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alcohol, but insoluble in ether; it has a neutral reaction and a bitter taste.

The mother-liquor contains tetramethylammonium hydrate, together with the betaïne, and by addition of platinic chloride and systematic crystallisation the two compounds can be separated. Trimethyl-a-amidobutyrobetaine platinochloride forms elongated, pointed, orange-yellow prisms, which are almost insoluble in alcohol; they contain 1 mol. HO, but become anhydrous at 100°. The hydrochloride is obtained from the platinochloride, but will not crystallise. If its solution is mixed with auric chloride, a precipitate seems to form, but this is really an emulsion of the aurochloride, which after some time separates as a yellow oil; this dissolves readily on heating, but is reprecipitated as an oil when the liquid cools. After some time it solidifies and forms lamellar crystals.

Attempts to obtain the corresponding ethyl-derivative were unsuccessful. A small quantity of triethyl-a-amidopropiobetaïne was, however, obtained by the action of ethyl-a-amidopropionate on triethylamine. C. H. B.

Action of Ammonia on Chlorethanes: Direct Union of Ammonia with Non-saturated Compounds. By R. ENGEL (Compt. rend., 104, 1621-1624).-Vinyl chloride, obtained by treating ethylene chloride with alcoholic potash, was washed with alcohol, and passed into alcoholic ammonia until no more was dissolved. At the ordinary temperature there is no action, even after several months. Vinyl bromide likewise has no action on alcoholic ammonia at the ordinary temperature. At 100° there is also practically no action, but at 150-160°, in presence of concentrated alcohol, a complex reaction takes place, the principal product being ethylenediamine. This result shows that certain non-saturated compounds are capable of combining directly with ammonia, a reaction which furnishes a new method of preparing amines. The author has obtained several acid amines by the action of ammonia on non-saturated acids.

In all cases when ammonia acts on ethylene chloriodide in aqueous or alcoholic solution, only ethylene bases are formed, both halogens being removed simultaneously. These results agree with Simpson's observations. Friedel and Silva have likewise shown that when ethylene chloriodide is treated with silver the products are ethylene and ethylene chloride.

Ammonia acts more readily on chlorethylene chloride in either alcoholic or aqueous ammonia even at the ordinary temperature. The product is always C2H2Cl2, boiling at 37°, and hence the action of ammonia under these conditions is similar to that of potash. The theoretical yield is obtained. C. H. B.

Red Dye from Chloral Hydrate. By J. Z. LERCH (Chem. Centr., 1887, 299).-Walz, Ogston, and others have noticed the formation of red colouring matter of the composition CH24S13NO, when ammonium sulphide is added to chloral hydrate. If hydrogen sulphide is passed into an ammoniacal solution of chloral hydrate a larger amount of the dye is produced. On prolonged passage of the

gas the red passes into a yellow coloration simultaneously with the disappearance of the alkaline reaction. A good result is obtained with sodium thioantimonate, the liquid becoming turbid with separation of sulphur and antimony pentasulphide. This reaction can be used for the detection of chloral hydrate. After acidification, the red colouring matter can be taken up by petroleum, chloroform, and carbon bisulphide to form yellow solutions, turning red on addition of alkali. From the solution in petroleum, the compound is obtained in fine crystals of a green, metallic lustre. Salts of mercury, lead, and silver form red compouuds with solutions of the crystals, which decompose slowly after a time, but more rapidly on heating, with separation of metallic sulphides. V. H. V.


Condensation of Normal Butyraldehyde. By G. A. RAUPENSTRAUCH (Monatsh. Chem., 8, 108-119).-x-Ethyl-B-propylacrylic hyde, CH2Me CH, CH: CEt CHO, is prepared by adding 35 grams of 10 per cent. aqueous soda to a mixture of 35 grams of normal butyraldehyde and 600 c.c. of water. The whole is shaken and heated for two hours at 40°. After 24 hours it is made neutral or slightly acid by dilute sulphuric acid, and steam-distilled in an atmosphere of carbonic anhydride. The oily product is dried and distilled in a current of carbonic anhydride. It is a colourless oil boiling at 172:4 -173·4° (corr.) ; it is almost insoluble in water, insoluble in hydrogen sodium sulphite. It reduces ammoniacal silver solution, and reacts with phenylhydrazine. When treated with bromine the compound CH1Br2O is formed. When oxidised with potassium dichromate and sulphuric acid, an acid, CH16O2, is obtained.

Ethylbutylacetaldehyde, CH, CHEt CHO, is obtained by reducing the above aldehyde with iron filings and 60 per cent. acetic acid; the product is distilled, and the fraction boiling below 179° treated with sodium hydrogen sulphite, and the crystalline double compound washed with ether and decomposed by sodium carbonate. It is then steam-distilled. It is an oily substance, boiling at 160-162° (uncorr). It reduces ammoniacal silver solution, and does not form an additive compound with bromine. The portion of the product which boils above 179° appears to consist of an unsaturated alcohol, CH13 CH2'OH, and the corresponding saturated octyl aldehyde. N. H. M.

