Thiophosphoryl compounds

Most of the phosphoryl and thiophosphoryl compounds are colourless gases or volatile liquids though PSBt3 forms yellow crystals, mp 37.8°, POI3 is dark violet, mp 53°, and PSI3 is red-brown, mp 48°. All are monomeric tetrahedral (C y) or pseudotetrahedral. Some physical properties are in Table 12.4. The P-O interatomic... 

In addition to the monophosphorus phosphoryl and thiophosphoryl compounds discussed above, several poly-phosphoryl and -thiophosphoryl halides have been characterized. Pyrophos-phoryl fluoride, 0=PP2—O—P(=0)p2 (mp —0.1°, bp 72° extrap) and the white crystalline cyclic tetramer [0=P(F)—0)4 were... 

Kudzin ZH, Kotynski A, Kielbasinski P. 1991. Application of the iodine-azide reagent for selective detection of thiophosphoryl compounds in thin-layer chromatography. J Chromatogr 588 307-313. 

S NMR spectra of thiocarbonyl, thiophosphoryl compounds, and of some sulphonium salts have also been published. Machiguchi et al. have reported the 33S NMR spectrum of tropothione41 2, a thiocarbonyl compound, and of its corresponding S-oxide, 3 and sulphenic acid, 4.42... 

The addition of 18-crown-6 to a mixture of a 4-nitrophenyl phosphoric triester (or of such an ester of a phosphonic acid) with alkoxide NaOR in ROH causes a catalytic deceleration in the solvolysis, whereas for the analogous thiophosphoryl compound a... 

Phosphorus(v) Compounds. X-Ray p.c. spectra for many phosphoryl and thiophosphoryl compounds have been analysed to give a series of substituent constants which accurately reproduce the experimental data/ There is now strong evidence for a monomeric metaphosphate, isoelectronic with sulphur trioxide, from pyrolysis experiments on methyl but-2-enyl phostonate (90)/ The... 

Therefore, the intramolecular S-alkylation is apparently inherent in various types of thiophosphoryl compounds with an co-halogenoalkyl fragment. Thus there is a good reason to believe that the method for the preparation of 2-oxo-l,2-... 

Studies of Equilibria, Reactions, and Solvent Effects.—Lanthanide shift reagents have been found to be effective for phosphines and phosphoryl compounds, but not for thiophosphoryl compounds. - In a comparison of various shift reagents, europium nitrate hexadeuterium oxide (26) was found to give large shifts of 8 for phosphates and phosphonates. A contact contribution to the Sp shifts was established. When there are two possible sites for co-ordination, as in the aminophosphine (27), steric effects play an important role. Co-ordination occurs at nitrogen in (27 R = H) but at phosphorus in (27 R = Me). The n.m.r. parameters... 

The only comprehensive and readily-available surveys of thio- and seleno-phosphonic and -phosphinic acids appear to be those in the compilation by Kosolapoff and Maier which appeared during the 1970s, and those in the Houben-Weyl volumes. Some further information relevant to heterocyclic systems which possess endo- or exo-cyclic phosphorus-sulphur bonds has been surveyed by Mann Gefter has also provided a useful compilation of syntheses and data for unsaturated thiophosphonates and related compounds. As in the preceding chapters concerned with the synthesis of the various classes of phosphonic and phosphinic acids, literature surveys have been presented for individual compounds and the field, as a whole, is surveyed annually". In addition. Hall and Inch reviewed the mechanistic implications of changes in stereochemistry following displacement reactions at phosphorus in cyclic phosphorus(V) esters and amides, and in so doing discussed the reaction s of many such thiophosphoryl compounds. 

DMSO is known to be an oxidant for thiophosphoryl compounds. Oxidation of the acid (90) (and its epimer) with this reagent occurs with about 90% inversion of configuration at phosphorus. Oxidation of OOO-triethyl phos-phorothioate with nitrosonium tetrafluoroborate yields bis(diethoxyphosphinyl) disulphide, whereas electrochemical oxidation at a platinum surface gives unidentified phosphorus-containing products. ... 

In the thiophosphoryl compounds (c), i>(P=S) is almost independent of the particular X group. This is probably because the... 

Mikrfajczyk M, Luczak J, Kielbasinski P, Colonna S (2009) Biocatalytic oxidation of thiophosphoryl compounds a new chemo-enzymatic approach to enantiomeric insecticidal thionophosphates and their oxons. Tetrahedron Asymmetry 20 1948-1951... 

Thiophosphoryl compounds, mercaptoacetic acid, thiourea and its derivatives, thiocyanate, thiosulfate azide, 0.05-0.1 M iodine 0.08-180 [8]... 

Kotynski, A. Ciesielski, W. Kudzin, Z.H. Okruszek, A. Krajewska, D. Lipka, P. Iodine-azide reagent for the detection of biologically oriented thiophosphoryl compounds in thin-layer chromatography systems. J. Chromatogr. A, 1998, 813, 135-143. 

For NR/XNBR blends, incorporation of thiophosphoryl compounds in the recipe has been proposed for reducing the swelling in a mixture of isooctane/ toluene (70/30). That was found after immersing the vulcanizates in the solvent for 48 h at 30 C. Naskar et credited this behaviour to crosslinking at the interface of NR with XNBR. 

Table 5.19 Equilibrium constants Kc (I mol j and diiodine basicity scales pKsi2 SLnd AC° (kj mol j for the complexes of diiodine with thiophosphoryl compounds.

Paetzold, R. and Niendorf, K. (1975) Molecular complexes. VI. Relations between the complex stability and the blue shift of iodine band in molecular complexes between phosphoryl and thiophosphoryl compounds and iodine. Z Phys. Chem., 256, 361-368. 

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