Investigations on organoantimony compounds. XV. The synthesis of heterocyclic antimony compounds via thermolysis of α,ω-bis(dimethylstibino)alkanes. A new route to the synthesis of 1-methylstibacycloalkanes.
article
The intramolecular disproportionation of α,ω-bis(dimethylstibino)alkanes provides a new route to small-ring stibacycloalkanes. 1-Methylstibacyclopentane and 1-methylstibacyclohexane have been prepared in good yield via thermolysis 1,4-bis(dimethylstibino)butane and 1,5-bis(dimethylstibino)pentane. Attempts to prepare 1,-methylstibacyclobutane and 1-methylstibacycloheptane via thermolysis of 1,3-bis(dimethylstibino)propane and 1,6-bis(dimethylstibino)hexane instead resulted in intermolecular disproportionation leading to the formation of polymeric material. The α,ω-bis(dimethylstibino)alkanes used as starting materials were prepared by the reaction of dimethylstibylsodium with α,ω-dichloro- or α,ω-dibromo-alkanes in liquid ammonia. Upon reaction of dimethylstibylsodium with 1,4-dibromobutane and 1,5-dibromopentane in a 2/1 ratio, 1-methylstibacyclopentane and 1-methylstibacyclohexane were formed probably via intramolecular quaternization of intermediate α-methylstibino-ω-bromoalkanes. All antimony(III) compounds prepared have been converted into the corre- sponding dichloroantimony(V) derivatives. Quarternization with methyl iodide leads to the formation of 1,1-dimethylstibacyclopentane and 1,1-dimethylstiba- cyclohexane iodides. IR spectra of the stibacycloalkanes show a characteristic absorption in the region 460-470 cm-1. Moreover, the stibacyclohexane derivatives show two characteristic bands in the region 900-920 and 980-1010 cm-1, which are not observed in the spectra of the stibacyclopentanes. © 1976.
TNO Identifier
227975
ISSN
0022328X
Source
Journal of Organometallic Chemistry, 110(2), pp. 183-193.
Pages
183-193
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