Formation of spiro and ansa derivatives in the reaction of 2,2,3,3,4,4-hexafluoropentane-1,5-diol with cyclotriphosphazene: Comparison with 2,2,3,3-tetrafluorobutane-1,4-diol

Reaction of cyclophosphazene, N3P3Cl6 (1), with the sodium derivative of the fluorinated diol, 2,2,3,3,4,4-hexafluoropentane-1,5-diol (2), in THF solution at room temperature afforded five isolated products, whose structures have been characterised by X-ray crystallography and 1H, 19F and 31P NMR spectroscopy: the mono-spiro compound, N3P3Cl4(OCH2CF2CF2CF2CH2O) (3), its ansa isomer (4), a di-spiro derivative N3P3Cl2(OCH2CF2CF2CF2CH2O)2 (5), its spiro-ansa (6) isomer and the tri-spiro compound N3P3(OCH2CF2CF2CF2CH2O)3 (7). Quantitative 31P NMR measurements of the soluble portion of the reaction mixture show that in the reaction of (1) with the sodium derivative of the fluorinated pentanediol (2) there is a small preference for spiro compounds compared to ansa compounds (ratio ca. 1.3:1), similar to the analogous reaction of (1) with the sodium derivative of the fluorinated butanediol where there is a slightly greater proportion of spiro compared to ansa compounds (ratio ca. 1.5:1). The relative proportions of spiro and ansa compounds is likely to depend on the fine balance in stabilities of the different medium-sized rings in the fluorinated pentanediol (spiro, 8- and ansa, 10-membered rings) compared to the fluorinated butanediol (spiro, 7- and ansa, nine-membered rings) derivatives of cyclophosphazene.

The relative proportions of spiro and ansa compounds depend on the fine balance in stabilities of the different medium-sized rings formed in the reaction of cyclophosphazene with the fluorinated pentanediol (n = 3) compared to the fluorinated butanediol (n = 2).Figure optionsDownload as PowerPoint slide