Potassium diphenylphosphide

Quinolylphosphines have been prepared from the reaction of 8-chloroquinoline and potassium diphenylphosphide, or the quinolyl-lithium derivative and a chlorophosphine. ... 

In the early 1970 s, Bayer et al. reported the first use of soluble polymers as supports for the homogeneous catalysts. [52] They used non-crosslinked linear polystyrene (Mw ca. 100 000), which was chloromethylated and converted by treatment with potassium diphenylphosphide into soluble polydiphenyl(styrylmethyl)phosphines. Soluble macromolecular metal complexes were prepared by addition of various metal precursors e.g. [Rh(PPh3)Cl] and [RhH(CO)(PPh3)3]. The first complex was used in the hydrogenation reaction of 1-pentene at 22°C and 1 atm. H2. After 24 h (50% conversion in 3 h) the reaction solution was filtered through a polyamide membrane [53] and the catalysts could be retained quantitatively in the membrane filtration cell. [54] The catalyst was recycled 5 times. Using the second complex, a hydroformylation reaction of 1-pentene was carried out. After 72 h the reaction mixture was filtered through a polyamide membrane and recycled twice. 

An improved procedure has been reported for the synthesis of the C-functionalized tertiary phosphine (20), based on the reaction of potassium diphenylphosphide with ethyl chloroacetate.20... 

Halogen-lithium exchange cf. Section 4.7.3.2) at low temperatures with an alkyllithium followed by quenching with methanol or water results in stereospecific reduction of dihalocyclopropyl compounds.113 Stereospecific reduction has also been achieved by reaction with potassium diphenylphosphide (equation... 

In conjunction with the syntheses of (+)-NMDPP the relative effectiveness of lithium, sodium, and potassium diphenylphosphides was determined. Under a standard set of conditions the reaction of (-)-menthyl chloride with sodium diphenylphosphide gave the highest yield of (+)-NMDPP. The ratios of the yields of (+)-NMDPP were 1.0 1.55 1.16 for lithium, sodium, and potassium diphenylphosphide, respectively (17,32). 

Potassium diphenylphosphide can be obtained from Aldrich Chemical Company. 

Nucleophilic substitution of the chlorine atom of 1.1 with potassium diphenylphosphide (KP(C6H5)2) gives 3.1 [7, 8]. The reaction of 3.1 with Rh(I) and Pt(II) transition metal complexes (Eq. 1-3) yields compounds which can be used as models for silica supported catalysts [8],... 

Octa [3-(diphenylphosphino)-propyl]-silsesquioxane was prepared by treating [Cl-(CH2)3]g(SiOi 5)g dissolved in THF with a solution of potassium diphenylphosphide in THF at room temperature ... 

The red color of potassium diphenylphosphide was helpful to control the reaction, because all other compounds were colorless. 

Potassium organophosphide reagents also continue to find applications in synthesis. Direct displacement of fluoride from fluoroaromatic substrates by potassium diphenylphosphide is the key step in the synthesis of the phosphi-noarylsulfoxides (88), water-soluble phosphino-amino acid systems, e.g. (89), ° and the chiral benzoxazine system (90). Related displacement of fluoride by potassium monophenylphosphide has been used to prepare a series of hydrophilic triarylphosphines, e.g. (91). Among new phosphines prepared by conventional displacement reactions by potassium diphenylphosphide on... 

Nucleophilic substitution of the chloromethylated cross-linked polystyrene resin has been used to attach a wide variety of groups. Among these are those shown (5.31) Potassium diphenylphosphide was used to make the first phosphine.131 The microenvironmental effects of this catalyst in the formation of benzyl benzoate by the Mit-... 

For alkylation of phosphines containing C-H bonds their alkali salts are usually treated with alkyl halides. Thus primary and secondary phosphines can be obtained by metalation of phosphine itself with sodium in liquid ammonia and subsequent alkylation 208 phosphirane, which is unstable, is also prepared in this way, from sodium phosphide and ethylene dichloride.209 High yields of primary phosphines are afforded by alkylating lithium phosphide, which is formed almost quantitatively by metalating phosphine with butyl-lithium.210 Since the hydrogen can be replaced stepwise by metal, unsymmetrical secondary and tertiary phosphines can be built up from PH3 or a primary phosphine.211 Use of alkali phosphides is not limited to alkylation potassium diphenylphosphide reacts quantitatively with iodobenzene, yielding triphenyl-phosphine.212... 

Preparation of Phosphines from Metallated Phosphines. - Alkali metal-free phosphide anions have been shown to be formed under synthetically useful conditions in the equilibria between primary or secondary phosphines with the Schwesinger bases (23). Techniques have been developed for the preparation of alkali metal diphenylphosphide reagents in high purity, as evidenced by P nmr studies. The same paper reports a study of the course of the reactions between potassium diphenylphosphide and a series of aryl-, n-alkyl- and neopentyl-halides. The results provide the first evidence of the involvement of single electron transfer (SET) processes in the reactions of alkyl halides. This pathway is dominant in the case of neopentyl-type iodides, but plays only a minor role in the related reactions of neopentyl-type bromides and chlorides. No evidence was adduced of the involvement of SET processes in the reactions of unhindered... 

Two groups have reported syntheses of the chiral o-diphenylphosphino-oxazolines (55) which involve the displacement of fluorine from the related o-fluorophenyloxazolines using potassium diphenylphosphide. High yields of o-substituted arylphosphines, e.g., (56), have been obtained in a similar manner from the reactions of o-substituted aryl fluorides with potassium diphenylphosphide. Displacement of chlorine from a chloroarene by potassium diphenylphosphide in liquid ammonia is a key step in the synthesis of the phosphinobiaryl (57). The reaction of potassium diphenylphosphide with 1,2-bis(diphenylphosphino)ethyne generates the salt (58), treatment of which with chlorodiphenylphosphine gives the tetrakis(diphenyl-... 

The polycyclic phosphazenes 106 also present a propeller-type shape (07T4450). They have been obtained by reaction of the appropriate triol 103 in a three-step sequence (Scheme 28). This involves chlorination of a triol 103, using thionyl chloride, followed by reaction of the resulting trichloride derivative with in situ generated potassium diphenylphosphide to... 

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