THE SYNTHESIS OF SMALL RING COMPOUNDS CONTAINING SILICON.
Final rept., 1 Jun 65-15 Jan 67,
RESEARCH TRIANGLE INST DURHAM N C CHEMISTRY AND LIFE SCIENCES LAB
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The ring closure of 1,2-bischlorosilylethanes 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 bissilylketones 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-bistrimethyl-silylhydrazine, were similarly investigated. The reaction of a series of 1,2-bischlorosilylethanes 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
- Organic Chemistry