Glyceraldehyde. By E. GRIMAUX (Compt. rend., 104, 1276— 1278). Anhydrous glycerol oxidises somewhat rapidly in contact with comparatively inactive platinum-black, and if the platinum is very active it is necessary to dilute the liquid with about 2 vols. of water in order to moderate the energy of the reaction. The liquid acquires considerable reducing power and becomes acid, the acidity increasing as the reducing power diminishes if the action of the platinum is prolonged, owing to the conversion of the aldehyde into the acid. The product is extracted with water and the solution concentrated in a vacuum. It reduces Fehling's solution, gives a mirror with ammonio-silver nitrate, and becomes yellow when boiled with alkalis, lime, or baryta. If the concentrated solution is mixed with sodium hydrogen sulphite, heat is developed, and on addition of alcohol

a gummy mass is precipitated which seems to be a combination of the sulphite and glyceraldehyde. With phenylhydrazine hydrochloride and sodium acetate the solution yields coloured precipitates, some of which dissolve in potash, whilst the others are insoluble and have not yet been obtained pure. The hydrazine-derivative soluble in alkalis is recrystallised from benzene and afterwards from dilute alcohol. It then has a constant melting point.

The products of the oxidation of glycerol by platinum-black ferment in contact with beer yeast, and yield carbonic anhydride and ethyl alcohol. Fermentation is slow owing to the presence of a large quantity of unaltered glycerol, and is never complete.

The formation of hydrazine-derivatives soluble in alkalis, and the small quantity of carbonic anhydride evolved, compared with the reducing power of the product, indicate the formation of an aldehydic acid. Other oxidising agents, such as chromic acid, chlorine, bromine, or sunlight convert glycerol into substances having great reducing power.

Erythrol in contact with platinum-black is oxidised more slowly than glycerol, but seems to yield products which have a strong reducing power, and are fermented by yeast.

The author refers to a paper by Fisher and Tafel (this vol., p. 651) on azones derived from the products of oxidation of glycerol and erythrol.

C. H. B.

Alkyl Hypochlorites from Isonitroso-compounds. By R. MÖHLAU and C. HOFFMANN (Ber., 20, 1504-1507).—When an aqueous solution of hydroxylamine is treated with hypochlorous acid (equal mols.), a reaction takes place with formation of nitrogen, chlorine, and water.

Acetoxime hypochlorite, NOCI: CMe2, is obtained by adding a solution of hypochlorous acid (prepared by saturating a cold 10 per cent. solution of soda) to a saturated aqueous solution of acetoxime kept cold with ice. An excess of hypochlorous acid must be used, and the whole well shaken until the blue colour at first produced disappears. The ether is then separated, washed with water, and dried with calcium chloride. It is a mobile liquid of an agreeable odour, sparingly soluble in water, readily in alcohol and ether. When cooled by means of ether and carbonic anhydride, it solidifies to colourless prisms. It distils with steam. When suddenly heated it explodes, but when carefully heated, boils at 134° (uncorr.) with partial decomposition. Acetaldoxime hypochlorite, NOCI CHMe, is prepared in a manner similar to the above compound. It is a colourless liquid having a powerful odour; it decomposes very readily, giving off hydrogen chloride, and could not be analysed. It explodes when heated.

N. H. M. Capraldoxime and Methylhexylacetoxime. By A. BÉHAL (Bull. Soc. Chim., 47, 163-165).-The aldoxime and acetoxime were prepared from the capraldehyde and methyl hexyl ketone respectively, which were shown to be distinct compounds in a preceding memoir (this vol., p. 788). The compounds obtained are very similar to one another in appearance, being oleaginous liquids which do not yield

crystals when cooled with ice and salt; they have an aromatic odour and are lighter than water in which they are insoluble; they dissolve readily, however, in alcohol and ether. The aldoxime boils at 121° to 123°, and the acetoxime at from 116° to 117°.

A. P.

Synthetic Acetic Acid and its Derivatives. By L. HENRY (Compt. rend., 104, 1278-1281).-Synthetic acetic acid from acetonitrile has never been examined and compared with acetic acid produced in the ordinary way.

Acetonitrile was prepared by the action of methyl iodide on potassium cyanide, and was converted into acetic acid by mixing with 25 parts of hydrochloric acid of 40 per cent. in a well-cooled flask. When the reaction ceases the liquid is heated on a water-bath for several hours, the acid distilled off, converted into the anhydrous sodium salt, and decomposed by dry hydrogen chloride.

