5326-10-3Relevant articles and documents
Phosphoramides: Synthesis, spectroscopy, and x-ray crystallography
Gholivand, Khodayar,Shariatinia, Zahra,Oroujzadeh, Nasrin
, p. 404 - 412 (2013/09/23)
A series of new phosphoramides with general formula RP(O)X2, where R = amino/p-methylphenoxy and X = amine, were synthesized and characterized by 1H, 13C, 31P nuclear magnetic resonance (NMR), and infrared (IR) spectroscopy and elemental analysis. The 31P{1H} NMR spectra show that among compounds 7-9 containing 2-, 3-, and 4-aminopyridinyl moieties, respectively, the shielding order of the P atom decreases as 7 > 9 > 8. Also, the structure of compound 7 was determined by X-ray crystallography. In this structure, repeated noncentrosymmetric dimers are formed by two strong intermolecular N(1)-H(1N).N(2) and N(3)-H(3N).O(1) hydrogen bonds. Taking into account weak intermolecular C(17)-H(17C).N(4), C(17)-H(17E).N(4), C(2)-H(2A).O(2), and also weak aromatic C - H.C interactions, a three-dimensional polymeric chain is created in the crystalline network. The density functional theory calculations at B3LYP, B3PW91, and M06 levels using the 6-31+G * basis set were in good agreement with the X-ray crystallography data.
THIONO COMPOUNDS. 9. USE OF SPECTRA TO STUDY INTERMEDIATES IN THE OXIDATION OF THIONO PHOSPHORUS COMPOUNDS
Swinson, Joel,Field Lamar,Heimer, Norman E.,Michalska, Danuta,Muccio, Donald D.,et al.
, p. 159 - 172 (2007/10/02)
Intermediates in the oxidation by m-chloroperoxybenzoic acid (MCPBA) of 13 structurally different thiophosphoramides and phosphorothioates were studied at -25 deg C to 0 deg C using NMR, EPR, UV, IR and Raman spectra.The lifetimes of intermediates ascertained by NMR varied from a few minutes to many hours at the same temperature and were longer for thiono esters than for amides, for aryl than for alkyl constituents, and for electron-donating substituents on aryl groups than for electron-withdrawing groups.The major 31P NMR peaks for all intermediates appeared in the same region, about midway between the resonances of the P(S) starting materials and the P(O) products, indicating close structural similarly to one another for the intermediates; the range of 13-33 ppm for the major peaks indicates that the intermediates are tetracoordinate and supports phosphonium polysulfide structures for them of the type R3PSx (26, Scheme 1), or perhaps R3POSx.UV spectra also afforded support for polysulfide structures, since typical absorption develops and then disappears.Raman, 31P NMR, and UV spectra are consistent with longer-term presence of bisphosphonium species (e.g. 25, from reactions of 26; Scheme 1).EPR spectra gave no indication of homolysis. - Key words: Phosphorothioates, Raman Spectra, Infrared Spectra, Thionophosphorus, NMR Spectra, Thiophosphoramides
