•  
  •  
 

Turkish Journal of Chemistry

Abstract

This study demonstrated the kinetics of nucleophilic substitution reactions of butyl methyl chlorophosphate (2) with X-anilines (XC$_{6}$H$_{4}$NH$_{2})$ and deuterated X-anilines (XC$_{6}$H$_{4}$ND$_{2})$ in MeCN at 55.0 \textpm\ 0.1 \textdegree C together with the general optimized method for the synthesis of 2 under mild conditions. Different spectroscopic characterizations revealed the formation of 2 with high purity. The free energy relationship with the substituents X in the anilines exhibited biphasic concavity upwards with a break point at X $=$ H, which induced large negative $\rho_{X}$ and small positive $\beta_{X}$ values. The deuterium kinetic isotope effects (DKIEs) were secondary inverse ($k_{H}$/$k_{D}$ \textless\ 1: 0.702--0.918) and the magnitudes were increased with the change of nucleophiles from weakly basic to strongly basic anilines. A concerted mechanism with a rate-limiting leaving group departing from the intermediate is proposed based on the selectivity parameters and the variation of DKIEs with X.

DOI

10.3906/kim-1807-123

Keywords

Phosphoryl transfer reaction, concerted mechanism, butyl methyl chlorophosphate, Hammett and Br{\o}nsted constants, deuterium kinetic isotope effects

First Page

501

Last Page

510

Plum Print visual indicator of research metrics
PlumX Metrics
  • Usage
    • Downloads: 61
    • Abstract Views: 27
  • Captures
    • Readers: 7
see details

Included in

Chemistry Commons

Share

COinS