Phenyl dichloro phosphine

A range of reactions of 2-chlorocyclohexyl(dichloro)phosphine (60) with alcohols and epoxides has been described, largely with a view to the synthesis of polymer intermediates and flame-retardants.50 The copolymerization of dichloro(phenyl)-phosphine with styrene and vinyl butyl ether in the presence of maleic anhydride has been studied.61... 

Phosphine, (2-bromophenyl)dichloro-, 2,991 Phosphine, (w-chloroalkyl)dichloro-, 2, 991 Phosphine, chlorodimethyl-, 2, 991 Phosphine, chloro(dimethylamino)-, 2, 991 Phosphine, chlorodiphenyl-, 2, 990 Phosphine, cyclohexyl(o-anisyl)methyl-rhodium complexes asymmetric hydrogenation, 6, 251 Phosphine, [(dialkylphosphino)alkyl]diphenyl-, 2, 994 Phosphine, dichloromethyl-, 2, 991 Phosphine, dichlorophenyl-, 2, 990 Phosphine, diethylphenyl-, 2, 992 Phosphine, dimethyl-, 2,992 Phosphine, dimethylphenyl-, 2,992 Phosphine, diphenyl-, 2, 992 Phosphine, ethyldiphenyl-, 2, 992 Phosphine, ethylenebis(diethyl-, 2, 993 Phosphine, ethylenebis(diphenyl-, 2,993 Phosphine, ethylenebis(phenyl-, 2,992 Phosphine, ethylidynetris[methylene(diphenyl-, 2,994 Phosphine, [(ethylphenylphosphino)hexyl]diphenyl-, 2, 994... 

Dichloro-1 -phenyl-3-methy I-1-phospha-3-cyclopentene from isoprene and dichlorophenyl-phosphine, 43, 73... 

One exception to the use of primary phosphines is in the reported syntheses of the catASium M dass of ligands 20 [46-49]. In one report, reaction of the cyclic sulfate with P(TMS)3 yields the TMS-protected secondary phospholane, which could then be reacted with the appropriate 1,2-dichloro spedes [46]. An alternative procedure to the same intermediate involves preparation of 1-phenyl-phospholane via the bismesylate, subsequent lithium-induced P-Ph deavage, and quenching with TMSC1 [49]. The ligand based on 2,3-dichloromaleic anhydride (20a originally referred to as MalPHOS [46]) has been shown to be effective for the chiral reduction of a- and /1-deliydroarnino acid derivatives and itaconate derivatives. 

A study of the reactions of halogeno-phosphines with ketone derivatives has been extended to (44), which forms a heterocycle (45a) with dichloro(phenyl)phosphine38 under neutral conditions. The analogous oxide (45b) has already been isolated from... 

Compound 290 was reacted with dichloro(phenyl)phosphine in the presence of Et3N this led to a ring-opening reaction with the breakage of the 0-CH2 bond, insertion of the phosphorus atom, and formation of the intermediate 291, which gave upon hydrolysis the cyclic phosphoryl-containing product 292 <1998IC4945>. 

Attempted nitration of dichloro(phenyl)phosphine under mild conditions results only in oxidation at phosphorus.The phosphinate esters (95) have been isolated from the reactions of chlorodialkylphosphines with 1,l-dichloro-l-nitrosoalkanes. 

The cyclic phosphinate (96) has been isolated from the reaction of dichloro(methyl)phosphine with the ethoxycarbonylimine derived from hexafluoroacetone. Treatment of trichloro(organo)phosphonium-hexafluorophosphate salts with dichloro(diethylamino)phosphine results in the halophosphonium salts (97). Some reactions of dichloro(-)menthylphosphine have been reported.As usual, nucleophilic displacement reactions of halogenophosphines have received attention as routes to new systems of interest as ligands.Of particular interest in this connection is a report of the synthesis of the phosphorus-functionalised calixarenes (98). Only one chlorine atom of dichloro(phenyl)-phosphine is replaced on treatment with an excess of dicyclohexylamine, enabling the stepwise synthesis of the chiral aminophosphines (99), described as air-stable solids. 

On treatment with dichloro(phenyl)phosphine, the silylated imino... 

Since the double-bond isomerization was at first unrecognized and later recognized only in the hydrolysis products, the position of the double bond in most of the compounds described in the literature must be regarded as uncertain. The only proved facts seem to be that with isoprene dichloro(phenyl)-phosphine gives the 2-phospholene derivative, that dichloro(methyl)phosphine and dibromo(phenyl)phosphine give the 3-phospholene, whereas also with 2,3-dimethylbutadiene dichloro(phenyl)phosphine gives the non-isomerized product of type (1).38,39... 

The 1-phenyl derivative,43 which possesses structure (2),38,39 is obtained somewhat more conveniently (5-7 days at room temperature) in about 60% yield from dichloro(phenyl)-phosphine. 

Direct reaction of phosphorus halides with hydrocarbons in the absence of catalysts requires drastic conditions and is not really suitable for laboratory purposes. For example, phosphorus trichloride reacts with methane or ethane only at about 600° this affords moderate yields of alkyldichlorophosphines.142 The corresponding reaction with benzene at 550° is said to give good yields of dichloro(phenyl)phosphine.143... 

