Arsenious oxide, phenyl

Mercury diphenyl has been prepared in a number of ways. The most important methods are by the action of sodium on a mixture of bromobcnzene and mercuric chloride 1 from sodium amalgam and phenyl mercuric iodide 2 by the interaction of phenyl mercuric bromide and potassium sulfide2 or phenyl mercuric acetate and sodium stannite 3 from phenyl magnesium bromide and mercuric chloride 4 by the action of phenyl hydrazine on mercury compounds 5 from mercuric chloride and phenyl arsenious oxide 6 and from diphenyl mercuric ammonium acetate and sulfur compounds.7... 

Water. Phenyl dichloroarsine on treatment with water is hydrolysed to phenyl arsenious oxide ... 

This forms crystals melting at 142° C. and is insoluble in water and ether but soluble in alcohol, benzene and chloroform. A pol5aner of phenyl arsenious oxide is also formed, probably a dimer, of the formula ... 

Alkali Hydroxides. Phenyl dichloroarsine is also hydrolysed by the action of alkali hydroxide solutions. The phenyl arsenious oxide in presence of excess alkali is converted to the salt of the corresponding phenyl arsenious acid ... 

This forms crystals melting at 26-5° C. and decomposes rapidly with formation of phenyl arsenious oxide by the action (rf water or even on exposure to moist air ... 

This is readily hydrolysed by the action of moisture forming phenyl arsenious oxide and aniline hydrochloride. 

Silver Cyanide. By prolonged boiling (5 hours) of silver cyanide with phenyl dichloroarsine in benzene solution, phenyl dicyanoarsine, CgHsAs(CN)2, is formed as crystals with an odour which is both aromatic and also resembles hydrocyanic acid. It melts at 78-5° to 79-5° C., and is readily decomposed by water or even by damp air, with formation of phenyl arsenious oxide and hydrocyanic acid. 

By the action of phenyl magnesium bromide on arsenious oxide. Triphenyl arsine is obtained at the same time. ... 

The mixture is stirred continuously and maintained for 3 hours at 15° C., when sodium phenyl arsenate is formed. This is neutralised with hydrochloric acid and filtered through a press in order to separate resinous substances which are formed. The phenyl arsenic acid in the filtrate is reduced to phenyl arsenious oxide by passing a current of sulphur dioxide through. A heavy oil deposits at the bottom of the vessel and this is removed by decantation and redissolved in 40° B. sodium hydroxide solution. After diluting with 8 cu. m. of water, the solution is cooled to 15° C. and run slowly into another solution of diazobenzene chloride prepared as before. The sodium salt of diphenyl arsenic acid which is formed is slightly acidified with hydrochloric acid, the diphenyl arsenic acid filtered off and redissolved in 20° B6. hydrochloric acid (i part of the arsenic acid requires 3 parts of hydrochloric acid) and the solution obtained is then run into an iron vessel, lined internally with tiles. Sulphur dioxide is then passed through for 8 hours while the temperature is maintained at about 80° C. Diphenyl chloroarsine then separates as an oil which forms a layer at the bottom of the vessel. It is separated off and dried in vacuo. 

Diphenylarsenoxide, [(CgHs)2As]20, may be obtained either by heating diphenylchloroarsine with alcohol potassium hydroxide, or by the interaction of magnesium phenyl bromide and powdered arsenious oxide in ether solution. It separates from ether in warty crystals, M.pt. 91° to 92° C., and yields diphenylarsenic oasychloride, [(CgHg) AsClgJO, with dry chlorine. 

The reduction of 3-methyldiphenylamine-6 -arsinic acid by sulphur dioxide in hot alcoholic hydrochloric acitl. solution yields this )roduct, M.pt. 216° to 217° C., obtained as a homogeneous body identical with the reduction product of 3-methyldiphenylamine-C-arsinic acid. The substance also results when arsenious chloride is condensisl with phenyl-m-tolylamine. Oxidation with hydrogen jicroxide or Chloramiue-T gives a product indistinguishable from synthesised 1-methyl- or. 3-metliyl-phenarsazinic acid. The action of concentrated hydrochloric acid on... 

The body shows decomposition if heated above 270° C. and burns in air with a reddish flame and the separation of lead oxide. It is moderately soluble in chloroform, benzene, or carbon bisulphide when hot, and difficultly soluble in alcohol, ether, ligroin, or acetic acid. If heated in a sealed tube with hydrochloric acid decomposition occurs, lead tetrachloride and benzene being produced. By the action of halogens or concentrated nitric acid two phenyl groups are split off, and a lead diphenyl dihalide or dinitrate formed. A similar action takes place with iodic acid, formic, acetic, trichloracetic, propionic, valeric, and p-nitrobenzoic acids. With metallic chlorides the following derivatives are formed arsenic trichloride — lead diphenyl dichloride and diphenyl arsenious chloride antimony trichloride — lead diphenyl dichloride and diphenylstibine chloride antimony penta-chloride — lead diphenyl dichloride and diphenylstibine trichloride bismuth tribromide —> lead diphenyl dichloride and diphenylchloro-bismuthine thallie chloride —> lead diphenyl dichloride and thallium diphenyl chloride tellurium tetrachloride —> lead diphenyl dichloride and tellurium diphenyl dichloride. 

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