Reactivity of fluorinated sulfur-containing heterocycles towards nucleophilic and oxidizing reagents |
| |
Authors: | Viacheslav A Petrov Steve Lustig |
| |
Institution: | a DuPont Central Research and Development, Experimental Station, P.O. Box 80328, Wilmington, DE 19880-0328, USA1 b DuPont Corporate Center for Analytical Sciences, Experimental Station, P.O. Box 80328, Wilmington, DE 19880-0328, USA |
| |
Abstract: | The reaction of 5,5-bis(trifluoromethyl)-6-thia-bicyclo2.2.1]hept-2-ene, 5,5-bis(trifluoromethyl)-6-thia-bicyclo2.2.2]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)tricyclo5.2.1.02,5]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-bicyclo2.2.1]hept-2-ene and 5,5-bis(trifluoromethyl)-6-thia-bicyclo2.2.2]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. |
| |
Keywords: | Diels-Alder adducts of hexafluorothioacetone Reaction with iso-propyl magnesium chloride Oxidation m-Chloroperoxybenzoic acid |
本文献已被 ScienceDirect 等数据库收录! |
|