Hydrolysis Pathways for Aminophosphazenes

Harry R. Allcock, T. J. Fuller, K. Matsumura

Research output: Contribution to journalArticle

131 Citations (Scopus)

Abstract

The hydrolysis behavior of the aminocyclotriphosphazenes (NPR2)3, where R = NH2, NHCH3, NHCH2COOC2H5, NHCH2CONHCH3, N2C3H3 (imidazolyl), NHCH2CF3, NHCH2C6H5, NHC6H5, NC4H4 (pyrrolyl), NC4H8 (pyrrolidino), NC5H10 (piperidino), and NC4H8O (morpholino), has been examined in water or aqueous dioxane, acid, and base. The ease of hydrolysis in aqueous dioxane declined with changes in R in the order N2C3H3 > NHCH2COOC2H5 > NHC-H2CONHCH3 > NH2 > NHCH3 > NHC6H5 > NHCH2C6H5 > NHCH2CF3 > NC4H4, NC4H8, NC5H10, and NC4H8O. Two different but interconnected mechanistic pathways appear to be followed. In the first, hydrolytic removal of one amino residue from phosphorus occurs to yield species of type N3P3R5OH before cleavage of the phosphazene ring takes place. In the second, cleavage of the phosphazene ring is a fast reaction following protonation of the ring nitrogen atoms. Those compounds which contained amino acid ester or amide side groups hydrolyzed only after prior initial conversion of the ester or amide units to free carboxylic acid groups. Comparisons are made with the behavior of the open-chain high polymers of formula (NPR2)n, where R = NHCH3, NHCH3 and N2C3H3, NHCH2COOC2H5, and NHCH2CONHCH3, and the overall trends are considered in terms of the potential biomedical behavior of these compounds.

Original languageEnglish (US)
Pages (from-to)515-521
Number of pages7
JournalInorganic chemistry
Volume21
Issue number2
DOIs
StatePublished - Jan 1 1982

Fingerprint

phosphazene
Amides
hydrolysis
Hydrolysis
Esters
Morpholinos
amides
esters
cleavage
rings
Protonation
Carboxylic Acids
Phosphorus
Polymers
high polymers
Nitrogen
Amino Acids
carboxylic acids
Atoms
nitrogen atoms

All Science Journal Classification (ASJC) codes

  • Physical and Theoretical Chemistry
  • Inorganic Chemistry

Cite this

Allcock, Harry R. ; Fuller, T. J. ; Matsumura, K. / Hydrolysis Pathways for Aminophosphazenes. In: Inorganic chemistry. 1982 ; Vol. 21, No. 2. pp. 515-521.
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Hydrolysis Pathways for Aminophosphazenes. / Allcock, Harry R.; Fuller, T. J.; Matsumura, K.

In: Inorganic chemistry, Vol. 21, No. 2, 01.01.1982, p. 515-521.

Research output: Contribution to journalArticle

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AB - The hydrolysis behavior of the aminocyclotriphosphazenes (NPR2)3, where R = NH2, NHCH3, NHCH2COOC2H5, NHCH2CONHCH3, N2C3H3 (imidazolyl), NHCH2CF3, NHCH2C6H5, NHC6H5, NC4H4 (pyrrolyl), NC4H8 (pyrrolidino), NC5H10 (piperidino), and NC4H8O (morpholino), has been examined in water or aqueous dioxane, acid, and base. The ease of hydrolysis in aqueous dioxane declined with changes in R in the order N2C3H3 > NHCH2COOC2H5 > NHC-H2CONHCH3 > NH2 > NHCH3 > NHC6H5 > NHCH2C6H5 > NHCH2CF3 > NC4H4, NC4H8, NC5H10, and NC4H8O. Two different but interconnected mechanistic pathways appear to be followed. In the first, hydrolytic removal of one amino residue from phosphorus occurs to yield species of type N3P3R5OH before cleavage of the phosphazene ring takes place. In the second, cleavage of the phosphazene ring is a fast reaction following protonation of the ring nitrogen atoms. Those compounds which contained amino acid ester or amide side groups hydrolyzed only after prior initial conversion of the ester or amide units to free carboxylic acid groups. Comparisons are made with the behavior of the open-chain high polymers of formula (NPR2)n, where R = NHCH3, NHCH3 and N2C3H3, NHCH2COOC2H5, and NHCH2CONHCH3, and the overall trends are considered in terms of the potential biomedical behavior of these compounds.

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