Substituent Exchange and Carbon-Oxygen Bond Cleavage with Aryloxycyclophosphazenes

H. R. Allcock; L. A. Smeltz

doi:10.1021/ja00430a022

Substituent Exchange and Carbon-Oxygen Bond Cleavage with Aryloxycyclophosphazenes

H. R. Allcock, L. A. Smeltz

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23 Scopus citations

Abstract

Aryloxycyclotriphosphazenes, [NP(OAr)₂]₃, such as I-IV, undergo substituent exchange reactions with organic nucleophiles. This constitutes a route for the preparation of mixed substituent organophosphazenes, some of which are inaccessible by other methods. The ease of displacement of OAr in [NP(OAr)₂]₃ by CF₃CH₂O^- decreased with OAr in the order, OC₆H₄NO₂-o or -p > OC₆H₅Cl-p ≫ OC₆H₅. When OAr was OC₆H₄NO₂-o or -p, ligand exchange was either accompanied by or replaced by nucleophilic attack at the α-carbon of the aromatic residue. This effect was significant when the attacking nucleophile was C₆H₅O- or C₆H₅S^-, and it predominated when the nucleophile was C₆H₅NH^- or an uncharged primary or secondary amine. The mechanisms of these reactions are discussed.

Original language	English (US)
Pages (from-to)	4143-4149
Number of pages	7
Journal	Journal of the American Chemical Society
Volume	98
Issue number	14
DOIs	https://doi.org/10.1021/ja00430a022
State	Published - Jul 1 1976

All Science Journal Classification (ASJC) codes

Catalysis
General Chemistry
Biochemistry
Colloid and Surface Chemistry

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title = "Substituent Exchange and Carbon-Oxygen Bond Cleavage with Aryloxycyclophosphazenes",

abstract = "Aryloxycyclotriphosphazenes, [NP(OAr)2]3, such as I-IV, undergo substituent exchange reactions with organic nucleophiles. This constitutes a route for the preparation of mixed substituent organophosphazenes, some of which are inaccessible by other methods. The ease of displacement of OAr in [NP(OAr)2]3 by CF3CH2O- decreased with OAr in the order, OC6H4NO2-o or -p > OC6H5Cl-p ≫ OC6H5. When OAr was OC6H4NO2-o or -p, ligand exchange was either accompanied by or replaced by nucleophilic attack at the α-carbon of the aromatic residue. This effect was significant when the attacking nucleophile was C6H5O- or C6H5S-, and it predominated when the nucleophile was C6H5NH- or an uncharged primary or secondary amine. The mechanisms of these reactions are discussed.",

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T1 - Substituent Exchange and Carbon-Oxygen Bond Cleavage with Aryloxycyclophosphazenes

AU - Allcock, H. R.

AU - Smeltz, L. A.

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N2 - Aryloxycyclotriphosphazenes, [NP(OAr)2]3, such as I-IV, undergo substituent exchange reactions with organic nucleophiles. This constitutes a route for the preparation of mixed substituent organophosphazenes, some of which are inaccessible by other methods. The ease of displacement of OAr in [NP(OAr)2]3 by CF3CH2O- decreased with OAr in the order, OC6H4NO2-o or -p > OC6H5Cl-p ≫ OC6H5. When OAr was OC6H4NO2-o or -p, ligand exchange was either accompanied by or replaced by nucleophilic attack at the α-carbon of the aromatic residue. This effect was significant when the attacking nucleophile was C6H5O- or C6H5S-, and it predominated when the nucleophile was C6H5NH- or an uncharged primary or secondary amine. The mechanisms of these reactions are discussed.

AB - Aryloxycyclotriphosphazenes, [NP(OAr)2]3, such as I-IV, undergo substituent exchange reactions with organic nucleophiles. This constitutes a route for the preparation of mixed substituent organophosphazenes, some of which are inaccessible by other methods. The ease of displacement of OAr in [NP(OAr)2]3 by CF3CH2O- decreased with OAr in the order, OC6H4NO2-o or -p > OC6H5Cl-p ≫ OC6H5. When OAr was OC6H4NO2-o or -p, ligand exchange was either accompanied by or replaced by nucleophilic attack at the α-carbon of the aromatic residue. This effect was significant when the attacking nucleophile was C6H5O- or C6H5S-, and it predominated when the nucleophile was C6H5NH- or an uncharged primary or secondary amine. The mechanisms of these reactions are discussed.

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Substituent Exchange and Carbon-Oxygen Bond Cleavage with Aryloxycyclophosphazenes

Abstract

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