Trisubstituted Hydrazonium Chlorides

Submitted by Harry H. Sisler and George Omietanski Checked by Charles J. A. VoLzf and Bernard RuDNERt 

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The 1,1,1-trisubstituted hydrazonium chlorides are colorless, crystalline compounds which are very soluble in water, many being highly hygroscopic. They are also soluble in ethanol but are only slightly soluble in ethyl ether. 1,1,1-Trimethylhydrazonium chloride melts at about 245° in a sealed capillary with decomposition. 1,1,1-Triethylhydrazonium chloride melts at about 177 to 178° in a sealed capillary. 

The chloramidation of tertiary amines by introducing gaseous chloramide (chloramine) into the anhydrous amine or a solution of the amine in an inert solvent results in the formation of 1,1,1-trisubstituted hydrazonium chlorides. It has been found that a similar chloramidation reaction with tertiary phosphines can be made to yield analogous compounds of the general formula [R3PNH2]C1, i.e., F,P,P-trisubstituted aminophosphonium chlorides. The following aminophosphonium chlorides were prepared by this reaction P,P,P-triphenyl P,P,P-tri-n-butyl P-phenyl-P,P-(cyclotetramethylene) and P-phenyl-P,P-(cyclopenta-methylene). The methodforthe preparation of (triphenyl)-aminophosphonium chloride is given as representative of the procedure. 

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