Sodium diphenylphosphine

Preparation. This phosphine is prepared in 35% yield by the reaction of sodium diphenylphosphine with (-)-menthyl chloride in THF. This material contains about 5% of neomenthyldiphenylphosphine oxide as a tenacious impurity. 

Aqueous NaOH reacts with a-hydroxyalkyl substituents to give sodium diphenylphosphinate and a ketone (6.122). This reaction proceeds via the initial production of diphenylphosphine oxide, which then disproportionates as in (6.133) below. 

Fusion of phenyl (and other aryl) tertiary oxides with NaOH at 200-300°C gives sodium diphenylphosphinate directly (6.124) while with nitric acid, the phosphoryl group acts as a meta director, and with sulphuric acid a phosphonium salt can be formed (6.123). 

Van Leeuwen et al. used several generations of carbosilane dendrimers with 4, 8, 24, and 36 diphenylphosphine end-groups (Figure 4.15) for the allylic alkylation reaction of allyl trifluoracetate with sodium diethyl 2-methylmalonate.[31]... 

Nucleophihc attack of methoxide ion on olefinic and acetylenic groups of suitable unsaturated phosphine complexes of platinum(II) takes place to give cyclic, a-bonded complexes. This reaction appears to occur whether or not the unsaturated group is coordinated to the metal (22). But-3-enyl diphenylphosphine forms a chelate complex with platinum(II) chloride which on treatment with sodium hydrogen car-... 

The previous extension of solvent mixtures involved solvent interfaces. This organic-water interfacial technique has been successfully extended to the synthesis of phenylacetic and phenylenediacetic acids based on the use of surface-active palla-dium-(4-dimethylaminophenyl)diphenylphosphine complex in conjunction with dode-cyl sodium sulfate to effect the carbonylation of benzyl chloride and dichloro-p-xylene in a toluene-aqueous sodium hydroxide mixture. The product yields at 60°C and 1 atm are essentially quantitative based on the substrate conversions, although carbon monoxide also undergoes a slow hydrolysis reaction along with the carbonylation reactions. The side reaction produces formic acid and is catalyzed by aqueous base but not by palladium. The phosphine ligand is stable to the carbonylation reactions and the palladium can be recovered quantitatively as a compact emulsion between the organic and aqueous phases after the reaction, but the catalytic activity of the recovered palladium is about a third of its initial activity due to product inhibition (Zhong et al., 1996). 

To a stirred methylene chloride solution of 4.62 gm (15 mmoles) of 1-phenyl-2-(diphenylphosphine oxide)hydrazine maintained at —20°C is added over a 10 min period 2.67 gm (15 mmoles) of iV-bromosuccinimide. The solution is allowed to warm to room temperature, and stirring is continued for 10 min. The solids formed are removed by filtration and discarded. The solution is washed in turn with two portions of 5 % aqueous sodium thiosulfate solution, 0.1 N hydrochloric acid, water, dilute aqueous potassium bicarbonate, and again water. The methylene chloride solution is dried over anhydrous sodium sulfate and filtered. The filtrate is evaporated to incipient crystallization at room temperature at reduced pressure yield 4.1 gm (90%), m.p. 105°-106°C. 

Several mixed-metal clusters containing platinum and cobalt are known and some of them have been employed as methanol homologation catalysts.1 Among them, the title compound2 was first prepared unambiguously from the reaction of dichloro[l,2-ethanediylbis(diphenylphosphine)]platinum with sodium tetracarbonylcobaltate, Na[CO(CO)4]. The compound also may be prepared by the reaction of [l,2-ethanediylbis(diphenyl-phosphine)]bis(phenylethynyl)pIatinum with Co COJg.1... 

Sodium tetracarbonylcobaltate(l —) is prepared from Co2(CO)g (0.6 g) and 3% of Na-Hg (15 g) in tetrahydrofuran (THF).8 Dichloro[l,2-ethanediylbis-(diphenylphosphine)]platinum (1.0 g, 1.5 mmol) is suspended in freshly distilled, dry, and oxygen-free THF (20 mL) in a 100-mL two-necked flask fitted with a refluxing condenser, a Teflon-coated magnetic stirring bar, and an inlet for nitrogen connected to a mercury or mineral oil bubbler for venting excess gases. 

M 7/l-SULEONATOPHENYL)DIPHENYLPHOSPHINE, SODIUM SALT AND ITS COMPLEXES WITH RHODIUM , RUTHENIUM(II), IRIDIUM ... 

A. (MFT -SULFONATOPHENYL)DIPHENYLPHOSPHINE, SODIUM SALT (MONO-SULFONATED TRIPHENYLPHOSPHINE, TPPMS)... 

Meta-Sulfonatophenyl)Diphenylphosphine. Sodium Salt and Its Complexes 3... 

Sodium triacetoxyborohydride, 283 Titanium(III) chloride, 302 Tributyltin hydride, 316 Zinc borohydride, 167 of alkenes to alkanes (R)-(-F)- and (S)-(-)-2,2 -Bis(di-phenylphosphine)-l,1 -binaphthyl, 36 [1,4-Bis(diphenylphosphine)-butanej(cycloheptatriene)-rhodium(I) tetrafluoroborate, 89 [ 1,4-Bis(diphenylphosphine)butane]-(norbornadiene)rhodium(I) tetrafluoroborate, 37... 

Diphenylphosphine)lithium, 126 Nickel boride, 197 Samarium(II) iodide, 270 to 1,2-disubstituted compounds B-3-Pinanyl-9-borabicyclo-[3.3.1]nonane, 249 Titanium(III) chloride, 302 of phosphorus compounds Lithium aluminum hydride-Cerium(III) chloride, 159 of sulfoxides and sulfones Sodium iodide-Boron trifluoride ether-ate, 282... 

The coupling reaction of diphenylphosphine sulfide with A,A-disubstituted for-mamides in the presence of an excess of sodium hydride resulted in the corresponding aminomethyldiphenylphosphine sulfides in good yields. It is suggested that the carbon-oxygen bond is cleaved by sodium hydride (Scheme 12)308... 

Ethoxycarbonylation.1 Ally lie bromides (chlorides) undergo carbonylation in ethanolic sodium ethoxide when catalyzed by Na2PdCl4 in combination with bis-(diphenylphosphine)ethane, dppe, to provide (3,y-unsaturated esters in 70-95% yield. 

The reaction of (-)-menthyl chloride with sodium diphenylphosphide in tetra-hydrofuran requires 48-54 hr at reflux temperature for completion. The elimination side reaction is still observed. However, by-products (isomeric menthenes and diphenylphosphine) arising from the elimination reaction are easily removed by distillation. The overall conversion of (-)-menthyl chloride to (+)-NMDPP is about 34%, not counting the (+)-NMDPP oxide produced during a typical work-up. The (+)-NMDPP ligand is rather sensitive to air oxidation in solution and (+)-NMDPP oxide can be a very tenacious impurity, but careful crystallization of the phosphine from deoxygenated ethanol gives (+)-NMDPP in 95% (or higher) purity. 

A previous description of the synthesis of (CH3)3SiP(C6H5)2 in Inorganic Syntheses1 involves the initial preparation of sodium diphenylphosphide from diphenylphosphinous chloride. This method of preparation of the diphenylphosphide anion requires rigorous conditions and long reaction times. At least two other easier methods of preparation of the diphenylphosphide anion (lithium counterion) are known. One synthesis uses diphenyl-phosphine and n-butyllithium2 as reactants, whereas the second uses triphenylphosphine and elemental lithium.3,4 The second method is described here. 

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