Halomethyl-metal compounds L. Preparation of monohalomethyl derivatives of germanium, tin, lead and mercury via halomethylzinc halides

Abstract

The reaction of iodomethylzinc iodide or bromomethylzinc bromide in THF with the appropriate metal or organometallic halide was used in the present ation of Me3SnCH2I, Me3SnCH2Br, Me2Sn(CH2I)2, Me2Sn(CH2Br)2, Me2PhSnCH2I, Ph3SnCH2I, Sn(CH2I)4, Ph3PbCH2I, Hg(CH2I)2 and Hg(CH2Br)2. In most cases the product yields were very good. The reaction of iodomethylzinc iodide with trimethylchlorogermane gave in low yield both Me3GeCH2I and Me3GeCH2GeMe3. These compounds were obtained in much better yield when ICH2ZnI was allowed to react with germanium tetrachloride and the reaction product was methylated with MeMgBr. The reaction of iodomethyl-tin compounds with silver chloride and bromine in acetonitrile served well in the preparation of Me3SnCH2Cl, Me3SnCH2Br, Me2Sn(CH2Cl)2, Me2Sn(CH2Br)2 and Me2PhSnCH2Cl. Experiments in which mixtures of Et3SiD and n-Bu3SiH were allowed to react with ICH2ZnI in refluxing ether or with Hg(CH2I)2/Ph2Hg in refluxing benzene gave only Et3SiCH2D and n-Bu3SiCH3. This eliminates from consideration the possibility that these reactions proceed by a two-step alkylation-reduction or reduction-alkylation sequence. © 1971.