Ferrocene reacts with PC13/A1C13 with replacement of all three chlorine atoms, but the tertiary phosphine is sensitive to air and difficult to isolate. However, diferrocenylphenylpfiosphine [from dichloro(phenyl)phosphine] and ferrocenyldiphenylphosphine [from chloro(diphenyl)phosphine] are obtained analogously as stable compounds in 52% and 37% yield, respectively.156... 

Chloro-(/7-cyanophenyl)phenylphosphine 349 Dichloro(phenyl)phosphine (60 g) is added to a slurry of i -cyanobenzenediazonium tetrafluoroborate (72 g) and copper(i) bromide (2.4 g) in dry isopropyl acetate (300 ml). After about 20 min a violent reaction sets in which is moderated by external cooling so that the temperature remains between 20° and 40°. When gas evolution ceases, aluminum turnings (8 g) are added and the mixture is stirred for 2 h at 40-50°. Then the liquid is decanted from unused aluminum, and phosphorus oxychloride (51 g) is added to decompose the aluminum chloride complex. Distillation then affords a forerun (5 g), followed by the main fraction (39 g, 47%) between 15870.7 mm and 195°/ 3.1 mm (owing to unavoidable decomposition the pressure does not remain constant during the distillation). Further distillation gives a product boiling at 16270.2 mm. 

The most convenient method of preparing (chloro)diphenylphosphine is by disproportionation of the readily accessible dichloro(phenyl)phosphine ... 

Chloro)diphenylphosphlne 357 Dichloro(phenyl)phosphine (390.5 g) and anhydrous aluminum chloride (10 g) are heated under reflux in a flask carrying a Vigreux column under a distillation head. The phosphorus trichloride (136 g) distils in 12 h. The residue is then distilled at 130-156°/2-3 mm and the distillate is fractionated in a vacuum, giving dichloro-(phenyl)phosphine (168 g, 70%), b.p. 110-112°/0.35 mm, nD20 1.6356. 

Unsymmetrical alkylarylchlbrophosphines can be prepared in good yield from aryldichlorophosphines and tetraethyllead.380 1,4-Dilithiotetraphenyl-butadiene, which is relatively easily accessible from diphenylacetylene, reacts with dichloro(phenyl)phosphine to give pentaphenylphosphole (cf. page 698) in 84% yield.381... 

A rationalization of the reactions between )8-keto-alcohols and halogenophosphines has been presented by a Russian group. In particular, the reaction between dichloro(phenyl)phosphine (26) and diacetone alcohol to give the oxide (27) has been shown to occur in stages (Scheme 9), and physical and chemical evidence has been presented for the initial formation of mesityl oxide (28) and the acid (29), followed by the addition product (30). A less detailed study of the analogous reaction of chlorodiphenyl-phosphine (5) with diacetone alcohol has also been published. ... 

Miscellaneous. Boron tribromide treatment of dichloro(phenyl)-phosphine (26) gives the dibromide quantitatively. Phenyl radicals and... 

An alternative method to prepare aromatic halo- or dihalo-phosphines is the reaction of a phosphorus trihalide with an arylmetal compound. Like the alkyl compounds, the metal must be a less electropositive one to avoid the formation of a tertiary phosphine, unless the arylmetal compound is sterically hindered. Older examples of syntheses by this method are the preparation of dichloro(l-naphthyl)phosphine (equation 25) and some dichloro(4-substituted-phenyl)phosphines (equation 26)". More recently, hindered aryllithium compounds have been treated with PCI3 to give dichloro(mesityl)phosphine or chlorodime-sitylphosphine" (equation 27), dichloro (2,4,6-tri-r rr-butylphenyl)phosphine (15) and dichloro[2,6-bis(trifluormethyl)phenyl]phosphine (16)." Aryldifluorophosphines have... 

Other methods to prepare aromatic halo- or dihalo-phosphines are occasionally used. Arylbis(dialkylamino)phosphines have been converted into aryldihalophosphines with dry HCl or HBr, e.g. dichloro(2-methoxy- or 2-dimethylaminophenyl)phosphine (equation 29) the o- and m-phenylenebis(dichlorophosphine)s 20 and 21" and the p-phenylenebis(dichlorophosphine) 22. The c -phenylenebis(dibromophosphine) 23 has been prepared similarly Aryldiazonium tetrafluoroborates with PCI3 give chlorophos-phonium salts, which can be reduced to aryldichlorophosphines (equation 30). Primary and secondary phosphines may be chlorinated with phosgene to give chlorophosphines, e.g. hexamethylenebis[chloro(phenyl)phosphine] (equation 31) and 20 ". ... 

The preparation of aminophosphines from chlorophosphines and an amine is usually straightforward. Two equivalents of the amine or the addition of one equivalent of a tertiary amine per chloro group is necessary to neutralize the acid formed, unless a trimethylsi-lylamine is used good yields of aminochlorophosphines are obtained from dichlorophos-phines and 2 mol of an amine or 1 mol of a trimethylsilylamine. Representative examples are the preparation of aminophosphines from dichloro(phenyl)phosphine (equations 36 and 37 ) and the preparation of some functionalized aminophosphines (equations 38 and 39 ). Examples of reactions with trimethylsilylamines are given in equations 40 and 41. Hydrazinophosphines are known and may be prepared from chlorophosphines, e.g. 2,2-dimethylhydrazinodiphenylphosphine (equation 42). ... 

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