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Bulletin of the Korean Chemical Society (BKCS)

ISSN 0253-2964(Print)
ISSN 1229-5949(Online)
Volume 34, Number 4
BKCSDE 34(4)
April 20, 2013 

Kinetics and Mechanism of the Anilinolyses of O-Methyl, O-Propyl and O-Isopropyl Phenyl Phosphonochloridothioates in Acetonitrile
Hasi Rani Barai, Md. Ehtesham Ul Hoque, Mijin Lee, Hai Whang Lee*
Thiophosphoryl transfer reaction, Anilinolysis, O-Methyl, O-propyl and O-isopropyl phenyl phosphonochloridothioates, Deuterium kinetic isotope effect
The kinetic studies on the reactions of O-methyl (1), O-propyl (3) and O-isopropyl (4) phenyl phosphonochloridothioates with substituted anilines and deuterated anilines have been carried out in acetonitrile at 55.0 oC. A concerted SN2 mechanism is proposed for the anilinolyses of 1, 3 and 4. The anilinolysis rates of the phosphonochloridothioates are predominantly dependent upon the steric effects over the inductive effects of the two ligands. The deuterium kinetic isotope effects (DKIEs; kH/kD) are primary normal with 1 and 3, while secondary inverse with 4. Primary normal and secondary inverse DKIEs are rationalized by frontside and backside nucleophilic attack transition state, respectively. The DKIEs of the phosphonochloridothioates do not have any consistent correlations with the two ligands.
1096 - 1100
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