L. S. Zakharov

Catalytic phosphorylation of polyfluoroalkanols. 15. Catalytic phosphorylation of α-polyfluoroalkylbenzyl alcohols by bis(polyfluoroalkyl) chlorophosphates

The catalytic phosphorylation of α-polyfluoroalkylbenzyl alcohols by bis(polyfluoroalkyl) chlorophosphates is a convenient method for the synthesis of various bis(polyfluoroalkyl)(α-polyfluoroalkylbenzyl) phosphates, including those having donor substituents in the benzene ring. It was shown that in the series of p-methyl-α-trifluoromethylbenzyl phosphates p-CH3C6H4CH-(CF3)OP(O)XY (where X, Y=Cl, CF3CH2O), the ability to act as O-alkylating agents with respect to polyfluorinated alcohols is a common characteristic, and the alkylating ability increases symbatically with increase in the overall electron-acceptor strength of the X and Y substituents at the phosphorus atom.

Synthesis and Thermal Transformations of 1-Polyfluoro-Alkyl-2-Trialkylsilylethyl Esters of Phosphorus Acids

Abstract We have studied the phosphorylation of 1-polyfluorolkyl-2-trialkylsilylethanols (I) with phosphorus acids chlorides.

Catalytic phosphorylation of polyfluoroalkanols Communication 10. Catalytic phosphorylation of α-polyfluoroalkylbenzyl alcohols by diaryl chlorophosphates

ConclusionsIrrespective of the structure of the alcohol and the reaction conditions, catalytic phosphorylation of α-polyfluoroalkylbenzyl alcohols by diaryl chlorophosphates leads exclusively to α-polyfluoroalkylbenzyl diaryl phosphates.

Preparation of polyfluoroalkyl esters of dialkyl- and diarylphosphinic acids by catalytic phosphorylation of polyfluoroalkanols

A number of polyfluoroalkyl esters of dialkyl- and diarylphosphinic acids was obtained by the phosphorylation of polyfluoroalkanols with dialkyl- or diarylchlorophosphinates in the presence of catalytic amounts of a calcium or magnesium salt.

Catalytic Methods for Synthesis of (Polyfluoroalkyl)-Arylchlorophosphates and Unsymmetrical Bis(Polyfluoroalkyl)Arylphosphates and Their Stereochemistry

Abstract Catalytic methods for the synthesis of (polyfluoroalkyl)arylchlorophosphates (I) have been developed

Synthesis and study of the thermal stability of siliconcontaining esters of phosphorus acids. 4. Thermal rearrangement of trimethylsilylmethyl esters of phosphorus acids

NMR spectroscopy has been used to study the thermal rearrangement of siliconeopentyl esters of phosphorus acids Me3SiCH2OP(O)R2 (I, R=CF3CH2O, PhO, t-BuCH2O, Bu). It has been established that in all cases the products of the rearrangement are the respective silyl esters Me2EtSiOP(O)R2 (II). The thermal rearrangement of (Me3SiCH2O)2P(O)OR′ (III, R=Ph, t-BuCH2, Me3SiCH2) is similar. It has been shown that electronic and steric attributes of the substituents R and R′ on the phosphorus atom are practically without effect on the extent of the thermal rearrangement. The presence of acidic additives, and initiators and inhibitors of radical reactions did not significantly influence the course of the rearrangement. It was concluded that this rearrangement apparently takes place as a result of heterolysis of the C-OP bond and simultaneous nucleophilic attack on the silicon atom by the phosphoryl part of the molecule.

Catalytic phosphorylation of o-carboranylmethanol

In previous work [I], we showed that the phosphorylation of weakly nucleophilic polyfluoroalkanols, such as l,l-dihydroperfluoroalkanols, is catalyzed by several metals and their chlorides. We have found that such catalytic phosphorylation is also applicable for rather weakly nucleophilic o-carboranylmethanol (I). Thus, the corresponding chloride and ester derivatives are formed when POCI a and chlorophosphates are used as the phosphorylating agents in the presence of magnesium as the procatalyst upon heating for 0.5-3 h.

Catalytic phosphorylation of polyfluoroalkanols. 14. Synthesis and diastereomeric conversion of aryl(α-polyfluoroalkylbenzyl) chlorophosphates

Aryl(α-polyfluoroalkylbenzyl) chlorophosphates are formed upon catalytic phosphorylation of α-polyfluoroalkylbenzyl alcohols with excess aryl dichlorophosphates. Reaction stereochemistry is under thermodynamic control; the product aryl(α-polyfluoroalkylbenzyl) chlorophosphates consist of equilibrium mixtures of diastereomers with a statistical (1∶1) ratio of components. Diastereomeric interconversions of aryl(α-polyfluoroalkylbenzyl) chlorophosphates occur both in the melt (or in solution) as well as in the crystalline state, but in opposite direction.

The Catalytic Methods of Synthesis of the Phosphorus Esters with Tertiary Polyfluoroalkyl Groups

Abstract The phosphorylation of tertiary alcohols can be performed only in some exceptional cases. We established, that phosphorylation of tertiary fluoroalkanols H(CF2) nCMe2OH (I, n = 2,4) with aryl- and polyfluoroalkyl-phosphorodicnlor-idates or aryl- and alkylphosphonic dichlorides in the presence of metal of metal salt catalysts yields chloroan-hydrides (II) and (III). When benzyl phosphorochloridates (IV) are used as phosphorylating agents, either products of phosphorylation or products of alkylation are formed depending on the nature of the substituent in the aromatic ring.

Synthesis of silicon-containing esters of phosphorus acids and study of their thermal stability. 3. Thermal rearrangement of triorganosilylmethyl esters of diphenyl phosphoric acid

Conclusions1.A method has been developed for the preparation of a series of triorganosilylmethyl esters of diphenylphosphoric acid.2.All the triorganosilylmethyl esters of diphenylphosphoric acid which were examined undergo thermal rearrangement involving the migration of a radical from the Si atom to the methylene C atom according to a 1,2-shift. The influence of the type of radical at the Si atom on the rate of the rearrangement has been studied.