2J(P,C) and 3J(P,C) Coupling Constants in Some New Phosphoramidates. Crystal Structures of CF3C(O)N(H)P(O)[N(CH3)(CH2C6H5)]2 and4‐NO2‐C6H4N(H)P(O)[4‐CH3‐NC5H9]2

Some new phosphoramidates were synthesized and characterized by 1H, 13C, 31P NMR, IR spectroscopy and elemental analysis. The structures of CF3C(O)N(H)P(O)[N(CH3)(CH2C6H5)]2 (1) and 4‐NO2‐C6H4N(H)P(O)[4‐CH3‐NC5H9]2 (6) were confirmed by X‐ray single crystal determination. Compound 1 forms a centrosymmetric dimer and compound 6 forms a polymeric zigzag chain, both via ‐N‐H…O=P‐ intermolecular hydrogen bonds. Also, weak C‐H…F and C‐H…O hydrogen bonds were observed in compounds 1 and 6, respectively. 13C NMR spectra were used for study of 2J(P,C) and 3J(P,C) coupling constants that were showed in the molecules containing N(C2H5)2 and N(C2H5)(CH2C6H5) moieties, 2J(P,C)>3J(P,C). A contrast result was obtained for the compounds involving a five‐membered ring aliphatic amine group, NC4H8. 2J(P,C) for N(C2H5)2 moiety and in NC4H8 are nearly the same, but 3J(P, C) values are larger than those in molecules with a pyrrolidinyl ring. This comparison was done for compounds with six and seven‐membered ring amine groups. In compounds with formula XP(O)[N(CH2R)(CH2C6H5)]2, 2J(P,CH2)benzylic>2J(P,CH2)aliphatic, in an agreement with our previous study.