Phosphine Oxides and Phosphates

Organic derivatives of phosphorus excel by the strong tendency of trivalent phosphorus to combine with oxygen or sulfur to form phosphine oxides and phosphates or their sulfur analogs. 

From the product analyses of PET reactions of trivalent phosphorus compounds such as phosphines and phosphates, it is found that P reacts with nucleophiles such as water and alcohol to yield phosphine oxides and phosphates [92-95]. During a reaction of triphenylphosphines (P(CgH4-X-/ )3 with water to give phosphine oxides 0=P(C6H4-X-/ )3... 

Phosphine sulphides and thiophosphates have been converted into phosphine oxides and phosphates, respectively, by reaction with dimethyldioxirane (11). ... 

In addition to the ozonolysis of alkenes and a few aromatic compounds [93, 104], ozone oxidizes other groups. Thus saturated hydrocarbons containing tertiary hydrogen atoms are converted into tertiary alcohols [105, 106], and some alkenes are transformed into epoxides [107] or a,p-unsat-urated ketones [108], Benzene rings are oxidized to carboxylic groups [109, ethers [110] and aldehyde acetals [111] to esters aldehydes to peroxy acids [772] sulfides to sulfoxides and sulfones [775] phosphines and phosphites to phosphine oxides and phosphates, respectively [775] and organomer-cury compounds to ketones or carboxylic acids [114]. 

Phosphine Chalcogenides as Ligands. - The complexation of lanthanide and actinide ions by phosphine oxide ligands remains an active area, and a theoretical assessment of the coordination of phosphine oxides (and phosphate esters) by trivalent lanthanide ions has appeared." Trivalent lanthanide complexes of the functionalised enol phosphine oxide (265), (and a related phosphonate), have been describedComplexes of thorium(iv) with bis(di-phenylphosphino) ethane dioxide and bis(diphenylphosphinoyl)amide have also been characterised." Calixarene systems which bear phosphine oxide... 

Epoxide and curing agents based on phosphine oxide and phosphate... 

The phosphorus ylides of the Wittig reaction can be replaced by trimethylsilylmethyl-carbanions (Peterson reaction). These silylated carbanions add to carbonyl groups and can easily be eliminated with base to give olefins. The only by-products are volatile silanols. They are more easily removed than the phosphine oxides or phosphates of the more conventional Wittig or Homer reactions (D.J. Peterson, 1968). 

Phosphates, Phosphonates, Phosphine Oxides and Phosphine Sulfides 260, 544, 1433, 1513, 1564,1658... 

The same group studied the lithium cation basicities of a series of compounds of the general formula R R R PO, i.e. phosphine oxides, phosphinates, phosphonates and phosphates, by using Fourier Transform Ion Cyclotron Resonance (FTTCR) mass spectrometry. A summary of their results is shown in Figure 4. The effect of methyl substitution on LCA as well as the correlation between LCA and PA was also investigated by Taft, Yanez and coworkers on a series of methyldiazoles with an FTICR mass spectrometer. They showed that methyl substituent effects on Li binding energies are practically additive. 

Hydrophilic molecules are composed of ions (such as sulphonate, sulphate, carboxylate, phosphate and quaternary ammonium), polar groups (such as primary amines, amine oxides, sulphoxides and phosphine oxide) and non-polar groups with electronegative atoms (such as oxygen atom in ethers, aldehydes, amides, esters and ketones and nitrogen atoms in amides, nitroalkanes and amines). These molecules associate with the hydrogen bonding network in water. 

Walkenyl, W-(adenosine-2-yl), and Wphosphoryl bicyclic isoxazolidines were also obtained by HDA reactions of cyclopentadiene with nitroso alkenes, 2-nitrosoadenosine, P-nitroso phosphine oxides and P-nitroso phosphate, respectively <20000L1323, 2001J(P1)1908, 2002JOG6174>. 

General.—brief report indicates that phenylthiocarbamoylphosphonates (48) rearrange, evidently rather readily, to phosphate esters phosphinates are obtained from phosphine oxides and sulphides. ... 

Ozonation of Heteroatoms. Phosphines are converted to phosphine oxides and phosphites to phosphates by ozone. These reactions are quite general and a wide range of sub-stitutents can be tolerated. Phosphine oxides also can be produced by the ozonation of alkylidenetriphenylphosphoranes or of thio- or selenophosphoranes. Organic sulfides are converted to sulfoxides and sulfones by ozonation. Tertiary amines are converted to amine oxides, while nitro compounds can be produced in modest yields by ozonation of primary amines. This preparation of nitroalkanes compares well with alternate approaches using peroxides, peroxy acids, permanganate, or Monoperoxysulfuric Acid, but ozonation on silica gel has proven to be superior (see Ozone-Silica Get). Selenides are converted to selenoxides by ozone and this reaction is often used to achieve overall production of unsaturated carbonyl compounds. An example is shown in eq 25. ... 

Solvating reagents such as neutral compounds (e.g., ethers, ketones, alcohols, and esters of carboxylic acids, alkyl phosphates, phosphonates, phos-phinates, phosphine oxides, and phosphine sulfides) and also esters of pyridinecarboxylic acids and certain benzimidazole derivatives that have electron-withdrawing substituents form solvates with extracted neutral species. For example, dialkylpyridine-3,5-carboxylates extract Cu(II) at pH 3 from concentrated chloride solutions ... 

Phosphoms-eontaining flame retardants inelude inorganie phosphates, insoluble ammonium phosphate, organophosphates and phosphonates, halophosphates and chlorophosphonates, phosphine oxides, and red phosphoms. The mechanism for flame retardancy varies with the phosphoms eompound and the polymer type. A phosphoms eontaining flame retardant ean function in the condensed phase, the gas phase, or eoneurrently in both phases. 

Phosphines and Phosphonium Salts Quinquecovalent Phosphorus Compounds Halogenophosphines and Related Compounds Phosphine Oxides and Related Compounds Tervalent Phosphorus Acids Quinquevalent Phosphorus Acids Phosphates and Phosphonates of Biochemical Interest Nucleotides and Nucleic Acids Ylides and Related Compounds Phosphazenes Physical Methods. 

Another category of extractants is the neutral or solvating category. These are often phosphorus based, commonly consisting of substituted phosphine oxides or phosphate esters. Common examples applied to the extraction of U include tri-n-butyl phosphate and trioctyl phosphine oxide, whereas dibutyl butyl phosphonate has been used for the extraction of As species. They solvate the species of interest, thus making the target solute soluble in the membrane liquid phase. 

Shi, M. and Inoue, Y., Geometrical photoisomerization of (Z)-cyclooctene sensitized by aromatic phosphate, phosphonate, phosphinate, phosphine oxide and chiral phosphoryl esters, /. Chem. Soc., Perkin Trans. 2, 2421-2428, 1998. 

Garbodiimide Formation. Carbodiimide formation has commercial significance in the manufacture of Hquid MDI. Heating of MDI in the presence of catalytic amounts of phosphine oxides or alkyl phosphates leads to partial conversion of isocyanate into carbodiimide (95). The carbodiimide (39) species reacts with excess isocyanate to form a 2 + 2cycloaddition product. The presence of this product in MDI leads to a melting point depression and thus a mixture which is Hquid at room temperature. 

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