ISSN:
0009-2940
Keywords:
Silene, dichloroneopentyl-
;
Imines
;
Cycloaddition reactions
;
2-Silaazetidines
;
Thermolysis reactions
;
Chemistry
;
Inorganic Chemistry
Source:
Wiley InterScience Backfile Collection 1832-2000
Topics:
Chemistry and Pharmacology
Notes:
Silaheterocycles, XXIII[1]. - Synthesis and Thermolysis Reactions of Si-Functionalized 2-SilaazetidinesDichloroneopentylsilene (1) is formed in situ by the reaction of trichlorovinylsilane with LitBu. The [2 + 2] cycloaddition to imines yields Si, Si1-dichloro-functionalized 2-silaazetidines in a preparative scale. With aldimines as trapping agents for 1, the resulting SiN four-membered ring compounds are isolated as syn/anti1-isomers (e.g. syn/anti-15 and -16; syn/anti ≍ 2:1). Silene 1 is not liberated from the silaazetidines on heating, but the Si, Si1-dichloro-substituted silanimine Cl2Si=NtBu (24) is formed. This can be trapped by Me3SiOMe or Ph2C=NtBu to give the addition products 25 and 26, respectively. The pathways are discussed which lead to stereoisomeric SiN ring compounds by a multiple-step mechanism including zwitterionic intermediates (1,4-dipoles). In addition there is strong evidence for the formation of 1, depending on the trapping reagent used. This fact may be explained by donor→silene interactions. The thermolysis products of silaazetidines support the formulation of a stepwise decomposition to an alkene and Cl2Si=NR derivatives.
Additional Material:
4 Tab.
Type of Medium:
Electronic Resource
URL:
http://dx.doi.org/10.1002/cber.19931260306
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