Triphenylphosphine sulfide, oxidation

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... 

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. 

The stable dithiirane 5-oxide (4) is converted to sulfine (15) and triphenylphosphine sulfide upon treatment with triphenylphosphine (93JA4914). When heated, (4) decomposes to give thioketone (16), sulfine (15), and dicarbonyl compound (17). Compounds (16) and (15) result from loss of sulfur monoxide and sulfur, respectively, from (4). Thioketone (16) exists in equilibrium with oxathietane (18). The rate of thermal decomposition of (4) was found to be dependent on its concentration, with higher rates at higher concentrations. The authors suggest that this observation is indicative of a decomposition pathway involving the sulfur and sulfur monoxide products. Thermolysis of (4) also leads to isomerization of (12) in addition to the products described above. 

Structural and Physical Aspects. - The stability of the various conformers of the phosphines oxides (269)- 211) has received theoretical consideration. A new triclinic polymorph of triphenylphosphine sulfide has been structurally characterised, together with a related triclinic polymorph of triphenylphos-phine. Two reports of the solid state crystal structure of the phenolic phosphine oxide (272) have appeared. A crystallographic study has confirmed that the product of electrochemical oxidation of o-diphenylphosphinoben-zenethiol is the disulfide-bridged bis(phosphine oxide) (273). Solid-state structural studies of the dioxides (274), the (i )-(-I-)-isomer of (275), 1-hexynyl(diphenyl)phosphine oxide,tribenzylphosphine oxide, and tris(t-butyl)phosphine selenide," have also been reported. 

An interesting oxidative addition reaction leading to a pincer-type complex was reported by Matsumura and Inoue et al. [40]. The protocol involves the reaction of a 71-sulfurane (lO-S-3-tetraazapentalene) with Pd(PPh3)4. The hypervalent sulfur is reduced, and at the same time one of the phosphines and Pd(0) are oxidized to triphenylphosphine sulfide and Pd(II), respectively (see Scheme 6). 

A recent advancement consists of the nse of triphenylphosphine sulfide as ligand under conditions of oxidative carbonylation. Thus, styrene could be dicarbonylated to phenyl-succinic dimethyl ester in 80% yield at room temperature and atmospheric pressure. Enantioselection was observed with chiral bisphosphine sulfides. 

Anthrone heated 48 hrs. at 80° with 0,0-diethyl dithiophosphoric acid in benzene 9-anthracenethiol. Y ca. 100%. - Similarly during 100 hrs. Triphenylphos-phine oxide triphenylphosphine sulfide. Y ca. 100%. F. e. s. S. Oae, A. Naka-nishi, and N. Tsujimoto, Chem. Ind. 1972, 575 phosphine sulfides from phosphine oxides with B2S3, retention of configuration at P, s. B. E. Maryanoff, R. Tang, and K. Mislow, Chem. Commun. 1973, 273. 

Triphenylphosphine sulfide refluxed 3 hrs. with dimethyl sulfoxide and 50%-H2SO4 -> triphenylphosphine oxide. Y 93%.-Chiral compds. react with complete inversion of configuration. F. e., also arsine oxides from arsine sulfides, s. R. Ludcenbadh, Synthesis 7975, 307 replacement of P-sulfur and P-selenium by P-oxygen s. M. Mikolajczyk and J. Luczak, Chem. Ind. 7974,701. 

Triphenylphosphine oxide, triphenylphosphine sulfide and triphenylphosphine selenide recrystallized from light petroleum, benzene and ethanol, respectively. 

Likewise, pyridines such as methyl isonicotinate 1999 or quinolines are readily oxidized by BTSP 1949 in the presence of HOReOs in CH2CI2 to give, after 6 h at 24°C, 98% yield of, e.g., methyl isonicotinate N-oxide 2000 [174] (Scheme 12.49). The oxidation of diphenylsulfide with BTSP 1949 and triphenylphosphine dichloride in acetonitrile results, after 60 h at room temperature, in only 12% diphenyl sulfoxide 2001 and 88% recovered diphenyl sulfide [175] (Scheme 12.49), whereas thianthrene 5-oxide 2002 is oxidized by the peroxy-Mo complex 2003 to give 58% of a mixture of 2004 to 2007 in which the trans 5,10-thioxide 2005 predominates [176] (Scheme 12.50). 

