Triphenylphosphine sulfide

The use of other phosphorus-sulfur reagents for heterocyclic synthesis appears rare. It would be interesting to investigate in more detail the reaction of compounds, such as the phosphine sulfides, with organic substrates. Triphenylphosphine sulfide is an effective sulfur transfer agent, as it converts oxiranes into thiiranes in good yield. The reaction proceeds with retention of configuration.128... 

The hexafluorothioacetone is isolated as its dimer, 2,2,4,4-tetrakis(trifluoro-methyl)-f,3-dithietane, which forms immediately. In the case of the tri- and tetrasulfides, excess triphenylphosphine is used to remove the extra sulfur atoms by formation of triphenylphosphine sulfide. 

Complexes with Thiourea, Triphenylphosphine Sulfide and Related Ligands... 

When two equivalents of PPh3 were added to the cationic T7z-S = CH2 complex 51a, the yhde complex 52 together with triphenylphosphine sulfide was formed. The reaction very likely proceeds via the carbene complex intermediate [Re( CH2)(NO)(PMe3)(if-C-dL) j+ (5 ) which is rapidly trapped by PPh3. The trapping reaction is significantly faster than the for-... 

Reaction between 5-alkoxythiatriazole and triphenylphosphine, which is a weaker nucleophile, proceeds more sluggishly.18 At 25° triphenylphosphine reacted exothermically with 5-(4-chlorophenyl)thiatriazole in ether the products were those of total fragmentation, i.e., 4-chloro-phenyl cyanate and triphenylphosphine sulfide, in addition to nitrogen. Since thiatriazaphosphorines normally are stable at room temperature... 

Triphenylphosphine and phosphonium ylides are known as convenient reagents to extrude sulfur with formation of triphenylphosphine sulfide. Imino 1,2,3-dithiazoles 56 reacted with Ph3P in moist dichloromethane to give yV-arylcyanothioformamidines 71 (Scheme 6) <1996BML529>. These compounds can be obtained also from imines... 

Our result perfectly agrees with those presented by Malkin and Rabino-witz (33), and Keresztes-Nagy and Margoliash (23). (2) Triphenylphos-phine, known as a specific reagent for persulfide bond (22, 42), can bleach the visible color of adrenodoxin as shown in Fig. 11. (3) When adrenodoxin is treated with tritium-labelled triphenylphosphine, the product thereof, radioactive triphenylphosphine sulfide, can be isolated. The results from collaboration with Tsurugi s group show that 1 mole of adrenodoxin (equivalent to 2 moles of labile sulfur) reacts quantitatively with 2 moles of triphenylphosphine to produce 2 moles of triphenylphosphine sulfide. 

Several phosphorous compounds having a P=S bond are also catalysts for this reaction. For example, heating of phenyl isocyanate with triphenylphosphine sulfide at 160 °C affords diphenylcarbodiimide. Since triphenylphosphine sulfide was recovered unchanged, a different mechanism seems to be operative. A tricyclic P S compound, S=P[N(Me)CH2CH2l3N, also catalyzes the transformation of isocyanates to carbodiimides. Triphenylarsine oxide and triphenylantimony oxide also catalyze the conversion of isocyanates into carbodiimides. The catalytic activity of the oxides of phosphorous, arsenic and antimony are in agreement with the dipole moments of... 

Addition of the hgand can occur at both metals, as shown in equations (80) and (81). Interestingly, addition of triphenylphosphine sulfide does not proceed to yield products on both metals but an unsymmetrical product is formed (equation 82). 

Two complexes are known definitely to be monomeric—the triphenylphosphine sulfide complexes, CuX(Ph3PS) (X = Cl, Br). They were prepared by reacting the ligand with copper(I) halide in chloroform, and molecular weight determinations in this solvent show them to be monomeric (93). 

Both protactinium pentachloride and pentabromide react with triphenylphosphine sulfide and selenide to form stable 1 1 complexes... 

The reactions of [Ml2(CO)3(NCMe)2] with thiourea, A,A,A, /V -tetra-methylthiourea, and thioacetamide to give a number of seven-coordinate complexes have been described. A large series of 42 triphenylphos-phine oxide and triphenylphosphine sulfide complexes derived from [Ml2(CO)3(NCMe)2] have been prepared as shown in Scheme 5. Also, a series of tricyclohexylphosphinecarbondisulfide seven-coordinate complexes derived from the reactions of [MT(CO)3(NCMe)2], [MI,(CO)3(NC Me)L] L = PPhj, AsPhj, SbPhj, PCOPh),, and [Wl2(CO)3(PPh3)2] with PCy3CS2 have been reported. 

Oxazabicyclohexanes (e.g., 106) can be deoxygenated readily under mild conditions to afford the corresponding pyrrolines (e.g., 107). Deoxygenation reagents include thiourea, triphenylphosphine sulfide, potassium thiocyanate, potassium ethylxanthate, and potassium selenocyanate. The 6-tliia-l-azabicyclo[3.1.0]hexanes 135 liave been suggested as possible intermediates in some of these reactions. 

The electrooxidation of triphenylphosphine sulfide and 0,0,0-triethylphosphorotio-ate at a Pt electrode in anhydrous MeCN/Bu4NCl04 [226] gives a dimeric dication [Eq. (107)], similar to the result for thiocarbonyl compounds [219]. 

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