The reaction rates of substituted quinolines (6-Clqui., qui.) with p-substituted benzoylchlorides $(p-CH_3,\;p-H,\;p-NO_2)$ have been measured by conductometry in acetonitrile, and the rate constants are determined at various temperatures (10, 15, 20, $25^{\circ}C$) and pressures (1, 200, 500, 1000 bar). From the values of rate constants, the activation parameters $(Ea,\;{\Delta}V^{\neq},\;{\Delta}H^{\neq},\;{\Delta}S^{\neq}, \;{\Delta}G^{\neq})$and the pressure dependence of Hammett �� values were determined. The rate constants increased with increasing temperatures and pressures, and are further increased to introduction to the electron acceptor substituents in substrate $(p-NO_2)$ with quinoline. The activation volume and the activation entropy are all negative. And the Hammett p values are negative for nucleophile ${\rho}_X$ and positive for the substrate ${\rho}_Y$ over the pressure range studied. The results of kinetic studies for pressure and substituent show that these reactions proceed through a typical $S_N2$ reaction mechanism and "associative $S_N2$" favoring bond formation with increasing pressures.
@article{ JCGMDC_2003_v47n3_206}
,title={Kinetics on the Reaction of Substituted Quinolines and p-Substituted Benzoylchlorides under Various Pressures}
,volume={3}
, url={http://dx.doi.org/10.5012/jkcs.2003.47.3.206}, DOI={10.5012/jkcs.2003.47.3.206}
, number= {3}
, journal={Journal of the Korean Chemical Society}
, publisher={Korean Chemical Society}
, author={Jong-Wan, Lim
and
Se-Kyong, Kim}
, year={2003}
, month={Jun}
TY - JOUR
T2 - Journal of the Korean Chemical Society
AU - Jong-Wan, Lim
AU - Se-Kyong, Kim
SN - 1017-2548
TI - Kinetics on the Reaction of Substituted Quinolines and p-Substituted Benzoylchlorides under Various Pressures
VL - 47
PB - Korean Chemical Society
DO - 10.5012/jkcs.2003.47.3.206
PY - 2003
UR - http://dx.doi.org/10.5012/jkcs.2003.47.3.206
ER -
Jong-Wan, L.
,
&
Se-Kyong, K.
( 2003).
Kinetics on the Reaction of Substituted Quinolines and p-Substituted Benzoylchlorides under Various Pressures.
Journal of the Korean Chemical Society,
47
(3)
Korean Chemical Society.
doi:10.5012/jkcs.2003.47.3.206
Jong-Wan, L
,
&
Se-Kyong, K
2003,
Kinetics on the Reaction of Substituted Quinolines and p-Substituted Benzoylchlorides under Various Pressures,
Journal of the Korean Chemical Society,
vol. 3,
no. 3,
Retrieved from http://dx.doi.org/10.5012/jkcs.2003.47.3.206
[1]
L Jong-Wan
,
and
K Se-Kyong
,
“Kinetics on the Reaction of Substituted Quinolines and p-Substituted Benzoylchlorides under Various Pressures”,
Journal of the Korean Chemical Society,
vol. 3,
no. 3,
Jun
2003.
Jong-Wan, Lim
and
,
Se-Kyong, Kim
and
,
“Kinetics on the Reaction of Substituted Quinolines and p-Substituted Benzoylchlorides under Various Pressures”
Journal of the Korean Chemical Society,
3.
3
2003:
Jong-Wan, L
,
Se-Kyong, K
Kinetics on the Reaction of Substituted Quinolines and p-Substituted Benzoylchlorides under Various Pressures.
Journal of the Korean Chemical Society
[Internet].
2003.
Jun ;
3
(3)
Available from http://dx.doi.org/10.5012/jkcs.2003.47.3.206
Jong-Wan, Lim
,
and
Se-Kyong, Kim
,
“Kinetics on the Reaction of Substituted Quinolines and p-Substituted Benzoylchlorides under Various Pressures.”
Journal of the Korean Chemical Society
3
no.3
()
Jun,
2003):
http://dx.doi.org/10.5012/jkcs.2003.47.3.206
