CARBON-OXYGEN HYDROGEN-BONDING IN DEHYDROHALOGENATION REACTIONS - PM3CALCULATIONS ON POLYHALOGENATED PHENYLETHANE DERIVATIVES

Authors
ZUILHOF H LODDER G KOCH HF
Citation
H. Zuilhof et al., CARBON-OXYGEN HYDROGEN-BONDING IN DEHYDROHALOGENATION REACTIONS - PM3CALCULATIONS ON POLYHALOGENATED PHENYLETHANE DERIVATIVES, Journal of organic chemistry, 62(21), 1997, pp. 7457-7463
Citations number
58
Categorie Soggetti
Chemistry Inorganic & Nuclear
Journal title
Journal of organic chemistry → ACNP
ISSN journal
00223263
Volume
62
Issue
21
Year of publication
1997
Pages
7457 - 7463
Database
ISI
SICI code
0022-3263(1997)62:21<7457:CHIDR->2.0.ZU;2-8
Abstract
The dehydrohalogenation reactions of PhCH2-CH2Cl and PhCHCl-CX(2)LG (X = H, F; LG = F, Cl) with methoxide have been studied using PM3 quantu m chemical calculations in vacuo and within a dielectric medium. For P hCH2-CH2Cl and PhCHCl-CH2Cl the loss of HCl is predicted to occur via an E2 mechanism, while for the other three compounds loss of hydrogen halide occurs via a two-step mechanism, with a hydrogen-bonded carbani on as an intermediate. The mechanistic implications of these calculati ons are discussed in comparison with experimental data.