Phosphonitrilic Compounds. XII. the Alkaline Hydrolysis of Fluoroalkoxycyclophosphazenes

H. R. Allcock; E. J. Walsh

doi:10.1021/ja00756a023

Phosphonitrilic Compounds. XII. the Alkaline Hydrolysis of Fluoroalkoxycyclophosphazenes

H. R. Allcock, E. J. Walsh

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Abstract

Product analysis studies of the hydrolysis of [NP(OCH₂CF₃)₂]₃ in basic aqueous methanol revealed a nongeminal pathway for the removal of trifluoroethoxy groups from phosphorus. Kinetic studies of the removal of the first fluoroalkoxy group from [NP(OCH2CF3)2]3, [NP(OCH2C2F5)2]3, [NP(OCH2C3F7)2]3, [NP(OCH2CF3)2]4, and [NP(OCH2C3F7)2]4 in basic 25% aqueous diglyme showed that, for cyclic trimers, the ease of ligand displacement is in the order: OCH2C2F5 > OCH2CF3 > OCH2CF7. Cyclic tetramers hydrolyzed two to four times faster than the appropriate trimers. The mechanistic implications of these results are discussed.

Original language	English (US)
Pages (from-to)	119-124
Number of pages	6
Journal	Journal of the American Chemical Society
Volume	94
Issue number	1
DOIs	https://doi.org/10.1021/ja00756a023
State	Published - Jan 1 1972

All Science Journal Classification (ASJC) codes

Catalysis
General Chemistry
Biochemistry
Colloid and Surface Chemistry

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title = "Phosphonitrilic Compounds. XII. the Alkaline Hydrolysis of Fluoroalkoxycyclophosphazenes",

abstract = "Product analysis studies of the hydrolysis of [NP(OCH2CF3)2]3 in basic aqueous methanol revealed a nongeminal pathway for the removal of trifluoroethoxy groups from phosphorus. Kinetic studies of the removal of the first fluoroalkoxy group from [NP(OCH2CF3)2]3, [NP(OCH2C2F5)2]3, [NP(OCH2C3F7)2]3, [NP(OCH2CF3)2]4, and [NP(OCH2C3F7)2]4 in basic 25% aqueous diglyme showed that, for cyclic trimers, the ease of ligand displacement is in the order: OCH2C2F5 > OCH2CF3 > OCH2CF7. Cyclic tetramers hydrolyzed two to four times faster than the appropriate trimers. The mechanistic implications of these results are discussed.",

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N2 - Product analysis studies of the hydrolysis of [NP(OCH2CF3)2]3 in basic aqueous methanol revealed a nongeminal pathway for the removal of trifluoroethoxy groups from phosphorus. Kinetic studies of the removal of the first fluoroalkoxy group from [NP(OCH2CF3)2]3, [NP(OCH2C2F5)2]3, [NP(OCH2C3F7)2]3, [NP(OCH2CF3)2]4, and [NP(OCH2C3F7)2]4 in basic 25% aqueous diglyme showed that, for cyclic trimers, the ease of ligand displacement is in the order: OCH2C2F5 > OCH2CF3 > OCH2CF7. Cyclic tetramers hydrolyzed two to four times faster than the appropriate trimers. The mechanistic implications of these results are discussed.

AB - Product analysis studies of the hydrolysis of [NP(OCH2CF3)2]3 in basic aqueous methanol revealed a nongeminal pathway for the removal of trifluoroethoxy groups from phosphorus. Kinetic studies of the removal of the first fluoroalkoxy group from [NP(OCH2CF3)2]3, [NP(OCH2C2F5)2]3, [NP(OCH2C3F7)2]3, [NP(OCH2CF3)2]4, and [NP(OCH2C3F7)2]4 in basic 25% aqueous diglyme showed that, for cyclic trimers, the ease of ligand displacement is in the order: OCH2C2F5 > OCH2CF3 > OCH2CF7. Cyclic tetramers hydrolyzed two to four times faster than the appropriate trimers. The mechanistic implications of these results are discussed.

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Phosphonitrilic Compounds. XII. the Alkaline Hydrolysis of Fluoroalkoxycyclophosphazenes

Abstract

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