Premium
Kinetic study for addition of the phenylthio radicals to vinylpyridines
Author(s) -
Ito Osamu,
Matsuda Minoru
Publication year - 1984
Publication title -
international journal of chemical kinetics
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.341
H-Index - 68
eISSN - 1097-4601
pISSN - 0538-8066
DOI - 10.1002/kin.550160711
Subject(s) - chemistry , flash photolysis , radical , reaction rate constant , photochemistry , styrene , double bond , adduct , photodissociation , polar , kinetic energy , kinetics , organic chemistry , physics , quantum mechanics , copolymer , polymer , astronomy
The absolute rate constants for reversible addition of the substituted phenylthio radicals to vinylpyridines in solution at 23°C have been determined by flash photolysis method. For each phenylthio radical, the reactivities of vinylpyridines is 3–5 times lower than that of styrene. The relative equilibrium constants estimated with flash photolysis indicate that the stabilities of the adduct carbon‐centered radicals generated from vinylpyridines are similar to that from styrene. The Hammett plots suggest that the difference in the reactivities originates in the polar transition state; the nitrogen atom in 4‐vinylpyridine withdraws the electrons of vinylic double bond.