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

Abstract

Beşli, Serap; Coles, Simon J.; Davies, David B.; Eaton, Robert J.; Kılıç, Adem; 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][964][965][966][967][968][969][970][971][972][973][974] This is an author-produced version of a paper published in Polyhedron . This version has been peer-reviewed, but does not include the final publisher proof corrections, published layout, or pagination. All articles available through Birkbeck ePrints are protected by intellectual property law, including copyright law. Any use made of the contents should comply with the relevant law. AbstractReaction of hexachlorocyclotriphosphazene, N 3 P 3 Cl 6 (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 1 H, 19 F and 31 P NMR spectroscopy: the mono-spiro compound, N 3 P 3 Cl 4 (OCH 2 CF 2 CF 2 CH 2 O), (3), its ansa isomer, (4), a di-spiro derivative N 3 P 3 Cl 2 (OCH 2 CF 2 CF 2 CH 2 O) 2 , (5), its spiro-ansa (6) and non-gem cis bis-ansa (7) isomers and a tri-spiro compound N 3 P 3 (OCH 2 CF 2 CF 2 CH 2 O) 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 (1) with step-wise additions of (2) were also investigated at low temperature (-78 0 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 (1) with butane-1,4-diol/pyridine mixtures and with the reaction of hexafluorocyclotriphosphazene, N 3 P 3 F 6 (9), with the silyl derivative of the diol (2), (Me 3 SiOCH 2 CF 2 ) 2 , in a 1:0.4 mole ratio in the same solvent, THF.3

Chemistry of diphenyltetrafluorophosphazene: Reactions with dilithiated diols

“…We have also shown that lithiated diols react quite differently with fluorophosphazenes when compared to silylated diols with the former forming preferentially the kinetically controlled ansa substituted products [9]. Comparison of reactions of disodium and dilithium salts of a diol with N 3 P 3 Cl 6 also shows interesting differences in the nature and yield of cyclized products [12]. In this context, we were interested in exploring the reactions of gem-diphenyltetrafluorophosphazene, [1,1-(C 6 H 5 ) 2 ]P 3 N 3 F 4 (1) with difunctional reagents, especially with dilithiated diols.…”

Synthesis and Structural Characterization of Singly, Doubly, and Triply Bridged Derivatives of Hexachlorocyclotriphosphazene with Bis(2-hydroxyethyl) Ether and 2,2-dimethylpropane-1,3-diol

“…27,34 There are two different meso forms-one has a center of symmetry and the other has a plane of symmetry-which are formed with equal probability as mixture of diastereoisomers. In this case, two sets of closely spaced NMR signals of equal intensity should be expected for the mixture of diastereoisomers (which would indeed result in a doubling of the NMR signals for both the P(OR)Cl and PCl groups).…”

“…39 Similar results were also obtained from the reaction of 1 with 1,4-butane-, 1,5-pentane and 1,6-hexane fluorinated diols. 20,27,30 Bridged compounds were obtained in better yields and assumed significant importance for reaction of 1 with diamines of increasing chain lengths and for the diols having the linking -(CH 2 ) n -group with n = 5, 6, 8, and 10, respectively. 28 We have previously reported that the reaction of hexachlorocyclotriphosphazene 1 with 2,2-dimethylpropane-1,3-diol 1 and bis(2-hydroxyethyl) ether 2 leads, in general, to the formation predominantly of spiro and ansa structures (Schemes 1 and 2).…”

4′,4′,6′,6′-Tetrachloro-2-(6-methylpyridin-2-yl)-1H,2H-spiro[naphtho[1,2-e][1,3,2]oxazaphosphinine-3,2′-[1,3,5,2,4,6]triazatriphosphinine]

“…For products from the reaction of N 3 P 3 Cl 6 with bifunctional reagents, see: Beşli et al (2006). For N/O donor type bifunctional reagents used for the reaction of hexachlorocyclotriphosphazene giving spiro derivatives, see: Beşli et al (2007); Sournies et al (1997); Deutsch & Shaw (1990); Işıklan et al (2010); İlter et al (2004, 2007); Tercan et al (2004).…”