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High‐pressure effect on organic reactions in fluorophobic media
Author(s) -
Jenner Gérard,
Gacem Badra
Publication year - 2003
Publication title -
journal of physical organic chemistry
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.325
H-Index - 66
eISSN - 1099-1395
pISSN - 0894-3230
DOI - 10.1002/poc.601
Subject(s) - chemistry , solvophobic , conjugate , methacrylonitrile , acrylonitrile , ethylene glycol , organic chemistry , computational chemistry , copolymer , polymer , mathematical analysis , mathematics , molecule
The kinetic effect of fluorophobic interactions was examined in Diels–Alder reactions and the conjugate addition of amines to acrylonitrile at different pressures. Its magnitude is lower than for other solvophobic media (water, ethylene glycol). Activation volumes determined in perfluorohexane are less negative for Diels–Alder cycloadditions owing to reduced fluorophobic interactions under pressure, in line with a former study. At variance, the conjugate addition is more pressure sensitive in the fluorous medium owing to the combination of solvophobic acceleration and enhanced electrostriction. Some synthetic applications of the multiactivation method (pressure + fluorophobic activation) are presented with emphasis on the beneficial solvophobic properties of the fluorous medium. Copyright © 2003 John Wiley & Sons, Ltd.