A spiro to ansa rearrangement in cyclotriphosphazene derivatives
A spiro to ansa rearrangement in cyclotriphosphazene derivatives
Nucleophilic substitution reactions of cyclotriphosphazene derivatives having five-membered spiro rings, N3P3Cl4[O(CH2)2X] (X = NH or O) with alkoxides (of tetraethylene glycol and some mono-functional alcohols) give unexpected rearrangements to form stable seven-membered ring ansa compounds, even though crystallographic evidence shows ring distortion and compression of the cyclophosphazene ring. With weaker nucleophiles such as sodium phenoxide and pyrrolidine substitution at a PCl2 group is preferred and no rearrangement takes place. In contrast, reactions of the analogous phosphazenes containing six-membered spiro rings, N3P3Cl4[O(CH2)3X], with all of the above reagents give only normal substitution reactions at the PCl2 moieties and no rearrangement products. The spiro to ansa rearrangements in cyclophosphazenes are remarkable as the reported primary reaction products with the same difunctional reagents HO(CH2)2XH are predominantly spiro, with some dangling and bridging derivatives, but no ansa compounds.
cyclophosphazenes, rings, spectra, phosphonitrilic, conformation, hexachlorocyclotriphosphazene, phosphazenes, compounds, substitution-reactions, isomers, phosphorus-nitrogen-compounds
2792-2801
Beşli, Serap
63ec1cf4-d0d6-4982-9e0a-c632f1f98d08
Coles, Simon J.
3116f58b-c30c-48cf-bdd5-397d1c1fecf8
Davies, David B.
675b90e6-0c3c-468b-9996-326220517cc6
Hursthouse, Michael B.
57a2ddf9-b1b3-4f38-bfe9-ef2f526388da
Kılıç, Adem
565a42ec-2d18-4142-8b37-bb74b244b2f5
Shaw, Robert A.
a9ecde60-6fe9-4b5d-86e3-77cd5dcfaab8
2007
Beşli, Serap
63ec1cf4-d0d6-4982-9e0a-c632f1f98d08
Coles, Simon J.
3116f58b-c30c-48cf-bdd5-397d1c1fecf8
Davies, David B.
675b90e6-0c3c-468b-9996-326220517cc6
Hursthouse, Michael B.
57a2ddf9-b1b3-4f38-bfe9-ef2f526388da
Kılıç, Adem
565a42ec-2d18-4142-8b37-bb74b244b2f5
Shaw, Robert A.
a9ecde60-6fe9-4b5d-86e3-77cd5dcfaab8
Beşli, Serap, Coles, Simon J., Davies, David B., Hursthouse, Michael B., Kılıç, Adem and Shaw, Robert A.
(2007)
A spiro to ansa rearrangement in cyclotriphosphazene derivatives.
Dalton Transactions, (26), .
(doi:10.1039/b703541a).
Abstract
Nucleophilic substitution reactions of cyclotriphosphazene derivatives having five-membered spiro rings, N3P3Cl4[O(CH2)2X] (X = NH or O) with alkoxides (of tetraethylene glycol and some mono-functional alcohols) give unexpected rearrangements to form stable seven-membered ring ansa compounds, even though crystallographic evidence shows ring distortion and compression of the cyclophosphazene ring. With weaker nucleophiles such as sodium phenoxide and pyrrolidine substitution at a PCl2 group is preferred and no rearrangement takes place. In contrast, reactions of the analogous phosphazenes containing six-membered spiro rings, N3P3Cl4[O(CH2)3X], with all of the above reagents give only normal substitution reactions at the PCl2 moieties and no rearrangement products. The spiro to ansa rearrangements in cyclophosphazenes are remarkable as the reported primary reaction products with the same difunctional reagents HO(CH2)2XH are predominantly spiro, with some dangling and bridging derivatives, but no ansa compounds.
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Published date: 2007
Keywords:
cyclophosphazenes, rings, spectra, phosphonitrilic, conformation, hexachlorocyclotriphosphazene, phosphazenes, compounds, substitution-reactions, isomers, phosphorus-nitrogen-compounds
Identifiers
Local EPrints ID: 54247
URI: http://eprints.soton.ac.uk/id/eprint/54247
ISSN: 1477-9226
PURE UUID: 4ab8b449-5607-4cb0-ae81-a4ce7f50c9d5
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Date deposited: 30 Jul 2008
Last modified: 16 Mar 2024 03:05
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Author:
Serap Beşli
Author:
David B. Davies
Author:
Adem Kılıç
Author:
Robert A. Shaw
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