Diphenylmethylphosphine

Two papers have appeared on the reactions of halogenophosphines with tervalent phosphorus compounds. In a detailed study of the reactions at 20 °C of a range of tertiary phosphines with phosphorus trichloride, dichlorophenylphosphine, and chlorodiphenylphosphine, it has been shown that, in general, 1 1 adducts are formed, provided that the tertiary phosphine is a good nucleophile. With diphenylchlorophosphine, for example, an adduct (18) is formed with dimethylphenylphosphine, but not with diphenylmethylphosphine, although the relative importance of steric and electronic factors remains to be established. The related reactions of phosphorus trichloride and of dichlorophenylphosphine are much more complex, and the initial crystalline products are not amenable to analysis. The reactions at 280 °C of a similar system have been shown to lead to halogen exchange, e.g. the conversion of (19) to (20). 

P-oxidation. In an analogous manner to nitrogen and sulfur, phosphorus may also be oxidized to an oxide, as in the compound diphenylmethylphosphine. This is catalyzed by microsomal monooxygenases, both cytochromes P-450 and the FAD-requiring enzyme. 

Reactions of phosphines and phosphites have received some attention but their preparative value is limited. The zwitterion formed from diphenylmethylphosphine and benzyne rearranges to ylide (124) which can be captured by Wittig alkenation, with cyclohexanone, in about 20% yield.159 Some synthetically useful reactions of tellurium and selenium compounds with arynes have been reported. For example, heating diphenyl iodonium carboxylate and bis(p-ethoxyphenyl) ditelluride in dichlorobenzene affords the compound (125).160 The corresponding reactions with diphenyl selenide and diphenyl sulfide... 

P-Oxidation. P-oxidation, a little known reaction, involves the conversion of trisub-stituted phosphines to phosphine oxides, for example, diphenylmethylphosphine to diphenylmethylphosphine oxide. Although this reaction is described as a typical CYP-dependent monooxygenation, it too is now known to be catalyzed by the FMO also. 

Wan, I. Y. and McGrath, J. E., Synthesis and characterization of diphenylmethylphosphine oxide containing nylon-6,6 copolymers, Abstracts of Papers of the American Chemical Society, 1995, 209(2), 119. 

Table 3 Reaction of Diphenylmethylphosphine Adduct Sb with Aldehydes...

The addition of Grignard reagents to a-(diphenylphosphino)carbonyl compounds leads to alcoholates, which react with methyl iodide exclusively at phosphorus to yield betaines. Diphenylmethylphosphine is eliminated upon addition of strong base to yield isomerically pure alkenes (Scheme 8). ... 

Although metalation of aliphatic carbon attached to phosphorus is well documented (85,173), only recently has it been noted that the carbon-phosphorus bond in triphenylphosphine oxide can be cleaved with an equimolar amount of methyllithium at room temperature (185). Indeed, benzene is produced along with a new lithium reagent which, when hydrolyzed, gives diphenylmethylphosphine oxide in high yield (83.5%). 

This compound is a phosphine oxide derivative,with a methyl group replacing a hydrogen and two phenyl groups replacing two hydrogens. Its ncime is diphenylmethylphosphine oxide. 

Brock CP, Colhnan JP et al (1973) Bent vs. linear nitrosyl paradox. Infrared and X-ray photoelectron spectra of dichloronitrosylbis (L)cobalt (II) and crystal structure with L = diphenylmethylphosphine. Inorg Chem 12 1304—1313... 

In addition, during our studies on the MBH reaction of a-keto esters and cyclic enones, we found that the catalysts have a significant effect on the MBH adduct. The MBH reaction of a-keto esters with cyclopent-2-enone catalyzed by diphenylmethylphosphine provided the corresponding MBH adducts 155 in higher yields in the presence of p-nitrophenol, whereas the similar reaction of a-keto esters with cyclopent-2-enone catalyzed by tertiary-amine of DBU furnished the corresponding aldol adducts 156 with n-configuration exclusively (Scheme 1.67). " ... 

C2 7H2 6ClF3P2Pt, trans-Bis(diphenylmethylphosphine)chloro(trifluoro-methyl)platinum(ll), 45B, 880... 

C28H2sCrNOsSn 0.5 CH2CI2, Pentacarbonyl[diethylamino(triphenyl-tin)carbene]chromium(0) dichloromethane solvate, 45B, 882 C2 8 2 6ClF5P2Pt, trans-Bis(diphenylmethylphosphine)chloro(pen-tafluoroethyl)platinum(II), 45B, 880 C28H32W, Bis-(T -cyclopentadienyl)bis-(3,5-dimethylbenzyl)tungsten, 41B, 861... 

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