Phospha-s-triazines. VII. Phenyl-bridged phospha-s-triazines

Paciorek, K. J. L.; Ito, T.I.; Nakahara, J.H.; Harris, D.H.; Kratzer, R.H.

doi:10.1016/s0022-1139(00)81115-x

Cited by 6 publications

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“…For example, in contrast to the high temperature/time requirement for the thermal ring opening polymerization of N 3 P 3 Cl 6 , ∼250 °C, N 3 P 2 CCl 5 can be easily polymerized at 120 °C/3−4 h to form the linear polymer −[C(Cl)NP(Cl) 2 NP(Cl) 2 N−] n . On the other hand, perfluoroalkyl-substituted dicarbaphosphazenes of the type [R f CN] 2 [R 2 PN] [R f = perfluoroalkyl, perfluoroalkoxy] show high thermal stability and, therefore, find applications as additives for controlling and arresting oxidation and degradation of polyfluoroalkyl ether high-temperature lubricants and fluids. − The nature of these compounds complements some high molecular weight fluoro polyethers which are currently being investigated in our laboratories for similar purposes . The difference in the chemistry of these carbaphosphazenes is also reflected by the fact that while the alkoxy/fluoroalkoxy-substituted cyclotriphosphazenes and polytriphosphazenes are hydrolytically stable, their carbaphosphazene counterparts result in degradation when exposed to moisture .…”

Section: Introductionmentioning

confidence: 99%

Selective Reactivity of the Phosphorus−Chlorine and Carbon−Chlorine Bonds in Cyclic Chlorocarbaphosphazenes: An Unusual Activation of a Carbon−Nitrogen Bond in Trialkylamines

et al. 1997

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Acyclic tertiary amines such as triethylamine and tri-n-propylamine used as HCl scavengers in nucleophilic substitution reactions of cyclic chlorocarbaphosphazenes [N(3)PC(2)Cl(4) (I) and N(3)P(2)CCl(5) (II)] with (CF(2))(n)()(CF(2)CH(2)OH)(2) [n = 0 (III) or 1 (IV)] are found to undergo a facile C-N bond cleavage with the regiospecific substitution of the dialkylamino groups on the ring carbon atoms of the carbaphosphazene. In the case of cyclic amines such as 1-methylpiperidine and 4-methylmorpholine, the cleavage was found to occur regiospecifically at the N-CH(3) bond, resulting in the ring substitution of the cyclic secondary amino group on the dicarbaphosphazene ring carbon atoms. The polyfluoro diol III forms a spirocyclic ring exclusively at the phosphorus site in compounds [CF(2)CH(2)O](2)PN(3)C(2)[N(C(2)H(5))(2)](2) (1), [CF(2)CH(2)O](2)PN(3)C(2)[N(C(3)H(7))(2)](2) (2), [CF(2)CH(2)O](2)PN(3)C(2)[NCH(2)(CH(2))(3)CH(2)](2) (3), and [CF(2)CH(2)O](2)PN(3)C(2)[N(CH(2))(2)O(CH(2))(2)](2) (5) along with the formation of carbon-substituted carbaphosphazenes, Cl(2)PN(3)C(2)[NCH(2)(CH(2))(3)CH(2)](2) (4) and Cl(2)PN(3)C(2)[N(CH(2))(2)O(CH(2))(2)](2) (6). Reaction of II with III in the presence of triethylamine affords the dispiro product [CF(2)CH(2)O)(2)](2)P(2)N(3)C[N(C(2)H(5))(2)] (7), which crystallizes in a polar orthorhombic space group, Cmc2(1). Upon refluxing of I or II with R(3)N (R = C(2)H(5), n-C(3)H(7)) in toluene, the amino-substituted carbaphosphazenes, Cl(2)PN(3)C(2)[N(C(2)H(5))(2)](2) (8), Cl(4)P(2)N(3)C[N(C(2)H(5))(2)] (9), and Cl(4)P(2)N(3)C[N(n-C(3)H(7))(2)] (10) are obtained in good yields. Hydrolysis of 8 leads to the formation of Cl(O)PN(H)N(2)C(2)[N(C(2)H(5))(2)](2) (11). When lithium salts of the fluoro diols III and IV are reacted with I or II in diethyl ether, the P-Cl bond is selectively substituted, yielding the spirocyclic [CF(2)CH(2)O](2)PN(3)C(2)Cl(2) (12), [CF(2)(CF(2)CH(2)O)(2)]PN(3)C(2)Cl(2) (13), [CF(2)CH(2)O](2)P(2)N(3)CCl(3) (14), and [(CF(2)CH(2)O)(2)](2)P(2)N(3)CCl (15). The C-Cl bonds in 12 and 14 were easily substituted by their reaction with 4-FC(6)H(4)XNa (X = O or S) to form [CF(2)CH(2)O](2)PN(3)C(2)[4-FC(6)H(4)O](2) (16) and [CF(2)CH(2)O](2)PN(3)C(2)[4-FC(6)H(4)S](2) (17). Reactions of 12 and 13 with (CH(3))(3)SiN(CH(3))(2) under mild conditions result in the elimination of (CH(3))(3)SiCl along with the formation of [CF(2)CH(2)O](2)PN(3)C(2)[N(CH(3))(2)](2) (18). The X-ray analyses of 13 and 18 represent the first examples of eight-membered spirocyclic phosphazenes. The thermal behavior of II, 9, 10, 14, and15 has also been investigated at 120 degrees C. Single-crystal X-ray diffraction studies were carried out for 1, 2, 7, 9-14, and 16-19, and these compounds are also characterized using IR, (1)H, (13)C, (19)F and (31)P NMR spectroscopy, MS, and elemental analysis.

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Section: Introductionmentioning

confidence: 99%

Selective Reactivity of the Phosphorus−Chlorine and Carbon−Chlorine Bonds in Cyclic Chlorocarbaphosphazenes: An Unusual Activation of a Carbon−Nitrogen Bond in Trialkylamines

et al. 1997

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“…Other work examines the potential application of ionic liquids derived from cyclophosphazenes as additives in water lubrication of silicon nitride ceramics [6]. Dicarbaphosphazenes have been suggested as additives as high temperature lubricants when substituted with perfluoroalkyl chains [7].…”

Section: Introductionmentioning

confidence: 99%