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Competitive formation of spiro and ansa derivatives in the reactions of tetrafluorobutane-1,4-diol with hexachlorocyclotriphosphazene: a comparison with butane-1,4-diol

Competitive formation of spiro and ansa derivatives in the reactions of tetrafluorobutane-1,4-diol with hexachlorocyclotriphosphazene: a comparison with butane-1,4-diol
Competitive formation of spiro and ansa derivatives in the reactions of tetrafluorobutane-1,4-diol with hexachlorocyclotriphosphazene: a comparison with butane-1,4-diol
Reaction of hexachlorocyclotriphosphazene, N3P3Cl6 (1), in two stoichiometries (1:1.2 and 1: 3) with the sodium derivative of the fluorinated diol, 2,2,3,3-tetrafluorobutane-1,4-diol (2), in THF solution at room temperature afforded six products, whose structures have been characterized by X-ray crystallography and H-1, F-19 and P-31 NMR spectroscopy: the mono-spiro compound, N3P3Cl4(OCH2CF2CF2CH2O) (3), its ansa isomer (4), a di-spiro derivative N3P3Cl2(OCH2CF2CF2CH2O)(2) (5), its spiro-ansa (6) and non-gem cis bis-ansa (7) isomers and a tri-spiro compound N3P3(OCH2CF2CF2CH2O)(3) (8). The tri-spiro derivative 8 was also formed in the reaction of the ansa compound 4 with diol (2) in a 1:3 ratio in THF at room temperature. The reactions of I with step-wise additions of 2 were also investigated at low temperature (-78 degrees C) to give the same range of products as at room temperature. The results of all reactions are compared with previous work on the reactions of I with butane-1,4-diol/pyridine mixtures and with the reaction of hexafluorocyclotriphosphazene, N3P3F6 (9), with the silyl derivative of the diol (2), (Me3SiOCH2CF2)(2), in a 1:0.4 mole ratio in the same solvent, THF.
cyclophosphazenes, crystal structure, spiro, ansa, tetrafluorobutane-1, 4-dioxy derivatives phosphorus-nitrogen-compounds, ray crystal-structures, isomeric n3p3cl22 derivatives, nuclear-magnetic-resonance, substitution-reactions, structural investigations, phosphazene chemistry, replacement pattern, nmr-spectra, 1st example
0277-5387
963-974
Besli, Serap
0127fb56-1156-4946-b5cb-789828fe9ffb
Coles, Simon J.
3116f58b-c30c-48cf-bdd5-397d1c1fecf8
Davies, David B.
675b90e6-0c3c-468b-9996-326220517cc6
Eaton, Robert J.
e274676b-0499-47e1-8dbb-8d1ed908cdea
Kilic, Adem
1bf0a2d7-b8c6-4740-bd84-89b8db4c5769
Shaw, Robert A.
a9ecde60-6fe9-4b5d-86e3-77cd5dcfaab8
Besli, Serap
0127fb56-1156-4946-b5cb-789828fe9ffb
Coles, Simon J.
3116f58b-c30c-48cf-bdd5-397d1c1fecf8
Davies, David B.
675b90e6-0c3c-468b-9996-326220517cc6
Eaton, Robert J.
e274676b-0499-47e1-8dbb-8d1ed908cdea
Kilic, Adem
1bf0a2d7-b8c6-4740-bd84-89b8db4c5769
Shaw, Robert A.
a9ecde60-6fe9-4b5d-86e3-77cd5dcfaab8

Besli, Serap, Coles, Simon J., Davies, David B., Eaton, Robert J., Kilic, Adem and Shaw, Robert A. (2006) Competitive formation of spiro and ansa derivatives in the reactions of tetrafluorobutane-1,4-diol with hexachlorocyclotriphosphazene: a comparison with butane-1,4-diol. Polyhedron, 25 (4), 963-974. (doi:10.1016/j.poly.2005.10.027).

Record type: Article

Abstract

Reaction of hexachlorocyclotriphosphazene, N3P3Cl6 (1), in two stoichiometries (1:1.2 and 1: 3) with the sodium derivative of the fluorinated diol, 2,2,3,3-tetrafluorobutane-1,4-diol (2), in THF solution at room temperature afforded six products, whose structures have been characterized by X-ray crystallography and H-1, F-19 and P-31 NMR spectroscopy: the mono-spiro compound, N3P3Cl4(OCH2CF2CF2CH2O) (3), its ansa isomer (4), a di-spiro derivative N3P3Cl2(OCH2CF2CF2CH2O)(2) (5), its spiro-ansa (6) and non-gem cis bis-ansa (7) isomers and a tri-spiro compound N3P3(OCH2CF2CF2CH2O)(3) (8). The tri-spiro derivative 8 was also formed in the reaction of the ansa compound 4 with diol (2) in a 1:3 ratio in THF at room temperature. The reactions of I with step-wise additions of 2 were also investigated at low temperature (-78 degrees C) to give the same range of products as at room temperature. The results of all reactions are compared with previous work on the reactions of I with butane-1,4-diol/pyridine mixtures and with the reaction of hexafluorocyclotriphosphazene, N3P3F6 (9), with the silyl derivative of the diol (2), (Me3SiOCH2CF2)(2), in a 1:0.4 mole ratio in the same solvent, THF.

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More information

Published date: 2006
Keywords: cyclophosphazenes, crystal structure, spiro, ansa, tetrafluorobutane-1, 4-dioxy derivatives phosphorus-nitrogen-compounds, ray crystal-structures, isomeric n3p3cl22 derivatives, nuclear-magnetic-resonance, substitution-reactions, structural investigations, phosphazene chemistry, replacement pattern, nmr-spectra, 1st example

Identifiers

Local EPrints ID: 44383
URI: https://eprints.soton.ac.uk/id/eprint/44383
ISSN: 0277-5387
PURE UUID: c6cfd6af-306e-4136-9633-166f397d2a12
ORCID for Simon J. Coles: ORCID iD orcid.org/0000-0001-8414-9272

Catalogue record

Date deposited: 01 Mar 2007
Last modified: 14 Mar 2019 01:48

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