Kennedy and Stock reported the first use of Oxone for many common oxidation reactions such as formation of benzoic acid from toluene and of benzaldehyde, of ben-zophenone from diphenyhnethane, of frawi-cyclohexanediol Ifom cyclohexene, of acetone from 2-propanol, of hydroquinone from phenol, of e-caprolactone from cyclohexanone, of pyrocatechol from salicylaldehyde, of p-dinitrosobenzene from p-phenylenediamine, of phenylacetic acid from 2-phenethylamine, of dodecylsulfonic acid from dodecyl mercaptan, of diphenyl sulfone from diphenyl sulfide, of triphenylphosphine oxide from triphenylphosphine, of iodoxy benzene from iodobenzene, of benzyl chloride from toluene using NaCl and Oxone and bromination of 2-octene using KBr and Oxone . Thus, they... 

As cyano-substituted ozonides were easily reduced by triphenylphosphine, also p-tolyl sulfide can be used as a reducing agent and the corresponding sulfoxide could be isolated in quantitative yield. Alternatively, the 3-cyano-3-phenyl-ozonide 103 can oxidize 2,3-dimethyl-2-butene to the corresponding epoxide (Scheme 34). 

Adamantylideneadamantane has been prepared by (1) photolysis of 2-adamantylketene dimer,2 (2) reduction of 4< -chloroadaman-tylideneadamantane with sodium in liquid ammonia,3 (3) rearrangement of spiro[adamantane-2,4 -homoadamantan-5 -ol] with Lewis acids,4,5 (4) reduction of 2,2-dibromoadamantane with magnesium6 or zinc-copper couple,7 and (5) treatment of the azine of 2-ada-mantanone with hydrogen sulfide, followed by oxidation with lead tetraacetate and heating with triphenylphosphine.8... 

Tri-n-butyldifluorophosphorane was first obtained upon interaction between tri-re-butylphosphine and hexafluoro-thioacetone dimer.The method described here involves the reaction of tri-n-butylphosphine sulfide with antimony-(III) fluoride. The method is more generally apphcable in the synthesis of difluorophosphoranes from tertiary phosphine sulfides. The only previously reported difluoro-phosphorane, triphenyldifluorophosphorane, was obtained by the reaction of triphenylphosphine or triphenylphos-phine oxide with sulfur(IV) fluoride under autogenous pressure. ... 

Electrochemical regeneration of triphenylphosphine from triphenylphosphine oxides may be performed by transforming the oxide to the sulfide with P2S5, methylating it into the phosphonium compound, and cleaving it electrochemically [268] ... 

The architecturally novel macrolide (+)-zampanolide was synthesized in the laboratory of A.B. Smith. The C8-C9 ( )-olefin moiety was constructed using the Kocienski-modified Julia oleHnation. The required PT-sulfone was prepared from the corresponding primary alcohol via a two-step protocol employing sequential Mitsunobu reaction and sulfide-sulfone oxidation. The primary alcohol and two equivalents of 1-phenyl-1 H-tetrazolo-5-thiol was dissolved in anhydrous THF at 0 °C and treated sequentially with triphenylphosphine and DEAD. The desired tetrazolo sulfide was isolated in nearly quantitative yield. 

Potassium permanganate. Dimethyl sulfide-Chlorine. Dimethyl sulfoxide. Dimethyl sulfoxide-Chlorine. Dimethylsulf-oxide Sulfur trioxide. Dipyridine chro-mium(VI) oxide. Iodine. Iodine-Potassium iodide. Iodine tris(trifluoroacetate). Iodosobenzene diacetate. Isoamyl nitrite. Lead tetraacetate. Manganese dioxide. Mercuric acetate. Mercuric oxide. Osmium tetroxide—Potassium chlorate. Ozone. Periodic acid. Pertrifluoroacetic acid. Potassium ferrate. Potassium ferricyanide. Potassium nitrosodisulfonate. Ruthenium tetroxide. Selenium dioxide. Silver carbonate. Silver carbonate-Celite. Silver nitrate. Silver oxide. Silver(II) oxide. Sodium hypochlorite. Sulfur trioxide. Thalli-um(III) nitrate. Thallium sulfate. Thalli-um(III) trifluoroacetate. Triphenyl phosphite ozonide. Triphenylphosphine dibromide. Trityl fluoroborate. 

Basically, vanadium is an efficient mediator of 0x0 transfer reactions accompanied by reduction/oxidation processes. Equation (2.19) in Section 2.3, related to the oxidation of thiolate, is a specific example where 0x0 and non-oxo vanadium are involved in a catalytic cycle. More generally, selected vanadium-mediated 0x0 transfer reactions from or to a substrate, and involving the vanadium oxidation states h-II to h-V, can be summarised as depicted in Scheme 4.6,[ 1 where X can be dimethyl sulfide, iodobenzene, triphenylphosphine and other substrates. 

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