REACTIVITY OF NUCLEOPHILIC REAGENTS TOWARD P-NITROPHENYL PHOSPHATE DIANION
REACTIVITY OF NUCLEOPHILIC REAGENTS TOWARD P-NITROPHENYL PHOSPHATE DIANION
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DOI：
10.1021/ja01092a036
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发表时间：
1965-01-01
影响因子：
15
通讯作者：
JENCKS, WP
中科院分区：
文献类型：
--
作者：
KIRBY, AJ;JENCKS, WP
The nucleophilic reactivity of a series of amines toward the p-nitrophenyl phosphate dianion displays only a very small sensitivity to the basicity of the amine. Cationic substituents on the amine cause an enhanced reactivity, which is ascribed to an electrostatic effect. Substit-uents whichintroduce steric hindrance decrease nucleo-philic reactivity. The rate constant for the hydrolysis of p-nitrophenyl phosphate dianion falls on the same line as those of benzoyl phosphate dianions in a logarithmic plot against the pK of the leaving group. It is concluded that the principal driving force for the bimolecular re-actions of phosphoramidate monoanion, acetyl phosphate dianion, and p-nitrophenyl phosphate dianion arises from electron donation from the oxygen atoms and electron withdrawal by the leavinggroup, with little bond formation by the nucleophilic agent.As a continuation of the experiments described in the previous paper of this series, the reactivity of a number of nucleophilic reagents toward the dianion of p-nitrophenyl phosphate has been determined. This substrate has the advantage that its reaction rate may easily be followed spectrophotometrically and its reaction with basic amines may be studiedin alkaline solution.
