Organometallic oxides, alkoxides, and peroxides. Part IV. Reaction of phenylmercury(II) alkoxides, oxide, and hydroxide with organic isocyanates

Abstract

Crystalline 1 : 1 adducts (PhHgNR·CO₂R¹) are formed by reaction of phenylmercury(II) methoxide (R¹= Me), t-butoxide (R¹= Bu^t), or oxide (R¹= HgPh) with equimolar quantities of alkyl or aryl isocyanates. Phenylmercury(II) hydroxide gives 1 : 1 adducts (HNR·CO₂HgPh) with ethyl and t-butyl isocyanates but with methyl isocyanate a high melting, poorly soluble material of stoicheiometry [PhHgOH,(PhHg)₂O,MeNCO] is obtained. Aryl isocyanates and phenylmercury(II) hydroxide react with loss of carbon dioxide to yield NN′-diaryl-N-phenylmercurioureas (PhHgNAr·CO·NHAr) mixed with phenylmercury arylcarbamates (HNAr·CO₂HgPh) and/or N-phenylmercurio-arylamines (PhHgNHAr). The latter compounds have been synthesised by azeotropic dehydration of arylamine–phenylmercury(II) hydroxide mixtures and characterised as adducts with phthalic anhydride.