کد مقاله کد نشریه سال انتشار مقاله انگلیسی نسخه تمام متن
1314813 975987 2007 8 صفحه PDF دانلود رایگان
عنوان انگلیسی مقاله ISI
Reactivity of fluorinated sulfur-containing heterocycles towards nucleophilic and oxidizing reagents
موضوعات مرتبط
مهندسی و علوم پایه شیمی شیمی معدنی
پیش نمایش صفحه اول مقاله
Reactivity of fluorinated sulfur-containing heterocycles towards nucleophilic and oxidizing reagents
چکیده انگلیسی
The reaction of 5,5-bis(trifluoromethyl)-6-thia-bicyclo[2.2.1]hept-2-ene, 5,5-bis(trifluoromethyl)-6-thia-bicyclo[2.2.2]oct-2-ene and 2,2-bis(trifluoromethyl)-3,6-dihydro-4,5-dimethyl-2H-thiopyran with i-C3H7MgCl leads to the formation of ring opening products as the result of nucleophilic attack of the Grignard reagent on the sulfur atom. According to DFT calculations the reactivity of the sulphur-containing substrate correlates with the strain energy of the heterocycle. The oxidation of 3-thia-4,4-bis(trifluoromethyl)tricyclo[5.2.1.02,5]non-7-ene by hydrogen peroxide in hexafluoro-iso-propanol solvent resulted in formation of the corresponding sulfoxide however, the reaction with m-chloroperoxybenzoic acid produced the product of exhaustive oxidation of sulfur and the double bond. In sharp contrast, the oxidation of 5,5-bis(trifluoromethyl)-6-thia-bicyclo[2.2.1]hept-2-ene and 5,5-bis(trifluoromethyl)-6-thia-bicyclo[2.2.2]oct-2-ene by MCPBA (2d, 25 °C) proceeds with the preservation of the double bond, leading to the selective formation of the corresponding sulfones.
ناشر
Database: Elsevier - ScienceDirect (ساینس دایرکت)
Journal: Journal of Fluorine Chemistry - Volume 128, Issue 10, October 2007, Pages 1227-1234
نویسندگان
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