The acid thus obtained was carefully compared with acetic acid produced by fermentation and by the destructive distillation of wood. It was converted into monochloracetic acid, ethyl acetate, and acetamide, and a portion of the monochlor-derivative was converted into malonic acid by Kolbe and Muller's method.

Synthetic acetic acid and its derivatives are identical in every respect with the corresponding compounds prepared in the ordinary way, and hence they may be used in the preparation of the ß, y, and d monosubstitution-derivatives of methane (this vol., p. 711).

C. H. B.

Cyanacetic Acid, By L. HENRY (Compt. rend., 104, 1618-1621). -The hydrogen in the CH-group in malonitrile can be replaced by metals, notably by silver, and the hydrogen in hydrocyanic acid is distinctly basic. It was therefore to be expected that the hydrogen in the CH-group in cyanacetic acid, united as it is with a cyanogengroup and a carboxyl-group, would likewise be basic. Experiment confirms this conclusion.

A solution of ethyl cyanacetate in ether is rapidly and energetically decomposed by sodium, with evolution of hydrogen and separation of a white, pulverulent substance insoluble in ether. This product, ethyl cyanosodacetate, is a very light, very hygroscopic, and easily fusible solid, which reacts readily with haloïd ethers, forming liquids which have a more agreeable odour than that of cyanacetic acid, and are insoluble in, and heavier than, water. The following compounds were obtained in this way :-Ethyl methylcyanacetate, which boils at 194°, vapour-density 434; ethyl ethylcyanacetate, which boils at 204-205°; and ethyl allylcyanacetate, which boils at 215-220°

Ethyl cyanacetate is rapidly decomposed by aqueous ammonia, and if the solution is allowed to evaporate spontaneously, crystals of cyanacetamide separate. The alkyl-derivatives just described are only very slowly attacked by ammonia. Cyanacetamide, CN-CH, CONH2, crystallises from alcohol in small needles, which melt at 118°; ethylcyanacetamide, CN CHEt CONH2, forms small, nacreous plates which melt at 113°.

Ethyl cyanosodacetate readily reacts with carbonic chloride, yielding a crystalline product, CN CH(COOEt)2.

The alkyl-derivatives are very readily obtained by Conrad and Limpach's method, that is, by the action of the corresponding alkyliodides on the product of the action of an alcoholic solution of sodium ethoxide on ethyl cyanacetate.

The hydrogen of the CH2-group is very readily replaced by chlorine and bromine. The chlorine-derivative, CN-CHCI-COOEt, is a colourless liquid which has a pungent odour like that of chloropicrin, and boils at about 190°; vapour-density 5.11.

Pure cyanacetic acid is readily obtained in well-defined, white crystals which melt at 65-66°, and not at 55° as stated by Van t' Hoff. C. H. B.

Ethyl Cyanacetate. By A. HALLER (Compt. rend., 104, 16261627). When a solution of ethyl cyanacetate in its own volume of absolute alcohol is treated with the theoretical quantity of sodium ethoxide, it yields a crystalline magma of ethyl cyanosodacetate, CN CHNA COOEt, which is dried on porous plates and then over sulphuric acid in a vacuum. This compound forms white crystals almost insoluble in alcohol, but soluble in water, by which it is decomposed. When exposed to air it absorbs water and carbonic anhydride.

If the alcohol is present in sufficient quantity to keep the sodiumderivative in solution, the corresponding derivatives of the other metals can be obtained by double decomposition, but have not yet been analysed. The silver-derivative is yellow, but rapidly becomes brown when exposed to light, and black when boiled with water; the copper-derivative is greenish-blue, and becomes grey when heated with water; the zinc-derivative is white.

When an alcoholic solution of ethyl cyanosodacetate is treated with ethyl iodide, it yields a product which boils at 210-215°; with an ethereal solution of acetic chloride it yields ethyl cyanacetoacetate, identical with the product obtained by the author and Held by the action of cyanogen chloride on ethyl acetosodacetate. C. H. B.

a-Methylamidovaleric Acid. By A. MENOZZI and C. BELLONI (Gazzetta, 17, 116-119).--Methylamidovaleric acid,


a homologue of sarcosine, is formed by warming a mixture of butaldehyde and hydrocyanic acid in molecular proportion, then adding the required quantity of methylamine; the nitrile thus obtained is then saponified. The acid crystallises in long, glistening needles very soluble in water; it sublimes slightly at 110°, more completely at 160°. The salts are very soluble in water and alcohol. The nitrate and sulphate crystallise in needles, the sulphate in prisms; the copper salt, Cu(CHNO2)2,2H2O, in violet-blue prisms. V. H. V.

Substituted Crotonic Acids. By W. AUTENRIETH (Ber., 20, 1531-1533).—Escales and Baumann (Abstr., 1886, 879) obtained a thiophenylcrotonic acid melting at 176-177° from ethyl B-dithiophenylbutyrate. The same acid can be obtained from chlorerotonic

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