Phenylhydrazine salts

Phenylhydrazine condenses with carbon disulphide to yield the phenylhydrazine salt of P phenyldithiocarbazic acid (I), which on heating at 96-98 until the first evolution of ammonia is detectable affords diphenylthiocarb-azide (II) ... 

If sodium nitrite solution is run drop by drop into an aqueous solution of a phenylhydrazine salt the yellow, poisonous a-nitrosophenyl-hydrazine is formed it can be converted, with elimination of water, into phenyl azide. 

A. Phenylhydrazine salt of ji-phenyldithiocarbazic acid. In a 1-1. three-necked flask, fitted with a mechanical stirrer, a condenser, and a dropping funnel, is placed a solution of 128 ml. (1.3 moles) of pure redistilled phenylhydrazine in 600 ml. of ordinary ether. To the vigorously stirred mixture, 52 ml. (0.86 mole) of carbon disulfide is added in the course of 30 minutes (Note 1). After the mixture has been stirred for an additional 30 minutes, the precipitate is filtered with suction, washed with 50 ml. of ether, and spread on filter paper for 15-20 minutes to allow evaporation of the ether. The yield of the salt is 181-185 g. (96-98%). 

Li Salt. Its IR spectrum is given in Ref 13 HgCl+ Salt. It is prepd by the action of Hg(II) chloride on the K salt in w (Ref 6) Phenylhydrazine Salt. It is prepd by the action of phenylhydrazine on dinitromethane in anhyd eth and obtd as intense yellow needles, mp 101° with gas evoln (Ref 3)... 

When the corresponding trichloride is treated with water this acid is produced, and crystallises from dilute alcohol as fine, colourless needles, M.pt. 135° C. The barium, lead, copper, silver and phenylhydrazine salts are known. Nitration in the usual manner yields 3 S -dinitro-4 4 -dimethyldiphenylphosphinic acid. 

Phenylhydrazine salt cryst. from CgHg-pet. ether. M.p. 64-5°. 

Sulfinic acids are generally unstable compounds (especially aliphatic ones), and they can be identified either as phenylhydrazine salts (58), or, better, by alkylation of their sodium salts with methyl iodide, during which sulfones are formed (59). 

Concerning the action of phenylhydrazine on these derivatives, Behrend and his students found that 6-methylisodialuric add gave a phenylhydrazine salt when treated in aqueous solution with phenylhydrazine. Levene found that isodialtuic acid was converted into 5,6-di-phenyl-hydrazinouracil (XX) by the action of a hot acetic acid solution of phenylhydrazine. This result becomes tmderstandable when we recall that Behrend, Koch, and von Vogd noticed that in hot acetic acid even bases like guanidine and thiourea isomerized isodialuric acid into dialuric acid (XIX). 

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