• Bulletin of the Korean Chemical Society
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• v.32 no.9
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• pp.3505-3508
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• 2011

• Bulletin of the Korean Chemical Society
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• v.32 no.9
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• pp.3245-3250
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• 2011

The nucleophilic substitution reactions of diisopropyl chlorophosphate (3) with substituted anilines ($XC_6H_4NH_2$) and deuterated anilines ($XC_6H_4ND_2$) are investigated kinetically in acetonitrile at $55.0^{\circ}C$. The anilinolysis rate of 3 is rather slow to be rationalized by the conventional stereoelectronic effects. The obtained deuterium kinetic isotope effects (DKIEs; $k_H/k_D$) are secondary inverse ($k_H/k_D$ = 0.71-0.95) with maximum magnitude at X = H.A concerted mechanism involving predominant backside nucleophilic attack is proposed on the basis of the secondary inverse DKIEs.

• Bulletin of the Korean Chemical Society
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• v.32 no.12
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• pp.4387-4391
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• 2011

The kinetic studies on the pyridinolysis of diisopropyl thiophosphinic chloride have been carried out in acetonitrile at $55.0^{\circ}C$. The free energy correlations for substituent X variations in the X-pyridines are biphasic concave upwards with a break point at X = 3-Ph. A concerted SN2 mechanism is proposed with a change of the attacking direction of the X-pyridine from a frontside attack for the strongly basic pyridines to a backside attack for the weakly basic pyridines. The factors to determine the rates and thio effects on the rates for the pyridinolyses of thiophophinic chloride, chlorothiophosphate, phosphinic chloride, phosphonochloridothioate, and chlorophosphate systems are briefly reviewed on the basis of the magnitude of the positive charge of the reaction center P atom and steric effects of the two ligands.