Sang Woo JOO, Mahbubur RAHMAN, Hasi Rani BARAI

Synthesis, kinetic study, and reaction mechanism: nucleophilic substitution reactions of butyl methyl chlorophosphate with substituted anilines and deuterated substituted anilines in acetonitrile

This study demonstrated the kinetics of nucleophilic substitution reactions of butyl methyl chlorophosphate(2) with X-anilines (XC6 H4 NH2) and deuterated X-anilines (XC6 H4 ND2) in MeCN at 55.0 ± 0.1 °C together with thegeneral optimized method for the synthesis of 2 under mild conditions. Different spectroscopic characterizations revealedthe formation of 2 with high purity. The free energy relationship with the substituents X in the anilines exhibited biphasicconcavity upwards with a break point at X = H, which induced large negative ρX and small positive βX values. Thedeuterium kinetic isotope effects (DKIEs) were secondary inverse (kH /kD < 1: 0.702–0.918) and the magnitudes wereincreased with the change of nucleophiles from weakly basic to strongly basic anilines. A concerted mechanism witha rate-limiting leaving group departing from the intermediate is proposed based on the selectivity parameters and thevariation of DKIEs with X.

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