Dual Substituent Effects on Anilinolysis of Bis(aryl) Chlorothiophosphates

Barai, Hasi Rani; Lee, Hai Whang

doi:10.5012/bkcs.2013.34.12.3597

Bulletin of the Korean Chemical Society

2013

DOI: 10.5012/bkcs.2013.34.12.3597

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Dual Substituent Effects on Anilinolysis of Bis(aryl) Chlorothiophosphates

Hasi Rani Barai¹,

Hai Whang Lee

Abstract: The reactions of bis (Y-aryl) chlorothiophosphates (1)

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2014

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“…6 The sign of ρ XY was negative with 2, while the sign of ρ XY was positive for both electrondonating and -withdrawing Y substituents despite biphasic concave upward free energy relationships. This indicated that the reaction mechanism was changed from a concerted (or a stepwise with a rate-limiting bond formation) with 2 to a stepwise with a rate-limiting bond cleavage with 1 due to additional substituent Y.…”

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Dual Substituent Effects on Pyridinolysis of Bis(aryl) Chlorothiophosphates in Acetonitrile

Barai¹,

Lee

2014

Bulletin of the Korean Chemical Society

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The nucleophilic substitution reactions of bis(Y-aryl) chlorothiophosphates (1) with X-pyridines are investigated kinetically in acetonitrile at 35.0 o C. The free energy relationships with both X and Y are biphasic concave upwards with a break point at X = 3-Ph and Y = H, respectively. The sign of cross-interaction constants (CICs; ρ XY ) is positive with all X and Y. Proposed mechanism is a stepwise process with a rate-limiting leaving group departure from the intermediate with all X and Y. The kinetic results of 1 are compared with those of Yaryl phenyl chlorothiophosphates (2). In the case of Y = electron-withdrawing groups, the cross-interaction between Y and Y, due to additional substituent Y, is significant enough to change the sign of ρ XY from negative with 2 to positive with 1, indicative of the change of mechanism from a rate-limiting bond formation to bond breaking.

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Dual Substituent Effects on Pyridinolysis of Bis(aryl) Chlorothiophosphates in Acetonitrile

Barai¹,

Lee

2014

Bulletin of the Korean Chemical Society

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Dual Substituent Effects on Anilinolysis of Bis(aryl) Chlorothiophosphates

Abstract: The reactions of bis (Y-aryl) chlorothiophosphates (1)

Cited by 1 publication

References 22 publications

Dual Substituent Effects on Pyridinolysis of Bis(aryl) Chlorothiophosphates in Acetonitrile

Dual Substituent Effects on Pyridinolysis of Bis(aryl) Chlorothiophosphates in Acetonitrile

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