Degradation of halogenophosphazenes to a new phosphorane system

H. R. Allcock; R. L. Kugel

doi:10.1039/C19680001606

Degradation of halogenophosphazenes to a new phosphorane system

H. R. Allcock
, R. L. Kugel

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

Original language	English (US)
Pages (from-to)	1606-1607
Number of pages	2
Journal	Chemical Communications (London)
Issue number	24
DOIs	https://doi.org/10.1039/C19680001606
State	Published - 1968

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General Chemistry

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@article{4b82a5e41b7543bbbac8d06ca501a46d,

title = "Degradation of halogenophosphazenes to a new phosphorane system",

author = "Allcock, \{H. R.\} and Kugel, \{R. L.\}",

note = "Funding Information: The reactions of (I) also confirmed its structure. For example, in solution the compound underwent reactions expected of (Ia) . Thus, treatment with acetyl chloride yielded an acyl derivative, m.p. 218-220”, of structure (11). I.r., lH n.m.r., and mass spectrometry confirmed the structure of this species. The 31P spectrum showed one peak at +46 p.p.m., relative to triethyl phosphate. Compound (I) closely resembles (111), which was reported previously as a product formed from the almost instantaneous reaction of (NPCl,) or tris(o-pheny1enedioxy)cyclotriphosphazene with catechol and triethylamine., However, there is no evidence that the direct interaction of catechol and (NPCl,)] in the absence of base yields a species comparable to (I). In the penta-co-ordinate structure (Ia), the “free” o-aminophenoxy-ligand probably occupies an equatorial position, since this would allow both 0-P-N bond angles to approach 90”. The driving force for the ready formation of (I) from a phos- phazene may be the bond angle minimization at phosphorus which occurs in this process. In structure (Ia), a free NH,-group is present rather than an OH-group. This is an important result for the interpretation of substitution mechanisms at penta-co-ordinate phosphorus. We thank the U.S. Public Health Service for the support of this work, and American Cyanamid Co. for an educational leave of absence fellowship (to R. L. K). (Received, October loth, 1968; Cum. 1387.) N. B. Colthup, L. H. Daly, and S. E. Wiberley, “Introduction to Infrared and Raman Spectroscopy”, Academic H. R. Allcock, J . Amer. Chew. SOL, 1963, 85, 4050; ibid., 1964, 86, 2591. Press, New York, 1964, p. 282. Copyright: Copyright 2007 Elsevier B.V., All rights reserved.",

year = "1968",

doi = "10.1039/C19680001606",

language = "English (US)",

pages = "1606--1607",

journal = "Chemical Communications (London)",

issn = "0009-241X",

publisher = "Royal Society of Chemistry",

number = "24",

}

TY - JOUR

T1 - Degradation of halogenophosphazenes to a new phosphorane system

AU - Allcock, H. R.

AU - Kugel, R. L.

N1 - Funding Information: The reactions of (I) also confirmed its structure. For example, in solution the compound underwent reactions expected of (Ia) . Thus, treatment with acetyl chloride yielded an acyl derivative, m.p. 218-220”, of structure (11). I.r., lH n.m.r., and mass spectrometry confirmed the structure of this species. The 31P spectrum showed one peak at +46 p.p.m., relative to triethyl phosphate. Compound (I) closely resembles (111), which was reported previously as a product formed from the almost instantaneous reaction of (NPCl,) or tris(o-pheny1enedioxy)cyclotriphosphazene with catechol and triethylamine., However, there is no evidence that the direct interaction of catechol and (NPCl,)] in the absence of base yields a species comparable to (I). In the penta-co-ordinate structure (Ia), the “free” o-aminophenoxy-ligand probably occupies an equatorial position, since this would allow both 0-P-N bond angles to approach 90”. The driving force for the ready formation of (I) from a phos- phazene may be the bond angle minimization at phosphorus which occurs in this process. In structure (Ia), a free NH,-group is present rather than an OH-group. This is an important result for the interpretation of substitution mechanisms at penta-co-ordinate phosphorus. We thank the U.S. Public Health Service for the support of this work, and American Cyanamid Co. for an educational leave of absence fellowship (to R. L. K). (Received, October loth, 1968; Cum. 1387.) N. B. Colthup, L. H. Daly, and S. E. Wiberley, “Introduction to Infrared and Raman Spectroscopy”, Academic H. R. Allcock, J . Amer. Chew. SOL, 1963, 85, 4050; ibid., 1964, 86, 2591. Press, New York, 1964, p. 282. Copyright: Copyright 2007 Elsevier B.V., All rights reserved.

PY - 1968

Y1 - 1968

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U2 - 10.1039/C19680001606

DO - 10.1039/C19680001606

M3 - Article

AN - SCOPUS:8344274119

SN - 0009-241X

SP - 1606

EP - 1607

JO - Chemical Communications (London)

JF - Chemical Communications (London)

IS - 24

ER -

Degradation of halogenophosphazenes to a new phosphorane system

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