride when its aqueous solution is heated at 50°. Its salts, on the contrary, are very stable. A. J. G.

Inosite. By LORIN (Bull. Soc. Chim., 48, 235-237).-The author showed 10 years ago, from its behaviour with oxalic acid, that inosite is a polyhydric alcohol (Abstr., 1878, 398). C. H. B.

Carbohydrates. By Å. G. EKSTRAND and C. J. JOHANSON (Ber., 20, 3310-3317).—The authors have obtained a new carbohydrate from the haulm of the Phleum pratense. The haulm is thickened at its lower end to a bulb and in the autumn this bulb increases in size and becomes filled with a concentrated solution of a carbohydrate to which the authors give the name graminin. This substance is a powder resembling starch, of the formula 6C, H10O5 + H2O, and fuses with decomposition at 215°. It is soluble in water and in caustic potash, insoluble in alcohol. From its aqueous solutions, baryta-water throws down a precipitate which redissolves in excess of the precipitant. It does not give a blue coloration with iodine: it reduces silver nitrate, but not Fehling's solution. Under the microscope, graminin shows spheroïdal granules which are sometimes concentrically striated : on the addition of water a part dissolves, but the larger part remains in the form of half-spheres which show radial striæ. The authors have also obtained graminin from the rhizome of Baldingera arundinacea, but in this case a part of the carbohydrate occurs in a less soluble modification. This latter modification shows decided cruciform or semicircular striæ in polarised light. Graminin also seems to be present in the rhizomes of Calamagrostis agrostis and of Teisetum hierochloa. This carbohydrate seems closely related to inulin and irisin, as is apparent from the following comparison of their properties :

From Dracaena australis the author has obtained a carbohydrate, 6C6H10O5 + H2O, which very closely resembles triticin from Triticum repens. It differs, however, from the latter in its rotatory power, which is [a]p = -36.61°, whilst that for triticin, is [a]D = -41.07°.

L. T. T. Inulin. By M. HÖNIG and S. SCHUBERT (Monatsh., 8, 529–560). -Braconnot, Berzelius, and Payen have observed the formation of certain dextrins and saccharine substances when inulin is heated; whilst Dragendorff has described intermediate products between inulin and lævulose formed by heating inulin with water under pressure. In this paper, a long account is given of experiments on the saccharification of inulin, effected either by heating inulin in glycerol or with dilute mineral acids: the specific rotatory and cupric oxide reducing powers of the various intermediate products are also set forth in a series of tables. The principal results obtained are as follows (1.) The intermediate products obtained by heating inulin with dilute mineral acids, so far as they are directly comparable, seem to be identical with the products obtained by heating inulin by itself. (2.) These dextrin-like substances differ from one another by their specific rotatory power, as also by their solubility in water and alcohol, and their precipitability by barium hydrate. At a lower

temperature, the substances formed more nearly resemble inulin as regards their sparing solubility, whilst at a higher temperature, at first certain products, metinulin and inuloid are produced, which are readily soluble in water, and not precipitated by barium hydrate. After a more profound change, the substance formed shows successively a slight lævorotatory, then no rotatory power, and finally a dextrorotatory power. The specific rotatory power varies from [a];=-415, that of inulin, to [a]; = +30-68, that of the final dextrin. (3.) The substances without specific rotatory power are not identical with lævuloses. (4.) The saccharification of inulin is effected rapidly by dilute acids, reaching its maximum in 15 to 30 minutes, according to the concentration; lævulose and the abovementioned dextrins are simultaneously produced.

The authors have also succeeded in obtaining lævulose in crystals sufficiently well developed for measurement, by frequently recrystallising the crude crystalline lævulose from absolute alcohol, the crystallisation in each case being induced by dropping in a solid crystal; a similar product was also obtained by the saccharification of inulin. Lævulose crystallises in the rhombic system, individual crystals being of the prismatic and combined crystals of the octohedral type. The axial ratio is a b c = 0·80067: 1: 0.90674, whilst 110: 110 = 77° 22′ and 011: 011 = 84° 24'. The crystals are slightly biaxial, resembling, as regards their action on polarised light, certain mixtures of sodium-ammonium and potassium-sodium tartrates. The specific rotatory power of an aqueous solution of the pure lævulose was [a]; -8974, L = 200 mm., c = 3.6555; t = 22°. This value when calculated by means of the factor 1.129 gives for [a]D the value -87.84°. Analyses are also given of the pure product, which prove that the formula C6H12O6 expresses the composition of lævulose. V. H. V.

