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Effect of chain length on the formation of intramolecular and intermolecular products: reaction of diols with cyclotriphosphazene

Effect of chain length on the formation of intramolecular and intermolecular products: reaction of diols with cyclotriphosphazene
Effect of chain length on the formation of intramolecular and intermolecular products: reaction of diols with cyclotriphosphazene
The reactions of cyclotriphosphazene, N(3)P(3)Cl(6) (1), in a 1:1.2 stoichiometry with the sodium derivative of seven diols [ethane- (2a), 1,3-propane- (2b), 1,4-butane- (2c), 1,5-pentane- (2d.), 1,6-hexane- (2e), 1,8-octane- (2f) and 1,10-decane- (2g) diol] in THF solution at room temperature have been used to investigate the effect of chain length on the formation of reaction products. Although no new products were found for the reaction of 1 with diols 2a-c compared to those in the literature using other bases and solution conditions, the reactions of 1 with the diols 2d-g gave six different types of products, whose structures have been characterized by elemental analysis, mass spectrometry, I H and (31)P NMR spectroscopy; ansa compounds N(3)P(3)Cl(4)[O(CH(2))(n)O], (5d-5g): single-bridged compounds N(3)P(3)Cl(5)[O(CH(2))(n)O]N(3)P(3)Cl(5) (6d-6f); double-bridged compounds N(3)P(3)Cl(4)[O(CH(2))(n)O](2)N(3)P(3)Cl(4) (7d-7g, syn and anti) and triple-bridged compounds, N(3)P(3)Cl(3)[O(CH(2))(n)O](3)N(3)P(3)Cl(3) (8d-f). Where suitable single crystals were obtained, X-ray crystallographic studies confirmed the structures of two ansa compounds (5d and 5f), one single-bridged compound (6e), and five double-bridged compounds (meso-anti for 7d, 7e, 7f and meso-syn for 7d and 7f). (31)P NMR measurements of the reaction mixtures were used to quantify the formation of products for the reactions 1 with all the diols, 2a-g; it is found that, with increasing chain length of the diol, there is a decrease in the products formed by intramolecular reactions (spiro and ansa derivatives) and a concomitant increase in the amounts of products formed by intermolecular reactions (single-, double- and triple-bridged derivatives) of cyclophosphazene. (C) 2010 Elsevier Ltd. All rights reserved.
0277-5387
329-339
Beşli, Serap
63ec1cf4-d0d6-4982-9e0a-c632f1f98d08
Coles, Simon J.
3116f58b-c30c-48cf-bdd5-397d1c1fecf8
Davarcı, Derya
533335d1-fecd-47af-b1ad-24367bd38961
Davies, David B.
675b90e6-0c3c-468b-9996-326220517cc6
Yuksel, Fatma
fd4e915b-0424-4495-bd35-e89c707bacd5
Beşli, Serap
63ec1cf4-d0d6-4982-9e0a-c632f1f98d08
Coles, Simon J.
3116f58b-c30c-48cf-bdd5-397d1c1fecf8
Davarcı, Derya
533335d1-fecd-47af-b1ad-24367bd38961
Davies, David B.
675b90e6-0c3c-468b-9996-326220517cc6
Yuksel, Fatma
fd4e915b-0424-4495-bd35-e89c707bacd5

Beşli, Serap, Coles, Simon J., Davarcı, Derya, Davies, David B. and Yuksel, Fatma (2011) Effect of chain length on the formation of intramolecular and intermolecular products: reaction of diols with cyclotriphosphazene. Polyhedron, 30 (2), 329-339. (doi:10.1016/j.poly.2010.10.020).

Record type: Article

Abstract

The reactions of cyclotriphosphazene, N(3)P(3)Cl(6) (1), in a 1:1.2 stoichiometry with the sodium derivative of seven diols [ethane- (2a), 1,3-propane- (2b), 1,4-butane- (2c), 1,5-pentane- (2d.), 1,6-hexane- (2e), 1,8-octane- (2f) and 1,10-decane- (2g) diol] in THF solution at room temperature have been used to investigate the effect of chain length on the formation of reaction products. Although no new products were found for the reaction of 1 with diols 2a-c compared to those in the literature using other bases and solution conditions, the reactions of 1 with the diols 2d-g gave six different types of products, whose structures have been characterized by elemental analysis, mass spectrometry, I H and (31)P NMR spectroscopy; ansa compounds N(3)P(3)Cl(4)[O(CH(2))(n)O], (5d-5g): single-bridged compounds N(3)P(3)Cl(5)[O(CH(2))(n)O]N(3)P(3)Cl(5) (6d-6f); double-bridged compounds N(3)P(3)Cl(4)[O(CH(2))(n)O](2)N(3)P(3)Cl(4) (7d-7g, syn and anti) and triple-bridged compounds, N(3)P(3)Cl(3)[O(CH(2))(n)O](3)N(3)P(3)Cl(3) (8d-f). Where suitable single crystals were obtained, X-ray crystallographic studies confirmed the structures of two ansa compounds (5d and 5f), one single-bridged compound (6e), and five double-bridged compounds (meso-anti for 7d, 7e, 7f and meso-syn for 7d and 7f). (31)P NMR measurements of the reaction mixtures were used to quantify the formation of products for the reactions 1 with all the diols, 2a-g; it is found that, with increasing chain length of the diol, there is a decrease in the products formed by intramolecular reactions (spiro and ansa derivatives) and a concomitant increase in the amounts of products formed by intermolecular reactions (single-, double- and triple-bridged derivatives) of cyclophosphazene. (C) 2010 Elsevier Ltd. All rights reserved.

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Published date: February 2011
Organisations: Organic Chemistry: Synthesis, Catalysis and Flow

Identifiers

Local EPrints ID: 346127
URI: https://eprints.soton.ac.uk/id/eprint/346127
ISSN: 0277-5387
PURE UUID: f98b5981-fcfa-4e97-996e-2b320aff04ad
ORCID for Simon J. Coles: ORCID iD orcid.org/0000-0001-8414-9272

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Date deposited: 19 Dec 2012 12:25
Last modified: 19 Nov 2019 01:53

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