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pact, citron-yellow needles or prisms, melts at 143-143.5°, and is soluble in ether and light petroleum, readily soluble in boiling alcohol; 100 parts of alcohol dissolve 07 part of the oxide at 15°.

Methylphenylthiocarbamine chloride, CSCI-N Ph Me, prepared similarly to the ethyl-compound, forms pale-yellow crystals, melts at 345-35°, and is soluble in light petroleum; if heated with alcohol it yields methylphenylthiocarbamine oxide, (CS·NPhMe),O, in sulphur-yellow crystals, melting at 116.5°.

When either ethyl- or methyl-phenylthiocarbamine chloride (1 mol.) is heated with ethyl- or methyl-aniline (2 mols.) at 100°, a considerable rise of temperature occurs and tetra-substituted thiocarbamides are obtained; these are soluble in light petroleum and alcohol, but insoluble in alkalis. Diethyldiphenylthiocarbamide, CS(NPhEt), crystallises from light petroleum in white tables, from alcohol in long needles or prisms, and melts at 75.5°; the dimethyl-derivative forms monoclinic crystals and melts at 72.5°, and the methylethyl-derivative crystallises in forms resembling those of the methyl-derivative, and melts at 49.5°. W. P. W.

Orthamidophenyl Mercaptan. By A. W. HOFMANN (Ber., 20, 1788-1797). The action of carbon bisulphide on orthamidophenyl mercaptan or the corresponding disulphide gives, not as was expected, a thiocarbamide, but a mercaptan of the formula C.H.<>C.SH. This crystallises in lustrous, colourless needles, melts at 179°, has an intensely bitter taste, and is insoluble in water, soluble in alcohol, ether, and acetic acid. Proof of its constitution is given by its formation by the action of chlorophenylthiocarbimide on sodium hydrosulphide, and by its decomposition into orthamidophenyl mercaptan, carbonic anhydride, and hydrogen sulphide when fused with potash. The corresponding disulphide, S(C,H,NS), is obtained by adding potassium dichromate to an acetic acid solution of the compound. It forms silvery plates, melts at 180°, and is converted into a black, amorphous substance when further oxidised. The methyl ether, C,H,NS SMe, crystallises in short, colourless prisms and melts at 52°; it forms unstable salts, the platinochloride,

(C,H,NS SMe),H,PtCl,

crystallises in lustrous plates.

Thioanisidine, NH, CH,SMe, is prepared by the action of methyl iodide on orthamidophenyl mercaptan, and subsequent hydrolysis of the resulting hydriodide. It is a colourless liquid, distils with some decomposition at 234°, and yields well-defined salts, which can be recrystallised from water. The hydrochloride forms colourless needles.

Dithioanisylthiocarbamide, CS(NH CH, SMe), is prepared by digesting thioanisidine with carbon bisulphide for some hours in a reflux apparatus; it crystallises in small, colourless prisms, and melts at 162°; when further heated it yields thioanisylthiocarbimide,


and thioanisidine. The former is a light-yellow oil of burning taste, which boils about 270°, but could not be obtained pure. With alcoholic ammonia it yields thioanisylthiocarbamide,


a substance crystallising in prisms and melting at 168°. Anisylthiocarbimide, NCS.C,H,OMe, is obtained by distilling dianisyl thiocarbamide; it boils at 264-266°, and when treated with alcoholic ammonia is converted into anisylthiocarbamide,


which crystallises in colourless needles melting at 152°.

When a mixture of amidophenyl mercaptan and phenylthiocarbimide is heated, the substance previously described by the author (Abstr., 1880, 388) as anilidophenylthiocarbimide is obtained, he now regards it as having the constitution C,H,<>C•NHPh.

When an ethereal solution of amidophenyl mercaptan is mixed with ethyl chlorocarbonate, a colourless oil is obtained, which from its mode of formation and properties would seem to have the composition SH.C&H NH.COOEt. When distilled it yields alcohol and Hofmann's hydroxyphenylthiocarbimide.

A. J. G.

Xylyl Phosphorous Compounds: Toluphosphinic Acids. By J. WELLER (Ber., 20, 1718-1725. Compare Michaelis and Paneck, Abstr., 1882, 958).-Mercury dixylyl, Hg(C,H,Me2) [Hg: Me2 = 413], is obtained by heating bromometaxylene with 2 per cent. sodium amalgam at 140-150° for 12 hours. It crystallises in slender, felted needles, melts at 169-170°, and is sparingly soluble in ether, alcohol, and cold benzene, readily soluble in hot benzene. Hydrochloric acid on boiling readily decomposes it into mercuric chloride and metaxylene.

1.3.4 Xylylphosphochloride, CH,Me2 PCl2, is obtained by the action of phosphorous chloride on 1:3: 4 mercury dixylyl at 230240°. It is a colourless, highly refractive liquid, which fumes slightly in the air and boils at 256-258°. Water decomposes it with formation of xylylphosphinous acid. Chlorine unites vigorously with it, forming the viscous, yellow tetrachloride which is decomposed by water first into the oxychloride, then into xylylphosphinic acid melting at 194°.

