THE STRUCTURES AND MODE OF FORMATION OF SOME CYCLODIPHOSPH(V)AZANES AND THEIRCIS-TRANSISOMERISATION

Abstract

Methods of preparation and likely reaction mechanisms of the formation of [PhP(S)NR], fromPhP( S)CI and NH, R are discussed. These cyclodiphosph(V)azanes were investigated by means of N.M.R. spectroscopy and X-ray crystallography. The initial reaction products appear to be the trum-isomers. Cis-rmns isomerisation is discussed.

Lithiation of Tris(alkyl- and arylamido)orthophosphates EP[N(H)R]3 (E = O, S, Se): Imido Substituent Effects and PE Bond Cleavage

“…In 1903, Michaelis reported tris(ethylamido)thiophosphate, SP[N(H)R] 3 (R = Et) . Since then, numerous derivatives have been described with R = Me; n Pr; n Bu; i Bu; sec Bu; Bz; cyclo -pentyl; cyclo -hexyl; o -, m -tolyl; o -, m -, p -C 6 H 3 OMe; Ph; 2,4-C 6 H 3 F 2 ; 2,4-C 6 H 3 Cl 2 ; and 2,4-C 6 H 3 Me 2 . The i Pr ( 2a ), t Bu ( 2b ), and p -tol ( 2c ) 13 derivatives have also been previously synthesized, but only the 31 P NMR shifts were reported.…”

“…Preparation of SP[N(H) p -tol] 3 (2c). The following is a modified literature procedure . Thiophosphoryl chloride (10.00 mL, 16.67 g, 0.09847 mol) was added dropwise to an excess of para -toluidine (80.00 g, 0.7465 mol) in toluene (250 mL) at 0 °C.…”

“…28 Since then, numerous derivatives have been described with R ) Me; 20 n Pr; 20 n Bu; 28 i Bu; 20 sec Bu; 11 Bz; 29 cyclo-pentyl; 11 cyclo-hexyl; 29 o-, m-tolyl; 13 o-, m-, p-C 6 H 3 OMe; 12 Ph; 29 2,4-C 6 H 3 F 2 ; 30 2,4-C 6 H 3 Cl 2 ; 30 and 2,4-C 6 H 3 Me 2 . 30 The i Pr (2a), 11 t Bu (2b), 12 and p-tol (2c) 13 derivatives have also been previously synthesized, but only the 31 P NMR shifts were reported. The full characterization of 2a-c is now presented.…”

“…13 Thiophosphoryl chloride (10.00 mL, 16.67 g, 0.09847 mol) was added dropwise to an excess of para-toluidine (80.00 g, 0.7465 mol) in toluene (250 mL) at 0°C. A brown slurry formed, and the mixture was slowly warmed to 23°C and stirred for 2 h. Solvent was removed in vacuo, and dilute HCl (100 mL) was added to the brown solid to dissolve para-tolylammonium chloride.…”