A VARIABLE MECHANISM FOR THE NUCLEOPHILIC VINYLIC SUBSTITUTIONS IN A SERIES OF GEM-DIHALOGENATED ALKENES BY A BIDENTATE SULFUR NUCLEOPHILE - AN EXPERIMENTAL AND AM1 THEORETICAL-STUDY
gem-dihalogenated alkenes; nucleophilic substitution; ab initio calculations
Abstract :
[en] The nucleophilic substitutions of a series of gem-dihalogenated alkenes 3,5,7,8, and 9 (RS)2C=CX2 (X = Cl, F) with 1,2-benzenedithiolate b have been studied. Depending on the structures of the R groups (alkyl, saturated and unsaturated cycloalkyls, aromatic ring), the course of the reactions and the structures of the yielded products are modified. In the frame of the addition-elimination-type mechanism for these nucleophilic substitutions, the energy contents of the anionic intermediates, resulting from the additions of the nucleophile b to the unsaturated centers, is calculated at the AM1 method level. For the compounds 5, 7, 8, and 9, the calculated energies nicely corroborate the experimental results. For 3, anionic intermediates are no longer found by calculation, and a synchronous single-step substitution is strongly suggested.
Disciplines :
Chemistry
Author, co-author :
Gimbert, Yves
Moradpour, Alec
Dive, Georges ; Université de Liège - ULiège > Centre d'ingénierie des protéines
Dehareng, Dominique ; Université de Liège - ULiège > Centre d'ingénierie des protéines
Lahlil, Khalid
Language :
English
Title :
A VARIABLE MECHANISM FOR THE NUCLEOPHILIC VINYLIC SUBSTITUTIONS IN A SERIES OF GEM-DIHALOGENATED ALKENES BY A BIDENTATE SULFUR NUCLEOPHILE - AN EXPERIMENTAL AND AM1 THEORETICAL-STUDY
Publication date :
1993
Journal title :
Journal of Organic Chemistry
ISSN :
0022-3263
eISSN :
1520-6904
Publisher :
American Chemical Society, Columbus, United States - Ohio
Volume :
58
Issue :
17
Pages :
4685-4690
Peer reviewed :
Peer Reviewed verified by ORBi
Funders :
BELSPO - SPP Politique scientifique - Service Public Fédéral de Programmation Politique scientifique F.R.S.-FNRS - Fonds de la Recherche Scientifique DGTRE - Région wallonne. Direction générale des Technologies, de la Recherche et de l'Énergie
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