Phosphine sulfides, trialkyl

Examples of the intermolecular C-P bond formation by means of radical phosphonation and phosphination have been achieved by reaction of aryl halides with trialkyl phosphites and chlorodiphenylphosphine, respectively, in the presence of (TMSlsSiH under standard radical conditions. The phosphonation reaction (Reaction 71) worked well either under UV irradiation at room temperature or in refluxing toluene. The radical phosphina-tion (Reaction 72) required pyridine in boiling benzene for 20 h. Phosphinated products were handled as phosphine sulfides. Scheme 15 shows the reaction mechanism for the phosphination procedure that involves in situ formation of tetraphenylbiphosphine. This approach has also been extended to the phosphination of alkyl halides and sequential radical cyclization/phosphination reaction. ... 

By phosphites and phosphines. Triethyl phosphite76 and triethyl-,18 tributyl-,38 and triphenylphosphines1 18 have been reacted with a number of episulfides to yield practically quantitative amounts of triethyl thionophosphate and trialkyl- or triiirvl phosphine sulfides, respectively, and the olefin resulting from desulfurization of the episulfide (Eqe. 54 and 55). 

Ignition or explosive reaction with metals (e.g., aluminum, antimony powder, bismuth powder, brass, calcium powder, copper, germanium, iron, manganese, potassium, tin, vanadium powder). Reaction with some metals requires moist CI2 or heat. Ignites with diethyl zinc (on contact), polyisobutylene (at 130°), metal acetylides, metal carbides, metal hydrides (e.g., potassium hydride, sodium hydride, copper hydride), metal phosphides (e.g., copper(II) phosphide), methane + oxygen, hydrazine, hydroxylamine, calcium nitride, nonmetals (e.g., boron, active carbon, silicon, phosphoms), nonmetal hydrides (e.g., arsine, phosphine, silane), steel (above 200° or as low as 50° when impurities are present), sulfides (e.g., arsenic disulfide, boron trisulfide, mercuric sulfide), trialkyl boranes. 

Besides the thiocyanates, just mentioned, other 5-donor complexes which are of interest are the dialkyl sulfides, [MCl3(SR2)3], produced by the action of SR2 on ethanolic RhCl3 or on [IrClg] ". Phosphorus and arsenic compounds are obtained in similar fashion, and the best known are the yellow to orange complexes, [ML3X3], (M = Rh, Ir X = Cl, Br, I L = trialkyl or triaryl phosphine or arsine). These compounds may exist as either mer or fac isomers, and these are normally distinguished by their proton nmr spectra (a distinction previously made by the measurement of dipole moments). An especially... 

A further important application of P(III) reagents is deoxygenation of 5-oxides. Sulfoxides can be deoxygenated to the corresponding sulfides using triphenyl-phosphine in the presence of a Lewis acid catalyst or, more readily, by using a trialkylphosphine or trialkyl phosphite. One of the most effective reagents, however, is the P-chloro benzodioxaphosphole 5, whose use is illustrated in Protocol 2. 

The quaternary phosphonium iodide, R P+I", can be isolated after treatment of the reaction product with aqueous hydrogen sulfide. Thus, white phosphorus heated with excess ethyl iodide at 180° for 22 hr. gave a product from which tetraethylphosphonium iodide was obtained in 49% yield (4). The remainder of the phosphorus was said to be converted to triethylphosphine oxide, although this product was not isolated. When the reaction product is refluxed with ethanol and then distilled over potassium hydroxide, the major product is the trialkyl phosphine oxide (3). Both trialkyldiiodophosphoranes and quaternary phosphonium iodides would be converted to the tertiary phosphine oxide under these conditions. Table III summarizes the... 

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