The aminolysis of phosphinates; the kinetics and mechanism of the aminolysis of phosphinate esters in acetonitrile
The aminolysis of aryl diphenylphosphinates, p-nitrophenyl diphenylphosphinothionate, -phosphinothioate, and -phosphinodithioate by n-butylamine, by the secondary amines piperidine, pyrrolidine, morpholine, and dipropylamine, as well as by a series of diamines, has been studied in acetonitrile. The...
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| المؤلف الرئيسي: | |
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| مؤلفون آخرون: | , , , , , |
| التنسيق: | article |
| منشور في: |
1986
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| الوصول للمادة أونلاين: | http://hdl.handle.net/10725/3329 http://www.nrcresearchpress.com/doi/abs/10.1139/v86-037#.V5mw3rh97y0 |
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| الملخص: | The aminolysis of aryl diphenylphosphinates, p-nitrophenyl diphenylphosphinothionate, -phosphinothioate, and -phosphinodithioate by n-butylamine, by the secondary amines piperidine, pyrrolidine, morpholine, and dipropylamine, as well as by a series of diamines, has been studied in acetonitrile. The general reactivity order is diamines > butylamine > sec-amines. Butylaminolysis follows a two-term rate law, one first order in amine and the other second order in amine. The second order in amine term predominates. sec-Amines and diamines follow a rate law which is first order in amine only. Leaving group effects, solvent effects, and activation parameters support a pathway which involves rate-determining collapse of a zwitterionic pentacoordinate intermediate. In the case of butylamine this collapse is general base catalyzed and for the diamines the reaction is intramolecularly general base catalyzed. |
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