Arsine diphenylamine

Arsine Derivatives,Organic. Many arsine derivs were proposed as CWA s. More than 60 of such derivs are listed by Wachtel (Ref, pp 189-92). The most known of these compds is Lewisite or MI, which is f -cbloro-vinyldichloroarsine, C1-CH CH- AsC12, first isolated in 1917 by Dr W. Lee Lewis and developed as a war gas by the US Chemical Warfare Service (Ref, pp 202-6). Another important arsine CWA is Adamsite (Brit) (designated in the US as DM) or diphenylamine-chloroarsine ... 

No N-alkyl or N-dialkyl anilines have been arsonated by the Bechamp method. With diphenylamine as starting material, 4-arsonodiphenyl-amine, 4,4 -diarsonodiphenylamine, and some arsinic adds were obtained in a combined yield of 18-20%.74... 

DiPHENYLAMINE- and TErPHENYLAMINE-ARSINIC ACIDS AND THEIR DERIVATIVES. 

Diphenylamine-o-arsinic acid may be prepared either by the condensation of o-bromophaiylarsinic acid and aniline or o-aininophenyl-arsinic acid and bromobenzene, but the better yield is given by the first method ... 

Diphenylamine-p-arsinic acid inay be produced by the hydrolysis of p-phenylacetylaminophenylarsinic acid or by the direct arsenation of diphenylamine. The nitrodiphenylamine-p-arsinic acids may also be formed by the direct arsenation of nitrodiphenylamines. Direct arsenation of diphenylamine leads to the formation of two by-products, diphenylamine-p-p -diarsinic acid and iisdiphenylaminearsinic acid, the fonner yielding an arseno-compound on reduction. 

When the mixture used in the preparation of the preceding acid (Method 3) is heated at 160° to 170° C., only a small quantity of diphenylamine-o-arsinic acid results, the main product being triphenylamine-o-arsinic acid. This acid crystallises from ethyl alcohol in colourless, prismatic crystals, decomposing at 150° C. It is easily soluble in warm alcohols, very sparingly soluble in water, and insoluble in ether and acetone. Its acetic acid solution is coloured intense greeir on the addition of a little nitric acid. 

Nitrodiphenylamine-4 -arsinic acid, obtained from w-nitro-diphenylamine, crystallises in yellow needles, and yields a disodiwn salt containing 8 molecules of water. 

Diphenylamine-p-arsinic acid (0 5 gram) is suspended in 12 to 15 c.c. of 50 per cent, hypophosphorous acid and heated for a few seconds on a boiling water-bath, the mixture being rapidly stirred. Most of the solid dissolves the solution is cooled and filtered, and after a few seconds heating it is allowed to stand for five hours, the yellow precipitate washed witli water, ammonium hydroxide and alcohol, and then dried over sulphuric acid in an atmosphere of hydrogen. The arseno-compound is readily soluble in benzene, sparingly soluble in ethyl alcohol. The foregoing reaction readily proceeds further, with the formation of polyarsenides. 

Diphenylamine-o-arsinic acid (V), prepared by the condensation of o-bromophenylarsinic acid and aniline, when reduced in alcoholic hydrochloric acid by sulphur dioxide in the presence of iodine, gives lO-chloro-5 10-dihydrophenarsazine, or if boiled with concentrated hydrochloric acid yields the chloride of phenarsazinic acid, which may be reduced to the 10-chloro-compound under suitable conditions. 2-Methyl- and 4-methyldiphenylamine-6 -arsinic acids are also capable of undergoing similar reactions to those just indicated. 

Continuing examples of ring closure of diphenylamine arsinic, acids and their derivatives, 2-nitrodiphenylamine-6 -dichloroarsine when boiled in acetic acid solution for three hours is transformed into 10-chloro-4i-nitro-5 lO-dihydropkenarsazine (XIII), and reduction of... 

Condensation of benzidine (1 mol.) and o-bromoiphenylarsinic acid (2 mols.) yields 4t -his[diphenylamine-2 -arsinic acid) (XVI), which can be reduced in alcoholic hydrochloric acid by sulphur dioxide in the presence of iodine to 2 2 -hif 10-chhrt)-5 IQ-dihydrophenarsazine) (XVII) ... 

In the latter preparation, the dichloroarsine is obtained from 2-nibro-diphenylamme-Q -arsinic add. This is prepared by the condensation of o-aminophenylarsinic acid and o-bromonitrobenzene in amyl alcohol in the presence of copper powder and potassium carbonate. It crystallises in golden-yellow ne les, melting with decompositioir at 288° to 240° C. "When reduced in alcoholic concentrated hydrochloric acid solution by sulphur dioxide in the presence of iodine, it yields 2-nitro-diphenylamine-6 -dichloroarsine, which crystallises from benzene-light petroleum in deep red crystals, M.pt. 110° C. 

The preparation of this compound resembles that of diphenylamine-o-arsinic acid, the aniline used in the latter case being now replaced by monomethylaniline. It is a colourless, crystalline solid, M.pt. 182° to 184° C., with decomposition. 

Diphenylamine Ardnic Acids. 2-Nitrodiphenylamine-4-arsinic acid, ... 

Dihydrophenarsazines 21c and 2 Id formed in the first step were protonated at the benzene ring of the 5,10-dihydrophenarsazine system, where the endocyclic arsenic-carbon bonds are broken to form diphenylamine and arsines. 

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