Kinetics and Mechanism of the Anilinolysis of Aryl Ethyl Isothiocyanophosphates in Acetonitrile

Title
Kinetics and Mechanism of the Anilinolysis of Aryl Ethyl Isothiocyanophosphates in Acetonitrile
Authors
이해황
Keywords
Phosphoryl transfer reaction, Anilinolysis, Y-Aryl ethyl isothiocyanophosphate, Deuterium kinetic isotope effect, Cross-interaction constant
Issue Date
2013
Publisher
BULLETIN OF THE KOREAN CHEMICAL SOCIETY
Series/Report no.
BULLETIN OF THE KOREAN CHEMICAL SOCIETY ; Vol34 no.6 Startpage 1829 Endpage 1834
Abstract
The nucleophilic substitution reactions of Y-aryl ethyl isothiocyanophosphates with substituted X-anilines and deuterated X-anilines were investigated kinetically in acetonitrile at 75.0 oC. The free energy relationships with X in the nucleophiles exhibited biphasic concave downwards with a break point at X = H. A stepwise mechanism with rate-limiting bond formation for strongly basic anilines and with rate-limiting bond breaking for weakly basic anilines is proposed based on the negative and positive ρXY values, respectively. The deuterium kinetic isotope effects (DKIEs; kH/kD) changed gradually from primary normal with strongly basic anilines, via primary normal and secondary inverse with aniline, to secondary inverse with weakly basic anilines. The primary normal and secondary inverse DKIEs were rationalized by frontside attack involving hydrogen bonded, four-center-type TSf and backside attack involving in-line-type TSb, respectively.
URI
http://dx.doi.org/10.5012/bkcs.2013.34.6.1829
http://dspace.inha.ac.kr/handle/10505/33108
ISSN
0253-2964
Appears in Collections:
College of Natural Science(자연과학대학) > Chemistry (화학) > Local Access Journal Papers, Reports(화학 논문, 보고서)

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