Kinetics and Mechanism of Anilinolyses of Ethyl Methyl, Ethyl Propyl and Diisopropyl Chlorothiophosphates in Acetonitrile

Title
Kinetics and Mechanism of Anilinolyses of Ethyl Methyl, Ethyl Propyl and Diisopropyl Chlorothiophosphates in Acetonitrile
Authors
이해황
Keywords
Thiophophoryl transfer reaction, Anilinolysis, Chlorothiophosphate, Deuterium kinetic isotope effect, Steric effect
Issue Date
2013
Publisher
BULLETIN OF THE KOREAN CHEMICAL SOCIETY
Series/Report no.
BULLETIN OF THE KOREAN CHEMICAL SOCIETY ; Vol34 no.12 Startpage 3811 Endpage 3816
Abstract
Nucleophilic substitution reactions of ethyl methyl (2), ethyl propyl (4) and diisopropyl (7) chlorothiophosphates with substituted anilines and deuterated anilines are investigated kinetically in acetonitrile at 55.0 oC. A concerted mechanism is proposed based on the selectivity parameters. The deuterium kinetic isotope effects (DKIEs; kH/kD) are secondary inverse (kH/kD = 0.66-0.99) with 2, primary normal and secondary inverse (kH/ kD = 0.78-1.19) with 4, and primary normal (kH/kD = 1.06-1.21) with 7. The primary normal and secondary inverse DKIEs are rationalized by frontside attack involving hydrogen bonded, four-center-type transition state, and backside attack involving in-line-type transition state, respectively. The anilinolyses of ten chlorothiophosphates are examined based on the reactivity, steric effect of the two ligands, thio effect, reaction mechanism, DKIE and activation parameter.
URI
http://dx.doi.org/10.5012/bkcs.2013.34.12.3811
http://dspace.inha.ac.kr/handle/10505/33105
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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