Phosphinic acid chlorides phosphine oxides

In general, if the desired carbon—phosphoms skeleton is available in an oxidi2ed form, reduction with lithium aluminum hydride is a powerful technique for the production of primary and secondary phosphines. The method is appHcable to halophosphines, phosphonic and phosphinic acids as well as thein esters, and acid chlorides. Tertiary and secondary phosphine oxides can be reduced to the phosphines. 

Phosphine oxides, e.g., di-/ -octadecylphosphine oxide, are oxidized to phos-phinic acids by hydrogen peroxide. With chlorine or phosphorus pentachloride, phosphine oxides form dialkylphosphinyl chlorides, R2P(0)C1, which can be easily hydrolyzed to phosphinic acids [162,165] see Eqs. (96) and (97) ... 

B. By Hydrolysis Reactions.—Details have appeared of the synthesis of dibenzophosphorin oxides (15) from 5-alkyldibenzophospholes, by reaction with methyl propiolate in the presence of water, and of confirmatory syntheses from phosphinic acid chlorides, as shown below. Evidence for the suggested mechanism of the ring-expansion reaction is presented. The hydrolysis of enamine phosphine oxides is an efficient, although somewhat indirect, method for the preparation of j8-ketoalkylphosphine oxides (16) [see Section 3(iii), for the preparation of enamine oxides]. Reasonable yields (48—66%) of trialkylphosphine oxides (17) have been obtained by the alkaline hydrolysis of the products from the pyrolysis at 220 °C of red phosphorus with alkyl halides, in the presence of iodine. 

AUenic phosphonic acids, phosphonates and phosphine oxides can be easily prepared from propargylic alcohols and phosphinyl chloride (see Chapter 1). They readily react with both electrophilic reagents and nucleophilic reagents. 

Diacylphosphines may be prepared by treatment of bis(trimethylsilyl)phenyl-phosphine (65) with acid chlorides.60 A diphosphine derivative (66) is formed with benzoyl chloride.60 A series of complex reactions occurs between nitrobenzenes and diphenyl(trimethylsilyl)phosphine (67).61 The oxides noted below were the only isolable products, and the yields were not high.61... 

Normally, the most practical vinyl substitutions are achieved by use of the oxidative additions of organic bromides, iodides, diazonium salts or triflates to palladium(0)-phosphine complexes in situ. The organic halide, diazonium salt or triflate, an alkene, a base to neutralize the acid formed and a catalytic amount of a palladium(II) salt, usually in conjunction with a triarylphosphine, are the usual reactants at about 25-100 C. This method is useful for reactions of aryl, heterocyclic and vinyl derviatives. Acid chlorides also react, usually yielding decarbonylated products, although there are a few exceptions. Likewise, arylsulfonyl chlorides lose sulfur dioxide and form arylated alkenes. Aryl chlorides have been reacted successfully in a few instances but only with the most reactive alkenes and usually under more vigorous conditions. Benzyl iodide, bromide and chloride will benzylate alkenes but other alkyl halides generally do not alkylate alkenes by this procedure. 

The synthesis of dendritic carbosilanes functionalized with various diphenylphosphino carboxylic acid ester endgroups has also been reported by the Van Koten group in collaboration with Vogt et al. [40,41], The coupling of carbosilane supports containing benzylic alcohol moieties with phos-phinoxy carboxylic acid chlorides resulted in the formation of Go and Gi phosphine oxides, which subsequently were converted into the phosphino... 

Tetrakishydroxymethyl phosphonium chloride (THPC) is well established as a flame retardant agent with textiles (3). Collins (2) has suggested that THPC and urea break down to produce phosphoric acid via a phosphine oxide, phosphinic acid, and phosphonic acid. For cellulose, Collins concludes flameproofing is essentially caused by the dehydrating action of the phosphoric acid formed. 

Thus phosphaallenes react with HC1 or methanolate, respectively, adding to the PC double bond and forming the phosphinous acid chloride or the corresponding methyl ester. In these cases the phosphorus atom acts as an electrophilic center. During the turnover of la,c together with H202/H20 the phosphorus atom again is attacked in a nucleophilic way and is oxidized to phosphinic acid 4a,c (Scheme 15). 

Acylpalladium complexes are readily prepared through oxidative addition of Pd° complexes to acid chlorides. PdL4 compounds, where L is a tertiary phosphine, react with acid chlorides at room temperature to give trani-L2Pd(COR)Cl complexes. Since carbon monoxide does not insert into palladium acyl bonds, Pd(C0C02R) complexes are made from oxidative addition of oxalyl chloride monoesters. 

SAFETY PROFILE Poison by inhalation and ingestion. A corrosive eye, skin, and mucous membrane irritant. Potentially explosive reaction with water evolves hydrogen chloride and phosphine, which then ignites. Explosive reaction with 2,6-dimethylpyridine N-oxide, dimethyl sulfoxide, ferrocene-1,1 -dicarboxylic acid, pyridine N-oxide (above 60°C), sodium -L heat. Violent reaction or ignition with BI3, carbon disulfide, 2,5-dimethyl pyrrole + dimethyl formamide, organic matter, zinc powder. Reacts with water or steam to produce heat and toxic and corrosive fumes. Incompatible with carbon disulfide, N,N-dimethyl-formamide, 2,5-dimethylpyrrole, 2,6-dimethylpyridine N-oxide, dimethylsulfoxide, ferrocene-1,1-dicarboxylic acid, water, zinc. When heated to decomposition it emits highly toxic fumes of Cl" and POx. 

Complexes of uranyl chloride with a variety of oxygen donor ligands continue to be reported, notably with phosphine oxides (55), pyridine N-oxides (27), N,IV-dimethylformamide (7J), acetamide (15), and with the N,IV,IV, IV -tetramethyldicarboxylic acid amides (14), the last being mainly polymeric compounds. A few similar complexes of uranyl bromide (54) and iodide (71) are also known. 

Although Smh is more chemoselective than traditional dissolving metal reagents, it does react with sulfoxides, epoxides, the conjugated double bonds of unsaturated ketones, aldehydes and esters, alkyl bromides, iodides and p-toluenesulfonates. It does not, however, reduce carboxylic acids, esters, phosphine oxides or alkyl chlorides. In common with most dissolving metal systems, ketones with an a-hetero substituent suffer loss of the substituent rather than reduction of the carbonyl group. ... 

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