Thiophosphinic acid

The secondary phosphine oxides oi sulfides can be oxidized to phosphinic acids oi thiophosphinic acids. 

Mixed chalcogen derivatives of phosphinic and phosphoric acids are also known, the most studied being the mixed sulfur-oxygen species. Thiophos-phoric acids exist in two different isomeric forms - the thiono form (18a) and the thiolo form (18b). The equilibria usually sits somewhere in between these two species, being dependent upon the nature of the R substituents, the solvent and in some cases the concentration. Thiophosphinic acids are also able to interconvert between the thiono (19a) and thiolo (19b) tautomers, although the equilibrium position usually sits well on the side of the thiono tautomer.1... 

Sulfur-donor Extractants The CYANEX 301 Process. Various dialkyl-(mono/di)-thio(phosphoric/phosphinic) acids, such as di(2-ethylhexyl)-di-thiophosphoric acid (HDEHDTP), bis(2,4,4-trimethylpentyl)-thiophosphinic acid (CYANEX 272), bis(2,4,4-trimethylpentyl)-monothiophosphinic acid (CYANEX... 

Menoyo, B., Elizalde, M.R, Almela, A. 2002. Determination of the degradation compounds formed by the oxidation of thiophosphinic acids and phosphine sulfides with nitric acid. Anal. Sci. 18 799-804. 

The thiophosphinic acid derivative, (RO)jP(S)Me, reacts with phosgene in a similar way to the analogous phosphoryi compound see Equation (10.41), except that COS is eliminated in place of COj, Equation (10.46) [317] ... 

Enantiomers of t-butylphenyl-phosphinic and -thiophosphinic acids have been separated, and the absolute configuration of the (—)-menthyl ester of the former acid has been determined. ... 

The tautomeric equilibrium between secondary phosphane sulphides HR2P=S and thiophosphinic acids R2PSH lies completely on the side of the former at room temperature, and P—H bond cleavage does not occur until over 180°C. ° The proton-transfer reaction can, however, be brought about much more readily by co-ordination to transition metals, which initially takes place via the sulphur atom. On raising the temperature, quantitative conversion into the phosphorus-bonded form occurs. 

A) Dialkyl thiophosphinic acid Ai,R = C5Hu A2, R = C6Hii Thione type 4.14 Thiol type 2.90 Cassiterite 8.37 Malachite 7.58 Smithsonite 10.06 Calcite 16.11 Chalcopyrite 5.83 Sphaloite 7.26... 

Reaction of phosphorus(v) sulfide with aromatic hydrocarbons in the presence of aluminum chloride affords a simple method of preparing aromatic di-thiophosphinic acids 173 or the P4S10 can be replaced by the dithiophosphonic anhydride (9).172... 

One of the procedures most widely used for the preparation of thiophosphonic and thiophosphinic acid derivatives is that of chalcogen exchange and, in particular, the replacement of the phosphoryl oxygen by sulphur, a step which is conveniently brought about by the action of hot P4S10, with the liberation of P4O10. A common application has been the conversion of phosphonic dichlorides into phosphonothioic dichlorides (equation and the similar conversion of phosphinic chlorides into phosphinothioic... 

The alkylation, with the more reactive of alkyl halides, of the sodium salts of monoes-terified phosphonothioic acids (equation 22) (see also Scheme 11) or of the disodium salts 107 results in preferential S-alkylation, and the same situation obtains for the salts of phosphinothioic acid " methylation can also be carried out with dimethyl sulphate. Alkylations may also be performed under phase-transfer conditions. From both practical and theoretical perspectives, the subject is more complex, since the course of alkylation reactions depends on the nature of the alkylating agent, on the polarity of solvent and whether this is protic or non-protic and on the concentrations of reactants a study of these features has been the subject of two reports In non-polar or weakly polar aprotic media, or in EtOH, alkylation occurs almost exclusively on sulphur, but in dipolar aprotic solvents, O-alkylation also takes place. The relative yields of sulphur- and oxygen-substituted derivatives, [Qs/Qol depends, for a given solvent, on the nature of substituents on phosphorus, i.e. essentially, whether the substrate is a thiophosphoric, thiophosphonic or thiophosphinic acid. With alkyl tosylates as alkylating agents at 0.02 m in hmpt, the alkylation of sodium 0,0-dialkyl or diphenyl phosphorothioates results in 100% overall conversions with [Qs/Qo] 5 the overall yields for sodium diphenyl- or diisopropyl-phosphinothioates are lower (50-100%) with [Qs/Qo] 1 ... 

Only a few complexes of monothiophosphinic acids, R2P(S)OH, are known. Diphenyl-thiophosphinic acid, Ph2P(S)OH, forms polymeric complexes wiA Ni" and Al but the Cy" complex is monomeric. The Ni" complex is paramagnetic (/x, 3.86 BM) with a typically tetrahedral spectrum." Complexes of diethyldithiophosphinic add, Et2P(S)OH, with Co", Zn", In" and Pb" have been reported their degree of association in organic solvents, involving ligand brid ng, is concentration dependent. "... 

Diisooctyl sodium sulfosuccinate. See Sodium diisooctyl sulfosuccinate Diisooctylthiophosphinic acid. See Bis (2,4,4,-trimethylpentyl) thiophosphinic acid N,N-Diisopropanolamide of tallow fatty acids. See Tallow diisopropanolamide Diisopropanolamine... 

Phosphinothioic acid, bis (2,4,4-trimethylpentyl)-. See Bis (2,4,4,-trimethylpentyl) thiophosphinic acid Phosphite 1. See Tetrakis (2,4-di-t-butylphenyl)-4,4 -biphenylenediphosphonite Phosphite 2. See Bis (2,4-di-t-butylphenyl) pentaerythritol diphosphite PhosPho 642. See Hydroxylated lecithin PhosPho E-100, PhosPho F-97. See Lecithin PhosPho H-00, PhosPho H-150. See Hydrogenated lecithin... 

Bis (2,4,4,-trimethylpentyl) thiophosphinic acid extraction agent, cellulose derivs. 

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