Subject phosphine oxides

Compared with the variety of existing carbon or nitrogen nucleophiles that were subjected to nucleophilic addition to there are few examples for phosphorus nucleophiles. Neutral trialkylphosphines turn out to be to less reactive for an effective addihon to Cjq even at elevated temperatures [114], Trialkylphosphine oxides show an increased reactivity. They form stable fullerene-substituted phosphine oxides [115] it is not yet clear if the reaction proceeds via a nucleophilic mechanism or a cycloaddition mechanism. Phosphine oxide addition takes place in refluxing toluene [115], At room temperature the charge-transfer complexes of with phosphine oxides such as tri-n-octylphosphine oxide or tri-n-butylphosphine oxide are verifiable and stable in soluhon [116],... 

The first enzymatic desymmetrizations of prochiral phosphine oxides was recently reported by Kielbasinski et al.88 Thus, the prochiral bis(methoxycarbonylmethyl)-phenylphosphine oxide 93 was subjected to the PLE-mediated hydrolysis in buffer affording the chiral monoacetate (RJ-94 in 72% ee and 92% chemical yield. In turn, the prochiral bis(hydroxymethyl)phenylphosphine oxide 95 was desymmetrized using either lipase-catalyzed acetylation of 95 with vinyl acetate as acyl donor in organic solvent or hydrolysis of 97 in phosphate buffer and solvent affording the chiral monoacetate 96 with up to 79% ee and 76% chemical yield. 

The Michaelis-Arbuzov reaction is the most used and well-known method for the synthesis of phosphonates and their derivatives and may also be used to synthesize phosphinates and tertiary phosphine oxides. The simplest form of the Michaelis-Arbuzov reaction is the reaction of a trialkyl phosphite, 3, with an alkyl halide, 4, to yield a dialkyl alkylphosphonate, 6, and new alkyl halide, 7 (Scheme 2). During this transformation the phosphorus atom of a ter-valent phosphorus(III) species (3) acts as a nucleophile resulting in the formation of an intermediate alkoxy phosphonium salt 5, containing a new [P—C] bond. The precise structure of the intermediates 5 is a subject of debate—as reflected by common reference to them as pseudophosphonium salts —with a penta-coordinate species (containing a [P—X] bond) being proposed and detected in some cases.18 Decomposition (usually rapid under the reaction conditions) of the intermediate 5 by nucleophilic attack of X- on one of the alkyl groups R1, with concomitant formation of a [1 =0] bond yields the product pentavalent phosphorus(V) compound (6) and the new alkyl halide, 7. 

The cleavage of carbon phosphorus bonds in phosphoryl compounds is another matter for consideration. Once a carbon-phosphorus bond is generated, usually it is extremely difficult to cleave it without major damage to the remainder of the molecule. However, phosphonate and phosphinate esters, as well as phosphine oxides, in which a hydroxyl or carbonyl group is present at the carbon directly attached to phosphorus are subject to facile cleavage of the carbon-phosphorus bond. 

Because these fire-retardant salts are water-soluble and subject to leaching, several new methods have been developed which provide a water-resistant or permanent treatment for cotton fabrics and cellu-losic materials. Perkin developed a process involving successive treatment with sodium stannate and ammonium sulfate, which precipitates stannic oxide in the cellulose libers. Antimony oxide in combination with vinyl chloride or other chlorinated polymers has also been found effective. A more recent approach to this problem involves application of fire-retardant resin-forming or cross-linking compounds. " These include materials and methods based on the copolymerization of tetrakis(hydroxymethyl)phosphonium chloride and methylol — melamine, the reaction of bromoform and triallyl phosphate to form a cross-linked polymer, and the cross-linking reaction of tris(l-aziridinyl)phosphine oxide with cellulose, or its copolymerization with tetrakis(hydroxymethyl)phosphonium chloride and other materials. ... 

Mechanistic studies have been the subject of a great deal of recent work." Although at one time the Wittig reaction was thought to occur through the formation of zwitterionic betaine intermediates (100) and (101), the reaction of a nonstabilized triphenylphosphorus ylide (99) with an aldehyde forms observable (by NMR) 1,2-oxaphosphetanes (104) and (105), which eliminate to produce the alkene (102) and phosphine oxide (103) (Scheme 21). "... 

Another variation of the Wittig reaction is the Wittig-Horner reaction, in which the anion generated ot- to phosphine oxide is used as a nucleophile to react with carbonyl compounds. The intermediate formed in this reaction, -hydroxyphosphine oxide, is isolable particularly when bases with lithium counterion are used for deprotonation. Since the j6-hydroxyphosphine oxides are diastereomers, they can be separated and subjected to elimination to form the corresponding alkenes. Since the elimination of phosphonate moiety is syn, stereospecific alkenes are obtained from the elimination step. As expected, the generation of erythro and threo isomers is dependent on the solvent and the reaction conditions. 

Phosphine oxides have fallen upon hard times, judging by the current literature, which this year has provided fewer publications on the subject than were reviewed in the first volume of this series A timely reminder that the subject is nevertheless alive comes from the thorough reviews of phosphine oxides, sulphides, selenides, and tellurides in the new edition of Kosolapolf s compilation. These chapters are likely to be of particular value to chemists requiring a quick guide to known structures and their preparation. 

The adsorption kinetics of a surfactant to a freshly formed surface as well as the viscoelastic behaviour of surface layers have strong impact on foam formation, emulsification, detergency, painting, and other practical applications. The key factor that controls the adsorption kinetics is the diffusion transport of surfactant molecules from the bulk to the surface [184] whereas relaxation or repulsive interactions contribute particularly in the case of adsorption of proteins, ionic surfactants and surfactant mixtures [185-188], At liquid/liquid interface the adsorption kinetics is affected by surfactant transfer across the interface if the surfactant, such as dodecyl dimethyl phosphine oxide [189], is comparably soluble in both liquids. In addition, two-dimensional aggregation in an adsorption layer can happen when the molecular interaction between the adsorbed molecules is sufficiently large. This particular behaviour is intrinsic for synergistic mixtures, such as SDS and dodecanol (cf the theoretical treatment of this system in Chapters 2 and 3). The huge variety of models developed to describe the adsorption kinetics of surfactants and their mixtures, of relaxation processes induced by various types of perturbations, and a number of representative experimental examples is the subject of Chapter 4. 

Efficient and general methods for the synthesis of chiral phosphine oxides and related compounds are a permanent subject for research of organic chemists. Therefore, the application of biocatalytic methods for the preparation of optically active P-chiral compounds has attracted great attention and a number of successful syntheses were described [172-178]. 

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