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

Abstract

Abstract Some new phosphoramidates were synthesized and characterized by 1 H, 13 C, 31 P NMR, IR spectroscopy and elemental analysis. The structures of CF 3 C(O)N(H)P(O)[N(CH 3 )(CH 2 C 6 H 5 )] 2 ( 1 ) and 4‐NO 2 ‐C 6 H 4 N(H)P(O)[4‐CH 3 ‐NC 5 H 9 ] 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. 13 C NMR spectra were used for study of 2 J(P,C) and 3 J(P,C) coupling constants that were showed in the molecules containing N(C 2 H 5 ) 2 and N(C 2 H 5 )(CH 2 C 6 H 5 ) moieties, 2 J(P,C)> 3 J(P,C). A contrast result was obtained for the compounds involving a five‐membered ring aliphatic amine group, NC 4 H 8 . 2 J(P,C) for N(C 2 H 5 ) 2 moiety and in NC 4 H 8 are nearly the same, but 3 J(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(CH 2 R)(CH 2 C 6 H 5 )] 2 , 2 J(P,CH 2 ) benzylic > 2 J(P,CH 2 ) aliphatic , in an agreement with our previous study.