Synthesis, n.m.r. spectra, and X-ray crystal structure of 2-trans-4-diamino-2,4,6,6-tetra-n-propoxycyclotriphosphazatriene. The first example of a geminal to trans-nongeminal amino-group migration in phosphazene chemistry

Abstract

X-Ray crystallographic and n.m.r. spectroscopic investigations show that the geminal amino derivative N3P3C14(NH2)2 on treatment with sodium n-propoxide in n-propanol gives the trans-compound, N3P3(NH2)2(OPrn)4, this being the first example of a rearrangement of this type in phosphazene chemistry.

Phosphorus–nitrogen compounds. Part 54. The reactions of geminal N3P3(NH2)2Cl4and of N3P3(NH2)Cl5with alkoxide ions in alcohols. The geminal P(NH2)2to non-geminal P(NH2)(OR) rearrangement. The crystal structures of trans-N3P3(NH2)2(OPrn)4, cis-N3P3(NH2)2(OMe)4Fincham1, Parkes2, Shaw3 et al. 1988J. Chem. Soc., Dalton Trans.Self Cite21020View full textAdd to dashboardCite

“…Compound (5; R = Pr") was the first rearranged compound to be isolated and the first crystal structure of its type to be determined. 20,22 High thermal motions of the n-propyl groups prevented us from obtaining a good structure (R = 0.10). The structure is stabilised by extensive hydrogen bonding and within that framework the alkyl chains can take up different orientations.…”

Synthesis of phenoxy‐substituted spiro‐ansa phosphazene derivatives

“…Infrared spectra were recorded as KBr pellets in the range 400-4000 cm −1 on an ATI Unicam Mattson 1000 spectrophotometer. 1 H, 13 C, and 31 P NMR spectra were recorded using a Bruker ultra shield spectrometer operating at 300.13 MHz ( 1 H), 75.47 MHz ( 13 C), and 121.49 MHz ( 31 P). Chemical shifts (δ) are given in ppm relative to TMS and coupling constants, 2 J PP , in Hz.…”

“…Many papers deal with reactions of hexachlorocyclotriphosphazatriene with monofunctional reagents [1][2][3][4][5]. Especially, aryloxy-substituted phosphazenes are widely studied [6][7][8][9][10][11][12], but the reactions of phosphazenes with difunctional reagents are limited [13][14][15][16][17][18].…”

gem-2,2-Diamino-4,4,6,6-tetraphenoxy-1,3,5-cyclotriaza-λ5-phosphorine

“…For general background, see: Otsuka Chemical Company (1985); Allcock & Taylor (2000); Kanebo (1991); Allcock (2003). For related structures, see: Fincham et al (1985Fincham et al ( , 1988Fincham et al ( , 1986; Golinski & Jacobs (1994); Jacobs & Kirchgä ssner (1990); Marsh & Trotter (1971).…”