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http://dx.doi.org/10.5012/bkcs.2013.34.6.1829

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

Barai, Hasi Rani (Department of Chemistry, Inha University)
Adhikary, Keshab Kumar (Department of Chemistry, Inha University)
Lee, Hai Whang (Department of Chemistry, Inha University)
Publication Information
Bulletin of the Korean Chemical Society / v.34, no.6, 2013 , pp. 1829-1834 More about this Journal
Abstract
The nucleophilic substitution reactions of Y-aryl ethyl isothiocyanophosphates with substituted X-anilines and deuterated X-anilines were investigated kinetically in acetonitrile at $75.0^{\circ}C$. 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 ${\rho}_{XY}$ values, respectively. The deuterium kinetic isotope effects (DKIEs; $k_H/k_D$) 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.
Keywords
Phosphoryl transfer reaction; Anilinolysis; Y-Aryl ethyl isothiocyanophosphate; Deuterium kinetic isotope effect; Cross-interaction constant;
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