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RESEARCH ARTICLE
Contents Vol 70(1)

Concerted Pathway to the Mechanism of the Anilinolysis of Bis(N,N-diethylamino)phosphinic Chloride in Acetonitrile

Hasi Rani Barai
+ Author Affiliations
- Author Affiliations

Department of Mechanical Engineering, Yeungnam University, Gyeongsan 712-749, Korea. Email: hrbarai@ynu.ac.kr

Australian Journal of Chemistry 70(1) 101-105 https://doi.org/10.1071/CH16202
Submitted: 29 March 2016  Accepted: 10 June 2016   Published: 4 July 2016

Abstract

The kinetics of the nucleophilic substitution reactions of bis(N,N-diethylamino)phosphinic chloride with substituted anilines (XC6H4NH2) and deuterated anilines (XC6H4ND2) are investigated in MeCN at 65.0°C. The deuterium kinetic isotope effects (DKIEs) are secondary inverse (kH/kD < 1: 0.706–0.947) and the magnitudes of the secondary inverse DKIEs (kH/kD) increase constantly as the nucleophiles are changed from weakly basic to strongly basic anilines. The magnitudes of the selectivity parameters are ρX(H) = –6.34, and βX(H) = 2.24 with substituted anilines and ρX(D) = –6.13 and βX(D) = 2.17 with deuterated anilines. A concerted SN2 mechanism involving predominant backside attack is proposed based on the kH/kD values with substituent X.


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