Tris phosphine sulphide

A"-Ray structure determinations (see Chapter 11 for details) have been reported for triphenylphosphine oxide, tri-o-tolylphosphine oxide, sulphide, and selenide, and for cw-2,2,3,4,4-pentamethyl-l-phenylphos-phetan-1-oxide (5). Electron spectroscopic studies of phosphorus oxychloride and thiophosphoryl chloride in the gaseous state, and n.m.r., i.r., and u.v. spectra of phosphine sulphides have appeared. Dipole moments have been used to define the stereochemistry of 2-cyanoethylphosphine oxides, such as (6), which is shown in its preferred conformation. 

Tris(trimethylsilyl)silane reacts with phosphine sulfides and phosphine selen-ides under free radical conditions to give the corresponding phosphines or, after treatment with BH3-THF, the corresponding phosphine-borane complex in good to excellent yields (Reaction 4.45) [82]. Stereochemical studies on P-chiral phosphine sulphides showed that these reductions proceed with retention of configuration. An example is given in Reaction (4.46). 

Tris(aziridinyl)-para -benzoquinone Tris(l-aziridinyl)phosphine-oxide Tris(l-aziridinyl)phosphine-sulphide see Thiotepa)... 

It was shown that dipiperidyl sulphide is converted into tris(dimethyl-amino)phosphine sulphide on standing in HMPA overnight, and that the overall reaction of piperidyl-lithium with elemental sulphur may therefore be written ... 

The reaction of thiobenzophenone with tri-n-butylphosphine at 100 °C gives 1,1,2,2-tetraphenylethane, tetraphenylethylene, and the phosphine sulphide. A similar reaction occurs with dibenzocyclopentadienethione. ... 

Tris (1-aziridinyl) phosphine sulphide N, N, N"-Triethylenethio-phosphoramide Thiotepa USP BP,... 

Tri-biphenylphosphine sulphide, (CgH[5.CgH )3PS, obtained from the interaction of the phosphine and carbon disulphide saturated with sulphur, forms microscopic plates, M.pt. 241° to 242° C., with preliminary softening. 

Tris(aziridinyl)-para-benzoquinone (Triaziquone) Tris(l-aziridinyl)phosphine sulphide (Thiotepa) Uracil mustard... 

Formation.—A convenient and rapid synthesis of thiirans (yields 35— 90%) consists of treatment of epoxides with triphenyl- or tri-n-butyl-phosphine sulphide in the presence of acid. cis-Stilbene oxide gave exclusively cis-stilbene sulphide. (S)-(-)-Methylphenyl-n-propylphosphine sulphide gave, with a twofold excess of cyclohexene oxide, the (S)-(-)-oxide, indicating that this reaction proceeds with retention of configuration at phosphorus. " A mechanism involving two inversions was suggested for the conversion of 2a,3a-epoxycholestane into the 2, 3 3-epithio-isomer, as shown in Scheme 1. Epithiochlorohydrin is obtained by treatment of epichlorohydrin with di-(0-ethyl)dithiophosphoric acid and triethylamine. "... 

Alkyl lithiums Dodecacarbonyltetracobalt Barium sulphide Tri isopropyl phosphine... 

Restricted rotation has been observed in tris-o-tolylphosphine sulphide and selenide (39). The spectrum of the selenide shows two methyl environments in the ratio 2 1 at 30 °C but the methyl signals of the sulphide resolved to this pattern only upon cooling the sample. The corresponding oxide and the parent phosphine showed only one methyl environment down to — 60 °C. Y-Ray diffraction of the selenide showed that the methyl group on one aryl group is directly behind the phosphorus atom in the crystal, as shown in (39). 

Desulphurization of / -keto-sulphides by tris(dimethylamino)phosphine is thought to proceed via a phosphonium salt intermediate, e.g. (52), which can collapse to give a variety of products depending upon the substrate used and the reaction conditions. ... 

Tris(dimethylamino)phosphine desulphurizes / -keto-sulphides (60) to give ketones and enol ethers as major products a mechanism involving initial... 

A detailed study of I iSe and 3lp nuclear spin relaxation in tri(tertbutyI)phosphine selenide has been reported 6 and the kinetics and mechanism of formation of tetracoordinate P(V) sulphides from the reaction of tricoordinate phosphorus compounds with diaryl trisulphides have been investigated.1 ... 

Grignard reagents behave similarly,and a thioborane gives an un-symmetrical sulphide with a sulphenate ester. Tris(diethylamino)-phosphine converts cystine derivatives into corresponding lanthionines [NH2 CH(C02H) CH2]2S, 2 and the disulphide formed between penicillin sulphoxide and Bu SH (36 fine s in place of Me at S) forms the ethyl sulphide (36 Et in place of Me at S) by treatment with triethylphosphine. ... 

Colton et.al. [104,105] reported synthesis and characterization of a number of functionalized (chalcogens) tri- and tetra-tertiary phosphines. Dean and Hughes reported [106] characterization of complexes of Cd(II) with some phosphine oxides, sulphides and... 

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