New Phosphoric Triamides: Chlorine Substituents Effects and Polymorphism

作者：Gholivand Khodayar^*; Oroujzadeh Nasrin; Shariatinia Zahra

来源：Heteroatom Chemistry, 2010, 21(3): 168-180.

DOI：10.1002/hc.20592

New phosphoric triamides 1-10 were synthesized by the reaction of N-2,4-dichlorobenzoyl phosphoramidic dichloride with various cyclic aliphatic amines, and the products were characterized by (1)H, (13)C, (31)P NMR, and IR spectroscopy and elemental analysis. Surprisingly, the (1)H NMR spectra of compounds 1-7 demonstrate long-range (4)J (H,H) coupling constant from 1.5 to 1.9 Hz. Comparison of the NMR and IR spectra of N-benzoyl, N-4-chlorobenzoyl, and N-2,4-dichlorobenzoyl phosphoric triamide analogues indicates that N-2,4-dichlorobenzoyl derivatives have the most up field delta((31)P) and the highest nu(C=O) values. The crystal structures of 3, 4, 6, 6a, and 10 have been determined by X-ray crystallography. Interestingly, the structures of 6 and 6a are polymorphic. All structures form dimers through strong, intermolecular -P=O center dot center dot center dot H-N- hydrogen bonds. The dimers connect to each other via weak C-H center dot center dot center dot Cl and C-H center dot center dot center dot OH- bonds to produce two-dimensional polymeric chains for 4 and three-dimensional networks for others. Among new synthesized N-2,4-dichlorobenzoyl phosphoric triamides, one indicated polymorphism. All structures were characterized by (1)H, (13)C, (31)P NMR, and infrared spectroscopy and elemental analysis.

• 出版日期2010