The electronic effects of substituents on ⁿJ_PX (n = 2, 3; X = H, C) coupling constants and phosphorus chemical shifts; syntheses and spectroscopic investigation of some phosphoramidates

Article type: Research Article

Authors: Gholivand, Khodayar | Shariatinia, Zahra | Tadjarodi, Azadeh

Affiliations: Department of Chemistry, Tarbiat Modarres University, P.O. Box 14115/175, Tehran, Iran

Note: [] Corresponding author. Email: [email protected]

Abstract: New phosphoramidates with the general formulae Me2NP(O)Cl(p-NHC6H4-R) (A) and Me2NP(O)(p-NHC6H4-R)2 (B), where R = H, CH3 and NO2, F, Cl, Br, I, were synthesized and characterized by 1H, 13C, 31P NMR and IR spectroscopy and elemental analysis. The electronic effects of donor, acceptor and neutral groups on nJPX coupling constants (n = 2, 3; X = H, C) and phosphorus chemical shifts are discussed. NMR data show that only the 4-nitroaniline substituent resulted in the disappearance of all coupling (nJPX = 0.0 Hz). Two nearly linear correlations were obtained between para-substituent constants (σp) and phosphorus chemical shifts for the two series A and B.

Keywords: Phosphoramidates, NMR, Phosphorus chemical shifts, para-Substituent constants

DOI: 10.1080/03014460500144609

Journal: Main Group Chemistry, vol. 4, no. 2, pp. 111-119, 2005