Chlorophosphines phosphines

Mixed Alkyl-polyfluoroalkyl-phosphines. Chlorophosphines of the type RpRPCl (Rp = CFs or n-CjF, R = Me or CFj-CHa CHa) have been synthesized from the corresponding perhuoroalkyldihalogenophosphines CF,-Paj and n-CsF,- ... 

A number of (polyhalogenoaryl)phosphines have been synthesized by the addition of a chlorophosphine to a polyhalogenoaryl-lithium compound or a Grignard reagent. ... 

C. By Reduction.—The cyclic secondary phosphines phospholan and phosphorinan have been prepared by reduction of the corresponding chlorophosphines with lithium aluminium hydride. ... 

Although more hydrolytically sensitive than the phosphine boranes, diorganochlorophosphines can be more accessible than diorganophosphines and are not pyrophoric. Thus, the reaction of a chlorophosphine with an aryl halide or aryl triflate in the presence of zinc as a reducing agent and (DPPE)NiCl2 as catalyst provides a convenient procedure for P—C coupling (Equation (49)).150 A related nickel-catalyzed process driven by electrochemical reduction has also been reported 151... 

If trivalent phosphoms compounds are to be treated as electron-deficient species, then reactions of oxadiazoles with some Lewis acids should be reported here. 2-Phenyl-l,3,4-oxadiazole reacting with phosphoms trichloride in pyridine solution in the presence of triethylamine at low temperature furnished the respective dichlorophosphine and chlorophosphine, which were trapped by dimethylamine to give the corresponding amides. 2-Phenyl-l,3,4-oxadiazole also interacts over 24 h with the less reactive chlorodiphenylphosphine and dichlorophenylphosphine at room temperature to give phosphines (Scheme 14) <1999CHE1117>. These reactions of oxadiazoles resemble the behavior of 1-alkylimidazoles toward trivalent phosphorus derivatives. 

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... 

By far the most ubiquitous intermediates in synthesis of this class of phosphines are the alkali metal phosphides which can be prepared by either the KOH/DMSO method, by reaction of tertiary phosphines or chlorophosphines with alkali metals, or in the reaction of BuLi with appropriate secondary or tertiary phosphines. A number of the ligands in Figures 6 and 7 were prepared this way (60-69,72-74). 

Tetrakis(phenyldifluorophosphine)nickel-(0) could also be obtained, using arsenic trifluoride in the presence of catalytic amounts of antimony pentachloride, or zinc fluoride as fluorinating agents. Yields as high as 50% could be obtained, but sizable decomposition on the process of fluorination of the chlorophosphine nickel-(0) complexes in solution could not be entirely suppressed. The marked instability of zerovalent nickel-phosphine complexes in solution in organic solvents, even under strictly anhydrous and anaerobic conditions, has been noted by several workers (16,20), but is still lacking a detailed explanation. A closer examination of the system carbon tetrachloride-tetrakis(trichlorophosphine)nickel-(0) (23) showed the main pa h of the reaction to consist in the formation of hexachloro-ethane with conversion of zerovalent into bivalent nickel, while the coordinated... 

In the course of a study of the formation of fluorophosphoranes from chloro-phosphines (22) we observed one exception in the compound chloromethyldi-chlorophosphine, which reacted smoothly with antimony trifluoride to give the flammable fluorophosphine, C1CH2PF2, under conditions where many other chloro-phosphines were invariably converted into fluorophosphoranes. As this fluorophosphine is readily available, its interaction with a metal carbonyl derivative was studied, and cycloheptatriene molybdenum tricarbonyl, obtained from the reaction of molybdenum hexacarbonyl with cycloheptatriene (I, 2), was chosen as a starting compound. 

Phosphine groups are introduced to the benzylic position by addition of chlorophosphines to 2-lithiomethylpyr-idines <2003JCD1419>. Selenation at the benzylic position of 2-methylpyridines has been achieved in low yield by... 

The selective preparation of various chlorophosphines used as building blocks for the preparation of polyfunctional phosphines is achieved using dichloro (diethylamino)phosphine (Et2NPCl2). Alkylation of this phosphine with organozinc halides furnishes, after borane treatment, protected aminodi-organophosphines. These in turn can be converted to the corresponding... 

BASF s BASIL process [15] and the Dimersol process [16] have both been commercialized. The former uses the ionic liquid as a phase transfer catalyst to produce alkoxyphenylphosphines which are precursors for the synthesis of photoinitiators used in printing inks and wood coatings. The imidazole acts as a proton scavenger in the reaction of phenyl-chlorophosphines with alcohols to produce phosphines. The Dimersol process uses a Lewis acid catalyst for the dimerization of butenes to produce Cs olefins which are usually further hydroformylated giving C9 alcohols used in the manufacture of plasticizers. Several other processes are also at the pilot plant scale and some ionic liquids are used commercially as additive e.g. binders in paints. 

Organic halides have been converted electrochemically into tertiary phosphines using chlorophosphines. Electrochemical synthesis of a variety of tertiary mono- and diphos-... 

Dialkylphosphites add to isatin and 1-substituted derivatives at position C-3 generating dioxindolophosphonates366. Isatin-3-oximes react in a similar manner367. The use of chlorophosphines generates 3-(3-clorooxindolyl) phosphine oxides368 (Scheme 89). 

A complementary approach to the above method has recently been reported.35 Bis(diethylamino)chlorophosphine can be protected with borane, and then treated with lithium naphthalenide to generate 35, which reacts with organic electrophiles. These can be treated with HCI to yield the phosphonous halide borane compounds, RPCl2 BH3 (Scheme 15). These need not be isolated and can be treated directly with an organolithium and deprotected to yield a tertiary phosphine, R1R22P. 

Secondary phosphines, R2PH, can be chlorinated under controlled conditions to give the corresponding chlorophosphines. These compounds can be further oxidized in a number of ways (Scheme 30). The reaction of chlorodiphenylphosphine with dibenzoyl peroxide gives diphenylphosphinic acid... 

Several reports have appeared of the application of unusual organometallic reagents in phosphine synthesis. Treatment of 2-lithiopyridine with anhydrous zinc chloride results in the formation of a 2-pyridylzinc reagent which can be used to introduce the 2-pyridyl group at phosphorus in a controlled manner. Thus, e.g., in its reaction with phenyldichlorophosphine, the 2-pyridyl-(phenyl)chlorophosphine (15) is formed. This has then been converted via the phosphide route into a new class of binucleating ligands (16). The sterically crowded dichlorophosphine (17) (accessible from the reaction of phosphorus trichloride with lithium diphenyl(2-pyridyl)methanide) is converted into the thermally stable phosphirane (18) on treatment with calcium, strontium or barium cyclooctatetraenide.The reaction of phenyldichlorophosphine with the readily accessible titanacycle (19) affords a convenient route to the phosphetene (20). ... 

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