Carbon‐13 and phosphorus‐31 NMR spectroscopy of phenoxychlorocyclotriphosphazenes, N₃P₃Cl_6‐n(OC₆H₅)_n

Abstract

The "P and "C NMR spectra of all twelve phenoxychlorocyclotriphosphazenes of general formula N3P3Cb-,(OC6H5), (n = 1-6) were assigned in detail. With samples abundant in one homolog, but with a disparity between geometrical isomers, the signals due to the cis and trans isomers of N3P3C14(OC6H5)2 and N3P3Cl2(0C6H,), were also assigned. The "P chemical shifts and coupling constants correlate linearly with the level of substitution, n. The 13C NMR spectra exhibit complex multiplets for the ipso-and ortho-carbons. It is shown that each of these is the X part of one of the spin systems XAM2, XAA'M, XAA,', XAB, and XAA'B. The 13C chemical shifts of the ipso-and pQrQ-CarbOnS also exhibit correlations with n. The 13C-3'P coupling constants, both 'J(P0C) and 3J(POCC), are larger for the PCl(OC6H5) than for the P(OC6H,), moieties.

Preparation of the partially substituted (phenoxy)chlorocyclotriphosphazenes by phase-transfer catalysis

“…The eluent compositions used are listed in Table VI. The corresponding chemical shifts of the 31P NMR of each derivative obtained are listed in Table VII and compared with the reported data (Reuben, 1987). It was found that the condensation predominantly followed a nongeminal pathway (Allcock, 1972b).…”

1-Chloro-1,3,3,5,5-pentaphenoxycyclotriphosphazene: a precursor of functionalized cyclophosphazene derivatives

“…More recently, it has been used to synthesize a wide range of cyclotriphosphazene derivatives, such as cyclotriphosphazene hydrazides (Chandrasekhar et al, 2003), cyclotriphosphazene with N,N,N H ,N H -tetramethylguanidine groups (Bloy & Diefenbach, 2000), and cyclotriphosphazene with 2-, 3-and 4-pyridylmethoxy groups (Diefenbach et al, 1999). Its synthesis and NMR data have been described elsewhere (Reuben, 1987;Selvaraj et al, 1991). To date, however, structural data for (I) are not available in the Cambridge Structural Database (CSD, Version 5.24; Allen, 2002).…”

Stereodirective Effects in Mixed Substituent Vinyloxycyclotriphosphazenes

“…We have shown that the enolate ion of acetaldehyde reacts with hexahalocyclotriphosphazenes N 3 P 3 X 6 [X = F, Cl( 1 )] and that these reactions are stereoselective showing a preference for the cis isomer in the reactions of 1 . The cis isomer is also preferred in the reactions hexahalocyclophosphazenes with aryloxides. , The (vinyloxy)pentachlorocyclotriphosphazene, N 3 P 3 X 5 (OCHCH 2 ) ( 2 ), has also been used as a monomer in free radical polymerization . Allcock and Schmutz have previously explored the reaction of the sodium salt of trifluoroethanol with 1 and have shown that there is a strong preference for formation of the non-geminal trans isomer .…”