Syntheses and structures of four new mixed-amide phosphoric triamides

Abstract

Phosphoric triamides have extensive applications in biochemistry and are also used as O-donor ligands. Four new mixed-amide phosphoric triamide structures, namely rac-N-tert-butyl-N',N''-dicyclohexyl-N''-methylphosphoric triamide, C17H36N3OP, (I), rac-N,N'-dicyclohexyl-N'-methyl-N''-(p-tolyl)phosphoric triamide, C20H34N3OP, (II), N,N',N''-tricyclohexyl-N''-methylphosphoric triamide, C19H38N3OP, (III), and 2-[cyclohexyl(methyl)amino]-5,5-dimethyl-1,3,2λ(5)-diazaphosphinan-2-one, C12H26N3OP, (IV), have been synthesized and studied by X-ray diffraction and spectroscopic methods. Structures (I) and (II) are the first diffraction studies of acyclic racemic mixed-amide phosphoric triamides. The P-N bonds resulting from the different substituent -N(CH3)(C6H11), (C6H11)NH-, 4-CH3-C6H4NH-, (tert-C4H9)NH- and -NHCH2C(CH3)2CH2NH- groups are compared, along with the different molecular volumes and electron-donor strengths. In all four structures, the molecules form extended chains through N-H...O hydrogen bonds.

Association of Non‐covalent Interactions C−H…X(X=O, F, Cl, π) and Cl…π with Hydrogen Bond Interactions N−H…O in Molecular Assembly of New Phosphoramides: A Combined X‐Ray Crystallography and Topology (AIM and Hirshfeld) Analysis

“…In all structures, the P atom exhibits a distorted tetrahedral environment and the P═O bond lengths are standard for the phosphoramides [14,16] which is reflected in the surrounding bond lengths and angles at the P atom (Tables S1 and S2).…”

“…In the C(O)NHP(O) segment, the P−N bond is significantly longer than two other P−N bonds and the C−N−C angles are significantly smaller than two related P−N−C angles (Table S1, [17]). In the co‐crystal 6 , the P=O and P−N bond lengths and O−P−N and C−N−P angles in phosphoric triamide molecule are comparable to those in analogous compounds (Table S1) …”

“…In the co-crystal 6, the P═O and PÀ N bond lengths and OÀ PÀ N and CÀ NÀ P angles in phosphoric triamide molecule are comparable to those in analogous compounds (Table S1). [16] Figure 1. ORTEP-style plot and atom-labeling scheme for the structures 1 (left) and 2 (right).…”

“…Development of new applications of these compounds is certainly needed to more focus on the analysis of intermolecular interactions in the crystal structures and their molecular assemblies. More explored interactions in phosphoramides are those involving the functional groups such as P═O and NÀ H, i. e. the NÀ H…O hydrogen bond interactions, [12][13][14][15][16] while there are less studies on other intermolecular interactions, for example those involving π-systems or halogen atoms, in these compounds. [17] Herein, we further analyse the intermolecular interactions in phosphoramides focusing on weak interactions.…”

Decorated single-enantiomer phosphoramide-based silica/magnetic nanocomposites for direct enantioseparation

“…It should be noted that the removing of triethylammonium chloride salt (or other organic salt depending on HCl scavenger used) can be done by H 2 O for the phosphoramides non-sensitive to moisture. 68,73 For the water-sensitive compounds, a solvent with different solubilities of phosphoramide and organic salt is used. For examples, the syntheses of moisture-sensitive phosphoramides rac-XP(]O)(OC 6 H 5 )(Cl) [X ¼ (NHC 6 H 4 -p-CH 3 ) and (NH-cyclo-C 6 H 11 )] were reported 68 in dry chloroform, with low solubilities of p-toluidine hydrochloride and cyclohexylamine hydrochloride salts and high solubilities of phosphoramides.…”