Synthesis and Spectroscopic Study of Some New Phosphoramidates, Crystal Structures of N‐Benzoyl‐N′,N″‐bis(azetidinyl)phosphoric Triamide and N‐Benzoyl‐N′,N″‐bis(hexamethylenyl)phosphoric Triamide

Abstract

Some new N-carbonyl, phosphoramidates with formula C 6

Syntheses, spectroscopic study and crystal structures of some new N-benzoylphosphoric triamides

“…In compounds 4 and 5, the angles OPN amide (N amide is the nitrogen atom of P(O)N(H)C(O) moiety) are lower than the angles OPN amine (N amine is the nitrogen atom of P(O)NR moiety). This was also observed in our previously reported compounds [28,29,31]. The P=O bond lengths in molecules 4 and 5 are 1.4818(11) and 1.4842 (12) Å that are larger than the normal P=O bond length (1.45 Å) [30].…”

“…2 J(PNH) amine coupling constant for amine protons in compound 1 is 9.1 Hz in d 6 -DMSO and 13.2 Hz in CDCl 3 . This X = NH-CH(CH 3 ) 2 (1), NH-CH 2 -CH(CH 3 ) 2 (2), constant in both similar compounds 2 (containing isobutyl groups) and 3 (containing 2,2-dimethoxy-ethyl groups) is 16.1 Hz that is higher than those observed for acyclic phosphoramidates [14,27,28]. 3 J(PNCH) coupling constant in molecule 4 is 16.3 Hz, which is higher than the observed values for our previously reported acyclic phosphoramidates [27][28][29].…”

“…Considering weak C-H · · · O hydrogen bonds leads to three-dimensional polymeric clusters in the crystalline network of these molecules. The earlier studied N-benzoyl-and N-4-fluorobenzoylphosphoric triamides exist either in the form of dimmeric aggregates [15,19,29] or as polymeric chains [28,31].…”

“…Compound C 6 H 5 C(O)NHP(O)[NH-C(CH 3 ) 3 ] 2 showed two conformers in solution NMR spectra and solid state [14]. Moreover, compounds C 6 H 5 C(O)NHP(O)X 2 , X = NC 3 H 6 [15], NC 4 H 8 [16] 4-CH 3 -C 6 H 4 OP(O)(NH-CH (CH 3 )(CH 2 C 6 H 5 ) [17] and C 6 H 5 C(O)NHP(O)(NC 5 H 10 ) 2 [18] 4-F-C 6 H 4 C(O)NH P(O)(NC 5 H 10 ) 2 [19] exhibited two and four conformers, respectively, only in their crystalline states. The synthesis and structure of compound {(1R, 2S)-N-i Pr-ephedrine}P(S)NH[(Si(CH 3 ) 3 ], which is an oxazaphosphole molecule with three independent molecules in the crystalline lattice, was reported [20].…”

Puckering behavior in six new phosphoric triamides containing aliphatic six- and seven-membered ring groups and a database survey of analogous ring-containing structures

“…There are no three-membered carbon rings in the CSD. The ring in cyclobutane looks like a squared creased and bent along its diagonal, 40 similar to what is observed for the only structure with a "C3N" skeleton in the CSD (refcode LAYMII), 41 where the parameters of Q and torsion angle have been 42 show that the differences in the dihedral angles of fourmembered rings (within 0 to above 30 ), resulting from differing ring systems fused to the cyclobutane, are relatively independent of how the molecule packs in the crystal. Cyclopentane is non-planar and the two minimum energy geometries are the envelope and the half-chair conformations.…”