By the action of phosphorous chloride on metaxylene in presence of aluminium chloride, a mixture of the preceding a-compound with smaller quantities of an isomeride, B-xylylphosphochloride [Me2 : PCI, = 1:35?] is obtained. This mixture forms a colourless liquid boiling constantly at 256°, and of sp. gr. 1-24 at 18°. It absorbs chlorine to form a mixture of the tetrachlorides, which is obtained as a viscid mass having crystals interspersed through it. As the a-tetrachloride is liquid, the crystals must be those of the B-compound. When treated with sulphurous anhydride the tetrachlorides are converted into the oxychlorides which distil at 280-300°, but cannot be separated by distillation. The oxychlorides are therefore decom

posed by long boiling with water into the corresponding metaxylylphosphinic acids, which can then be separated by crystallisation.

a-Metaxylylphosphinic acid, CH ̧Me, PO(OH), [1:3:4], forms long, white needles, melts at 194, and is very readily soluble in alcohol, more sparingly in ether. 100 parts of water dissolve 1·5 parts of the acid at 20° and 6.9 parts at 100°. When heated with alkalis it is decomposed into metaxylene and phosphoric acid. Bromine acts on it in aqueous solution with formation of phosphoric acid and a mixture of brominated metaxylenes. The barium, cadmium, nickel, and silver salts are described. The metaxylylphosphinic acid (m. p. 186-187°) obtained by Michaelis and Paneck (loc. cit.), was probably a mixture of this acid with some of the acid of lower melting point. When treated with nitric acid it yields two isomeric nitro-acids, NO2 CH2Me, PO3H2, of which one, the less soluble in water, crystallises in needles and melts at 182°, whilst the other melts at 100°.

B-Metaxylylphosphinic acid, CH ̧Me2•PO(OH2) [1:3: 5?], crystallises in thin plates, melts at 161°, and is soluble in alcohol and ether. 100 parts of water dissolve 18 parts of the acid at 15° and 1173 parts at 100°. Its behaviour with alkalis and bromine resembles that of the a-acid, except that in the latter case a sparingly soluble bromoxylylphosphinic acid is also invariably formed. The salts of this acid resemble those of the a-acid but are somewhat more soluble. Nitric acid partly oxidises it to ẞ-toluphosphinic acid, partly converts it into a nitro-acid, NO, CH, PO3H2.


a-Toluphosphinic acid, COOH-C2H3Me PO(OH)2, is prepared by oxidising a-metaxylylphosphinic acid in dilute alkaline solution with the calculated amount of potassium permanganate. It crystallises in colourless prisms, melts at 262°, and is readily soluble in alcohol and hot water, sparingly soluble in ether. It is a strong tribasic acid, but its salts are difficult to prepare in a pure state, as there is a tendency to form mixtures of normal and acid salts. When strongly heated it is converted with partial carbonisation into metatoluic and metaphosphoric acids. The chloride, COCI·C,H,Me•POCl2, is a thick liquid which distils at about 310°.

B-Toluphosphinic acid melts at 220°, but otherwise resembles the a-acid from which, however, it is distinguished by not giving a crystalline precipitate when mixed with copper sulphate solution.

A. J. G. Condensation of Aldehydes with Phenols. By A. MICHAEL (Ber., 20, 1572-1573).-A reply to Claisen (Ber., 19, 3316, footnote).

Oxidation of Ketones with Potassium Ferricyanide. By K. BUCHKA and P. H. IRISH (Ber., 20, 1762–1767).—Claus' rule, that only those aromatic methyl ketones can be oxidised to a-ketonic acids which contain a side-group in the ortho-position to the methyl-group (Abstr., 1886, 462), although seemingly true for oxidations with potassium permanganate, is decidedly not correct if potassium ferricyanide is employed as the oxidising agent.

When paratolyl methyl ketone is oxidised with potassium ferri

cyanide in alkaline solution in the cold, it yields paratoluic acid and paratolylglyoxylic acid. The latter, C,H,Me•CO·COOH [= 1 : 4], is crystalline, melts at 95-97° (uncorr.), and is not volatile. The barium salt (+ 8 mols. H2O) and the potassium salt were prepared. It gives a crystalline compound with phenylhydrazine, melting at 144°, and when heated with concentrated sulphuric acid and benzene containing thiophen yields a red dye, in this resembling phenylglyoxylic acid. The acid when further oxidised yields terephthalic acid.

Orthoxylylglyoxylic acid, CH,Me, CO COOH [Me2 : CO·COOH = 4:31], is prepared in like manner from methyl orthoxylene ketone; it melts at 92° (uncorr.), and yields a barium salt crystallising in slender needles.

