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http://dx.doi.org/10.5012/bkcs.2013.34.12.3811

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

Barai, Hasi Rani (Department of Chemistry, Inha University)
Hoque, Md. Ehtesham Ul (Department of Chemistry, Govt. Brojomohun College)
Lee, Hai Whang (Department of Chemistry, Inha University)
Publication Information
Bulletin of the Korean Chemical Society / v.34, no.12, 2013 , pp. 3811-3816 More about this Journal
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 $55.0^{\circ}C$. A concerted mechanism is proposed based on the selectivity parameters. The deuterium kinetic isotope effects (DKIEs; $k_H/k_D$) are secondary inverse ($k_H/k_D=0.66-0.99$) with 2, primary normal and secondary inverse ($k_H/k_D=0.78-1.19$) with 4, and primary normal ($k_H/k_D=1.06-1.21$) 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.
Keywords
Thiophophoryl transfer reaction; Anilinolysis; Chlorothiophosphate; Deuterium kinetic isotope effect; Steric effect;
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