Accession Number : AD0645879

Title :   THE SYNTHESIS OF SMALL RING COMPOUNDS CONTAINING SILICON.

Descriptive Note : Final rept., 1 Jun 65-15 Jan 67,

Corporate Author : RESEARCH TRIANGLE INST DURHAM N C CHEMISTRY AND LIFE SCIENCES LAB

Personal Author(s) : Pitt,C. G.

Report Date : JAN 1967

Pagination or Media Count : 42

Abstract : The ring closure of 1,2-bis(chlorosilyl)ethanes with various metals, and the oxidative elimination of the hydrazo group from certain cyclic silylhydrazines, were investigated as potential syntheses of the 1,2-disilacyclobutane ring system. The fragmentation of gamma-haloalkylsilanes, the disproportionation tin-silicon compounds, halogen-metal interchange and decarbonylation of bis(silyl)ketones were briefly considered as routes to small ring compounds of silicon. The preparation of 3,3,6,6-tetramethyl-1,2-diaza-3,6-disilacyclohexane and 1-amino-2,2,5,5-tetramethyl-1-aza-2,5-disilacyclopentane is described. The two compounds are shown to be in equilibrium at room temperature even in the absence of added catalysts. The oxidation of these compounds with mercuric oxide and ethyl axodicarboxylate was studied and the oxidation products identified. The equilibration and oxidation of the acyclic analogs, N,N and N,N'-bis(trimethyl-silyl)hydrazine, were similarly investigated. The reaction of a series of 1,2-bis(chlorosilyl)ethanes with magnesium is shown to result in cleavage of the tetrahydrofuran solvent. The reactions with lithium, potassium or sodium amalgam give only polymeric products. The first example of vinyl hydrogen ligand exchange at silicon, catalyzed by chloroplatinic acid, is described. (Author)

Descriptors :   (*SILANES, SYNTHESIS(CHEMISTRY)), (*HETEROCYCLIC COMPOUNDS, SILANES), CYCLOBUTANES, HYDRAZINE DERIVATIVES, HALOGEN COMPOUNDS, TIN COMPOUNDS, DISPROPORTIONATION, CYCLOHEXANES, CYCLOHEXANES, CYCLOPENTANES, CHEMICAL EQUILIBRIUM, OXIDATION, PHOTOLYSIS, DIENES, KETONES, MOLECULAR ISOMERISM, CHEMICAL REACTIONS

Subject Categories : Organic Chemistry

Distribution Statement : APPROVED FOR PUBLIC RELEASE