Methyl metatolyl ketone, prepared by distilling calcium metatoluate and acetate, boils at 218-220°, and by oxidation with potassium ferricyanide is converted into an acid not volatile with steam; this is still under investigation. A. J. G.

Cyanacetophenone. By A. HALLER (Compt. rend., 104, 1448— 1451). Cyanacetophenone seems to have an acid function, and dissolves readily in alkalis, but the compounds formed are very unstable. The silver-derivative, COPh-CHAg CN, is obtained by adding silver nitrate to a dilute alcoholic solution of cyanacetophenone neutralised with soda or ammonia. It is insoluble in water and alcohol, and is decomposed when exposed to light.

When cyanacetophenone is boiled with concentrated potash it yields ammonia, potassium benzoate, and potassium acetate. A saturated solution in absolute alcohol when cooled at 0°, and treated with hydrogen chloride, deposits white needles of the composition CHO2NCI, insoluble in water and ether. This compound in all probability has the constitution COPh-CH, C(OEt): NH, HCl, and is the hydrochloride of ethyl benzoylacetonitrile. With ammonia it yields ammonium chloride and ethyl benzoylacetonitrile, and with potassium nitrate it yields a corresponding nitroso-derivative, which crystallises in needles melting at 117°. When the hydrochloride is heated with dilute alcohol it yields ammonium chloride and ethyl benzoylacetate.

The action of hydrochloric acid in excess on cyanacetophenone in presence of alcohol, yields ethyl benzoate and ammonium chloride.

Ethyl cyanacetate, when treated with metallic sodium, yields the derivative CN·CHNa·COOEt, and this in contact with iodo-derivatives and acid chlorides, yields compounds of the type CN CHR.COOEt.

C. H. B.

Isonitroso-compounds. By E. BECKMANN (Ber., 20, 1507-1510; compare Abstr., 1885, 618).-The intramolecular change which takes place when diphenylketoxime is treated with phosphorous pentachloride, is also produced by strong sulphuric acid at 100°. When the product of the reaction is poured into water, the precipitate treated with sodium carbonate and recrystallised from alcohol, pure benzonitrile is obtained. When the latter is heated for some time with sulphuric acid, benzoic acid and aniline are formed.

Methylphenylketoxime yields acetanilide when heated with sulphuric acid.

Benzaldoxime (2.5 parts) when poured into a mixture of 10 parts of sulphuric acid and 1 part of water, is converted into benzamide, and not into formonitrile, as was expected.

In a similar manner the dioxime of benzil is converted by sulphuric acid into a crystalline compound melting at 110°.

N. H. M.

Aromatic Ethylenediketones and Alkylated Benzoyl-ppropionic Acids. By A. CLAUS and others (Ber., 20, 13741378). The authors have obtained the above compounds by the action of succinic chloride on aromatic hydrocarbons in the presence of aluminium chloride. When 1 mol. of the hydrocarbon is used, the chief product obtained is a benzoylpropionic acid, whilst with 2 mols. of hydrocarbon it is a diketone.

1. By CLAUS and WERNER.-Diphenyl ethylene diketone,


prepared from benzene, crystallises in colourless needles, insoluble in water, soluble in alcohol, ether, and benzene, and melting at 140°. Benzoyl-3-propionic acid melts at 116°, and has already been obtained by Burker (Abstr., 1881, 273). Dimetarylyl ethylene diketone, C2H.(CO C6H3Me2); [CO: Me: Me 1: 2: 4], prepared from metaxylene, forms colourless needles, soluble in alcohol, ether, and chloroform, and melting at 129°. With phenylhydrazine, it yields a dihydrazide, crystallising in orange needles melting at 189°. The diisonitrosoderivative, C2H22(NOH)2, is white, and melts at 140°. When oxidised with dilute nitric acid, the diketone yields metaxylic (orthoparadimethylbenzoic) acid, thus proving the constitution to be as above. Orthoparadimethylbenzoyl-p-propionic acid,

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is almost insoluble in water, soluble in organic solvents. It crystallises in colourless needles melting at 108°. Several of the salts are


II. By CLAUS and SCHLARB.-Paraditolyl ethylene diketone,

C2H,(CO.C,H,Me), [CO : Me = 1 : 4],

crystallises in colourless needles melting at 159°. oxidises it to paratoluic acid. Paratoluyl-p-propionic acid,


Nitric acid

crystallises from water in minute needles melting at 127°. Dipseudocumyl ethylene diketone, C2H, (CO·CH2Me3)2, forms crystals melting at 120°, and yielding, with nitric acid, 2: 4: 5 trimethylbenzoic acid. 2:45 Trimethylbenzoyl-B-propionic (pseudocumyl-7-ketonic) acid, CH2Me, CO C2HCOOH, forms colourless crystals melting at 105°.

III. By CLAUS and MURTFELD.-Diparaxylyl ethylene diketone, C2H,(CO CH2Me), forms needles melting at 123°. Paraxylyl-4ketonic acid, CH3Me2 CO C2H, COOH, forms colourless needles melt

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