Phosphonitrilic Compounds. XIV.1 Basic Hydrolysis of Aryloxy- and Spiroarylenedioxycyclophosphazenes

H. R. Allcock; E. J. Walsh

doi:10.1021/ja00768a021

Phosphonitrilic Compounds. XIV.¹ Basic Hydrolysis of Aryloxy- and Spiroarylenedioxycyclophosphazenes

H. R. Allcock, E. J. Walsh

Research output: Contribution to journal › Article › peer-review

29 Scopus citations

Abstract

Bis(aryloxy)cyclophosphazenes, [NP(OAr)₂]₃, and spirocyclic arylenedioxycyclophosphazenes, (NPO₂-Ar)₃, have been hydrolyzed in basic 25 vol % water in diglyme. For the bis(aryloxy) derivatives, the ease of hydrolytic removal of the first aryloxy group in [NP(OR)₂]₃ from phosphorus is in the order OR = p-NO₂C₆H₄O– > w-NO₂C₆H₄O– > o-NO₂C₆H₄O– ≫ C₆H₅O– > p-CH₃C₆H₄O–. For the spirocyclic derivatives, the rate of cleavage of the first aryloxy-phosphorus bond is in the order [NP(O₂C₆H₄-1,2)]₃ > [NP(O₂C₁₀H₆-2,3)]3 ≫ [NP(O₂C₁₂H₈-2,2′)]₃ and [NP(O₂C₁₂H₆-1,8)]₃. The mechanisms of these reactions are discussed, and comparisons are made with related phosphate ester hydrolyses.

Original language	English (US)
Pages (from-to)	4538-4545
Number of pages	8
Journal	Journal of the American Chemical Society
Volume	94
Issue number	13
DOIs	https://doi.org/10.1021/ja00768a021
State	Published - Jun 1 1972

All Science Journal Classification (ASJC) codes

Catalysis
General Chemistry
Biochemistry
Colloid and Surface Chemistry

Access to Document

10.1021/ja00768a021

Cite this

@article{e877fe3ee60a418682721ad2bf299fda,

title = "Phosphonitrilic Compounds. XIV.1 Basic Hydrolysis of Aryloxy- and Spiroarylenedioxycyclophosphazenes",

abstract = "Bis(aryloxy)cyclophosphazenes, [NP(OAr)2]3, and spirocyclic arylenedioxycyclophosphazenes, (NPO2-Ar)3, have been hydrolyzed in basic 25 vol % water in diglyme. For the bis(aryloxy) derivatives, the ease of hydrolytic removal of the first aryloxy group in [NP(OR)2]3 from phosphorus is in the order OR = p-NO2C6H4O– > w-NO2C6H4O– > o-NO2C6H4O– ≫ C6H5O– > p-CH3C6H4O–. For the spirocyclic derivatives, the rate of cleavage of the first aryloxy-phosphorus bond is in the order [NP(O2C6H4-1,2)]3 > [NP(O2C10H6-2,3)]3 ≫ [NP(O2C12H8-2,2′)]3 and [NP(O2C12H6-1,8)]3. The mechanisms of these reactions are discussed, and comparisons are made with related phosphate ester hydrolyses.",

author = "Allcock, {H. R.} and Walsh, {E. J.}",

year = "1972",

month = jun,

day = "1",

doi = "10.1021/ja00768a021",

language = "English (US)",

volume = "94",

pages = "4538--4545",

journal = "Journal of the American Chemical Society",

issn = "0002-7863",

publisher = "American Chemical Society",

number = "13",

}

TY - JOUR

T1 - Phosphonitrilic Compounds. XIV.1 Basic Hydrolysis of Aryloxy- and Spiroarylenedioxycyclophosphazenes

AU - Allcock, H. R.

AU - Walsh, E. J.

PY - 1972/6/1

Y1 - 1972/6/1

N2 - Bis(aryloxy)cyclophosphazenes, [NP(OAr)2]3, and spirocyclic arylenedioxycyclophosphazenes, (NPO2-Ar)3, have been hydrolyzed in basic 25 vol % water in diglyme. For the bis(aryloxy) derivatives, the ease of hydrolytic removal of the first aryloxy group in [NP(OR)2]3 from phosphorus is in the order OR = p-NO2C6H4O– > w-NO2C6H4O– > o-NO2C6H4O– ≫ C6H5O– > p-CH3C6H4O–. For the spirocyclic derivatives, the rate of cleavage of the first aryloxy-phosphorus bond is in the order [NP(O2C6H4-1,2)]3 > [NP(O2C10H6-2,3)]3 ≫ [NP(O2C12H8-2,2′)]3 and [NP(O2C12H6-1,8)]3. The mechanisms of these reactions are discussed, and comparisons are made with related phosphate ester hydrolyses.

AB - Bis(aryloxy)cyclophosphazenes, [NP(OAr)2]3, and spirocyclic arylenedioxycyclophosphazenes, (NPO2-Ar)3, have been hydrolyzed in basic 25 vol % water in diglyme. For the bis(aryloxy) derivatives, the ease of hydrolytic removal of the first aryloxy group in [NP(OR)2]3 from phosphorus is in the order OR = p-NO2C6H4O– > w-NO2C6H4O– > o-NO2C6H4O– ≫ C6H5O– > p-CH3C6H4O–. For the spirocyclic derivatives, the rate of cleavage of the first aryloxy-phosphorus bond is in the order [NP(O2C6H4-1,2)]3 > [NP(O2C10H6-2,3)]3 ≫ [NP(O2C12H8-2,2′)]3 and [NP(O2C12H6-1,8)]3. The mechanisms of these reactions are discussed, and comparisons are made with related phosphate ester hydrolyses.

UR - http://www.scopus.com/inward/record.url?scp=0007445553&partnerID=8YFLogxK

UR - http://www.scopus.com/inward/citedby.url?scp=0007445553&partnerID=8YFLogxK

U2 - 10.1021/ja00768a021

DO - 10.1021/ja00768a021

M3 - Article

AN - SCOPUS:0007445553

SN - 0002-7863

VL - 94

SP - 4538

EP - 4545

JO - Journal of the American Chemical Society

JF - Journal of the American Chemical Society

IS - 13

ER -

Phosphonitrilic Compounds. XIV.¹ Basic Hydrolysis of Aryloxy- and Spiroarylenedioxycyclophosphazenes

Abstract

All Science Journal Classification (ASJC) codes

Access to Document

Other files and links

Fingerprint

Cite this