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Fermentation of Glyceraldehyde. By E. GRIMAUX (Compt. rend., 105, 1175-1177).- By oxidising glycerol by means platinum-black, the author had previously obtained a liquid which seemed to contain glyceraldehyde, although the latter could not be isolated (Abstr., 1887, 695). When this product is distilled in a vacuum with dilute hydrochloric acid, its rotatory power is considerably reduced, and a gummy residue is left which is soluble in absolute alcohol. The residue therefore contains no dextrin, and since dextrose is converted into dextrin under these conditions, it follows that the product of the action of platinum-black on glycerol contains no dextrose. With phenylhydrazine, it yields a compound identical with the hydrazine-derivative obtained by Fischer and Tafel from the products of the oxidation of glycerol by nitric acid. The author oxidised glycerol by Fischer and Tafel's process, neutralised with potassium hydroxide, extracted with alcohol, and evaporated the solution to dryness in a vacuum. The product thus obtained has very little reducing power, but if boiled with very dilute sulphuric acid it recovers its reducing power, and after neutralisation it ferments readily in contact with yeast. Glyceraldehyde is not converted into glucose by treatment with hydrochloric acid.

This is the first instance of the synthetical formation of a sugar which undergoes alcoholic fermentation. It is evident that the property of fermenting in this manner is not confined to carbohydrates containing C, and C12. C. H. B.

By H. v. PECHMANN (Ber.,

Decomposition of Nitrosoketones. 20, 3213-3214; compare this vol., p. 146).-When boiled with dilute sulphuric acid, fatty nitroketones are converted into hydroxylamine and diketones. When the liquid obtained by treating an alkaline solution of ethyl methylacetoacetate with sodium nitrite and sulphuric acid is distilled with much sulphuric acid, a yellow distillate containing diacetyl is obtained. N. H. M.

Action of Zinc Ethide and Zinc Iodoethide on Dipropylketone. By P. MENSCHIKOFF (J. pr. Chem. [2], 36, 347-352).— Both zinc ethide and zinc iodoethide form condensation-products with dipropyl ketone, but only the compound of the iodoethide yields a tertiary alcohol on treatment with water.

G. T. M.

Diacetyl and its Homologues. By H. v. PECHMANN (Ber., 20, 3162-3164).—By successive treatment with sodium hydrogen sulphite and dilute acids, the homologues of nitrosoacetone are converted into a-diketones (homologues of diacetyl), ammonia and sulphuric acid being also produced. From nitrosomethylacetone, diacetyl is obtained: COMe CMe:NOH + H2SO, COMe CMe:NSO,H+ H2O = COME COMe + NH,HSO..

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It is a yellowish-green oil which boils without decomposition at 87-88°, and does not solidify when placed in a freezing mixture of ice and salt; its odour resembles that of acetone, and its vapour is the colour of chlorine; it dissolves in 4 parts of water at 15°, forming a yellow solution, and is miscible with ordinary solvents. It is decomposed by alkalis or hot alkaline carbonates, forms a colourless, crystalline substance with ammonia, and with phenylhydrazine yields two hydrazides, melting at 133° and 242° respectively. With aniline, it forms a crystalline product; with orthodiamines, liquid quinoxalines are produced, and it combines readily with alkaline hydrogen sulphites. When reduced in acid solution, it is converted into a benzoïu which reduces Fehling's solution instantly at the ordinary temperature. Since in its physical properties diacetyl differs so considerably from glyoxal, the latter compound must be considered as a polymeric diformyl: diacetyl, however, resembles its higher homologues dibutyl and diisovaleryl. F. S. K.

Chlorinated Methyl Formates. By W. HENTSCHEL (J. pr. Chem. [2], 36, 305–317; compare Abstr., 1887, 1027, 1099).-Trichloromethyl chloroformate, CÒCI-OCC13, is obtained among other products of the chlorination of methyl chloroformate. When heated at 300°,

it decomposes into twice its volume of carbonyl chloride; at a dullred heat, it yields carbonic anhydride and carbon tetrachloride, whilst in presence of aluminium chloride it is rapidly and completely