Chlorophosphines

X-ray crystallographic analyses of the structures show that the P-S bond distance vary over one-half of an Angstrom (2.36-2.88 A). The derivatives were generated using procedures similar to those utilized to form pentaoxyphosphoranes with P-N bonds, that is (i) the oxidation of sulfur containing cyclic chlorophosphines with a quinone or (ii) treatment of phosphites with the sulfur-containing diol in presence of N-chlorodiisopropylamine. Two typical examples of these synthetic protocols are shown in Scheme 10. 

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

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

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

Using R = Ph, Y = S02CeH4Me or PS(OPh)2, the aminophosphine form was detected. A second mole of chlorophosphine was added and in all cases P-phosphinophosphazenes were obtained ... 

A series of methylenaminophosphines, R2P N=CR 2 has been obtained by condensation of a chlorophosphine, R2PCI, with an imine,... 

The use of the phenyl phosphate group as both a solid support attachment site and a crucial binding element represents what has been referred to as a pharmacophore-linking strategy [26]. We explored a variety of phenyl phosphate tether functionalities to provide resins varying in substitution pattern and in chemical flexibility (Scheme 1 and Table 4) [22]. All phenyl phosphate resins were synthesized in batch quantities of 20 g or more. Resin synthesis began with the addition of either /mnethoxy-benzyl alcohol or benzyl alcohol to commercially available bis(diisopro-pylamino)chlorophosphine, followed by addition of the diversity phenol [(Ri)-OFl, DIAT (diisopropylamino tetrazole)]. Displacement of the... 

This reagent, prepared in situ from butyllithium and chloropentafluoroethane as an ether solution, has several times decomposed violently on addition of a few drops of a chlorophosphine. This is attributed to running the preparation too cool (< —90°C), so that it had not proceeded. However ... 

The azide monomer, prepared in solution from the chlorophosphine and sodium azide, should not be isolated because it is potentially explosive. 

Apart from characterization of the individual types of six-membered heterocycles by routine spectroscopic methods, several cationic cyclic diketiminato-phosphenium ions and 1,8-diamidonaphthalene-derived P-chlorophosphines and phosphenium ions, respectively, were characterized by single-crystal X-ray diffraction studies. The P-halogen- and P-hydroxy-substituted cyclic diketiminato-phosphenium ions 28... 

Denis and coworkers [37] could trap transient simple phosphaalkene 33, generated by HC1 elimination from chlorophosphine 32 at low temperatures [38], by ethyl diazoacetate at -50°C. Aromatization of the initially formed isomeric E-/Z-cycloadducts 35 to [l,2,4]diazaphospholes 36 could be achieved via P-chlorination/ dehydrochlorination sequence at -30°C using /V-chIorosuccinimidc (Scheme 10). 

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. 

Next, the effect of ligand of palladium complex on the reaction of butadiene was studied. Only vinylcyclohexene (4) was obtained by the reaction of butadiene at 90°C using bis(7r-allyl)palladium (13) and tri-chlorophosphine (1 1). 

The cyclopolyphosphines that were used to prepare the carbene-phosphinidene complexes described earlier were formed by the reduction of higher oxidation state phosphorus compounds, typically di-chlorophosphines, RPC12 (47-49). However, in some cases a separate reduction step is not necessary and it is possible to prepare the car-bene-phosphinidene complex (74) directly by reaction of a stable nucleophilic carbene with RPC12 (44). 

Reaction of a chlorophosphine with a stabilized carbanion reagent... 

Chlorophosphines need to be manipulated carefully with gloves and eye protection. They can cause burns, irritation to eyes and irritation to the respiratory system. 

Different chlorophosphines can be synthesised, or are available from Strem or Digital Chemicals. 

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