Kinetics and Mechanism of the Anilinolysis of Dibutyl Chlorothiophosphate in Acetonitrile

Bulletin of the Korean chemical society

Md. Ehtesham Ul Hoque¹  Hai Whang Lee¹ 

关键词: Thiophosphoryl transfer reaction;    Anilinolysis;    Dibutyl chlorothiophosphate;    Deuterium kinetic isotope effect;   

DOI  :  

学科分类：化学（综合）

来源: Korean Chemical Society

【 摘 要 】

The nucleophilic substitution reactions of dibutyl chlorothiophosphate (4S) with substituted anilines (XC6H4NH2) and deuterated anilines (XC6H4ND2) are investigated kinetically in acetonitrile at 55.0 oC. The obtained deuterium kinetic isotope effects (DKIEs; kH/kD) are primary normal (kH/kD = 1.10-1.35). A concerted mechanism involving predominant frontside nucleophilic attack is proposed on the basis of the primary normal DKIEs and selectivity parameters. Hydrogen bonded, four-center-type transition state is proposed. The steric effects of the two ligands on the anilinolysis rates of the chlorothiophosphates are discussed. The anilinolyses of P=S systems are compared with those of their P=O counterparts on the basis of the reactivities, thio effects, selectivity parameters, and DKIEs.

【 授权许可】

Unknown