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Pyrolysis of 5‐chloropentan‐2‐one and 4‐chloro‐1‐phenylbutan‐1‐one. Participation of the carbonyl group
Author(s) -
Chuchani Gabriel,
Domínguez Rosa M.
Publication year - 1983
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.550151203
Subject(s) - chemistry , arrhenius equation , propene , allyl bromide , pyrolysis , medicinal chemistry , gas phase , bromide , torr , homogeneous , activation energy , organic chemistry , thermodynamics , catalysis , physics
The rates of elimination of 5‐chloropentan‐2‐one and 4‐chloro‐1‐phenylbutan‐1‐one in the gas phase have been determined in a static system, seasoned with allyl bromide, and in the presence of the chain inhibitor propene. The reactions are unimolecular and follow a first‐order rate law. The working temperature and pressure ranges were 339.4–401.1°C and 46–117 torr, respectively. The rate coefficients for the homogeneous reactions are given by the following Arrhenius equations: for 5‐chloropentan‐2‐one, log k 1 (s −1 ) = (13.12 ± 0.88) ‐ (207.8 ± 11.0)kJ/mol/2.303 RT ; and for 4‐chloro‐1‐phenylbutan‐1‐one, log k 1 (s −1 ) = (12.28 ± 1.09) ‐ (185.2 ± 12.0)kJ/mol/2.303 RT . The carbonyl group at the γ position of the CCl bond of haloketones apparently participates in the rate of pyrolysis. The five‐membered conformation appears to be a favorable structure for anchimeric assistance of the CO group in the gas‐phase elimination of chloroketones.