Phosphine sulfide, dimethyl

C H402, Acetic acid palladium complex, 26 208 tungsten complex, 26 224 C2H7PS, Phosphine sulfide, dimethyl-manganese complex, 26 162 C H,N2, 1,2-Ethanediamine chromium complex, resolution of, 26 24, 27... 

PRuC.mHjj, Ruthenium(II), [2-(diphenyl-phosphino)phenyl-C P](r) -hexamethyl-benzene)hydrido-, 36 182 PSC2H7, Phosphine sulfide dimethyl- and manganese complex, 26 162... 

SPC2H3, Phosphine sulfide, dimethyl-, and manganese complex, 26 162 SPOaCuH , 2//-1,2-Thiaphosphorin-2-ium, 3,4,5,6-tetrakis(methoxycarbonyl)-2,2-dimethyl-, manganese complex,... 

Phosphine sulfide, dimethyl-, 26 162 manganese complex, 26 162 Phosphinothioyl cyclo-cotrimerization, 26 161... 

A mixture of diphenyl-3-(2-morpholino-l-cyclohexenyl)phosphine sulfide (3.25 g, 8.5 mmol) and triethylamine (0.91 g, 9 mmol) in benzene (20 ml) was added to a solution of phosphorus tribromide (2.30 g, 8.5 mmol) in benzene (20 ml). After 2 h, a mixture of methanol (0.55 g, 17 mmol) and triethylamine (1.82 g, 18 mmol) in benzene (20 ml) was added with stirring to the solidified mass. After 1 h, the mixture was filtered, the filtrate was evaporated, and the residue was ground with petroleum ether. There was thus isolated pure dimethyl 3-dip henylthiophosphoryl-2-morpholino-l-cyclohexenylphospho-nous acid of melting point (mp) 193-196°C (3.14 g, 78%). 

Dimethyl sulfoxide (DMSO), (CH3)2SO, is a versatile reagent for the oxidation of alcohols to carbonyl compounds under gentle conditions. In addition to the previously mentioned dehydrogenations, it is capable of other oxidations acetylenes to a-diketones [997], alkyl halides to aldehydes 998, 999], tosyl esters to aldehydes [1000], methylene groups adjacent to carbonyl groups to carbonyls [1001, 1002], a-halocarbonyl compounds to u-dicarbonyl compounds [1003,1004,1005], aldehydes to acids [1006], and phosphine sulfides and selenides to phosphine oxides [1007]. 

Phosphorus nuclear magnetic shielding anisotropy in (1-hydroxyalkyl)dimethyl-phosphine sulfides has been studied using the IGLO method, and the tautomeric stability, molecular structure, and internal rotation of methylphosphonic dicyanide MeP(0)(CN)2, dicyanomethoxyphosphine MeOP(CN)2, and their isocyano analogues have been extensively followed using ab initio calculations. ... 

An interesting approach to develop an asymmetric allylic alkylation catalyst by using a peptide-based phosphine hgand was examined by Gilbertson (Scheme 3.70) [135]. Phosphine-sulfide amino acid 211 was incorporated into a peptide sequence on a polymer support After reduchon of the phosphine sulfide to phosphine, the polymer-supported pephde sequence having phosphine-(support-Gly-Pps-D-Ala-Pro-Pps-D-Ala-Ac) was prepared. The complex of the peptide with Pd was uhhzed for the asymmetric addition of dimethyl malonate 202 to 3-acetoxycy-clopentene 212 to give 213 in 59% yield and 66% ee. 

Dimethyl(phenyl)phosphine sulfide 418 Dimethylthiophosphinic bromide (16.4 g, 95 mmoles) in ether (75 ml) is added during 15 min, with stirring at 0-10°, to a solution of phenylmagnesium bromide (0.1 mole) in ether (110 ml). The mixture is set aside overnight and then poured into a mixture of ice and 10 % sulfuric acid. The aqueous layer is washed with ether, and the ethereal washings and the original ether layer are washed with water, dried over sodium sulfate, and evaporated. The residual oil crystallizes when cooled and rubbed, and on recrystallization from hexane-benzene gives the sulfide as colorless needles (14.2 g, 88 %), m.p. 47-47.7°. 

Nitrenes for the most part being electron deficient are highly electrophilic intermediates and therefore react with nucleophiles of all types. Tertiary amines, phosphines, sulfides, and sulfoxides all react with nitrenes to give ylides, in a reaction that is the reverse of their formation. In practice, dimethyl sulfoxide (DMSO) is often the most convenient nucleophilic trap since it can be used as the reaction solvent, and gives relatively stable sulfoximides (Scheme 6.40). Azo compounds, which are formally nitrene dimers, are common by-products in many nitrene reactions. However, the dimerization of two highly reactive species in solution is extremely unlikely on statistical grounds, and therefore the mechanism of azo compound formation probably involves the reaction of a nitrene, as an electrophile, with its precursor. 

Dimethyl-l-butyn-l-ylphosphine sulfide added in one portion to 3-7-fold excess ethereal ethylmagnesium bromide, then at least 1 equivalent cuprous chloride added, refluxed 4-6 hrs., and treated with NH4Cl-soln. and water -> dimethyl-l-(2-ethylbutenyl)phosphine sulfide. Y 87%. F. e. s. A. M. Aguiar and J. R. Smiley Irelan, J. Org. Chem. 34, 4030 (1969). 

Scheme 5.43 Enantioselective deprotonation-electrophilic quenching of dimethyl-phosphine sulfides.

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