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http://dx.doi.org/10.5012/bkcs.2014.35.4.1016

Nucleophilic Substitution Reactions of O-Methyl N,N-Diisopropylamino Phosphonochloridothioate with Anilines and Pyridines  

Barai, Hasi Rani (Department of Chemistry, Inha University)
Lee, Hai Whang (Department of Chemistry, Inha University)
Publication Information
Bulletin of the Korean Chemical Society / v.35, no.4, 2014 , pp. 1016-1022 More about this Journal
Abstract
The kinetic studies on the reactions of O-methyl N,N-diisopropylamino phosphonochloridothioate with X-anilines and X-pyridines have been carried out in acetonitrile. The free energy relationship with X in the anilines exhibits biphasic concave upwards with a break region between X = (H and 4-F), giving unusual negative ${\beta}_X$ and positive ${\rho}_X$ values with weakly basic anilines. The unusual phenomenon is rationalized by isokinetic relationship. A stepwise mechanism with a rate-limiting leaving group departure from the intermediate is proposed based on the selectivity parameter and variation trend of the deuterium kinetic isotope effects with X. The free energy relationship with X in the pyridines exhibits biphasic concave upwards with a break point at X = 3-MeO. A concerted mechanism is proposed based on relatively small ${\beta}_X$ value, and frontside and backside nucleophilic attack are proposed with strongly and weakly basic pyridines, respectively.
Keywords
Thiophosphoryl transfer reaction; Anilinolysis; Pyridinolysis; O-Methyl N,N-diisopropylamino phosphonochloridothioate; Biphasic concave upward free energy relationship;
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