From Halogenophosphines and

The reactions of lithium enolates, derived from the metallation 

2 Preparation of Phosphines from Metallated Phosphines.- This route contines to find wide application. New polydentate ligands, 

The tetraphosphinoalkene (20) has been isolated from the reaction of 1,2-dilithio-l,2-diphenylphosphinoethane with tetrachloroethene at -50°C. This compound has much greater stability to air and water than has the related acyclic product (21) isolated from the reaction of lithium diphenylphosphide with tetrachloroethene at -78°C. If 

The past year has seen many reports of the use of metallophosphide reagents in the synthesis of new heterocyclic phosphorus compounds 

Baudler s group, and others, continue to employ metallophosphide reagents in the development of the chemistry of cyclic polyphosphorus compounds. 

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A. From Halogenophosphine and Organometallic Reagent.—Mesityl-magnesium bromide reacts with chlorodiethylphosphine and dichloroethyl-phosphine at — 10 °C in THF to yield mesityldiethylphosphine and dimesitylethylphosphine respectively. ... 

From Halogenophosphines and Organometallic Reagents.- A greatly improved route to tris-t-butylphosphine is afforded by the addition of a benzene solution of phosphorus trichloride to a pentane solution of t-butyllithium. Direct metallation of benzenechromiumtricarbonyl with butyllithium at -30°C, followed by... 

Preparation.—From Halogenophosphine and Organometallic Reagents. The cyclo-pentadienylphosphines (1) have been obtained from the reaction of cyclopenta-dienylthallium with chlorophosphines in ether.1 Diphenyl(4-pyridyl)phosphine (2) is prepared from 4-pyridyl-lithium and chlorodiphenylphosphine,2 and an improved procedure for the synthesis of tri-(2-pyridyl)phosphine (3) from 2-pyridyl-lithium and phosphorus trichloride has been reported.3... 

Preparation.—From Halogenophosphines and Organometallic Reagents. A series of trimethylsilylcyclopentadienylphosphines, e.g. (1), has been prepared from the appropriate trimethylsilylcyclopentadienyl-lithium and halogenophosphine. Similarly, the reaction of pentamethylcyclopentadienyl-lithium with chlorodimethyl-phosphine gives the phosphine (2), which is reported to be thermally stable. ... 

Preparation.—From Halogenophosphine and Organometallic Reagents. An improved synthesis of trimethylphosphine from phosphorus trichloride and methyl-lithium at —78 °C has been described. Another improved high yield synthesis of the same phosphine uses the reaction of triphenyl phosphate with methylmagnesium iodide. Other trialkylphosphines have also been prepared by this latter method. 

Preparation.—Little significant preparative work has appeared this year. The preparation - of phosphoranes from halogenophosphines and carbonyl compounds is discussed above, and the conversion - of certain of these into phosphine oxides is discussed in Chapter 4. The perfluorophenylphosphorane (76) has been prepared. Dichlorotriethylphosphorane (77) is formed as a... 

From halogenophosphines and organometaUic reagents. This route continues... 

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