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In: Chemical Communications (London), No. 24, 1968, p. 1606-1607.
Research output: Contribution to journal › Article › peer-review
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