- Catalytic activity of various Lewis acids in the phosphorylation of primary polyfluoroalkanols with phosphoryl chloride
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The catalytic activity of SnCl2, SnCl4, SbCl3, SbCl5, and BiCl3 in the reaction of 2,2,3,3,4,4,4-heptafluorobutanol with POCl3 was studied. The mechanism of this reaction is discussed. Strong Lewis acids were found to be less active catalysts.
- Kudryavtsev,Zakharov,Kabachnik
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- Phosphorylation of heptafluorobutanol in the presence of metal chloride - Ether catalytic systems
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Catalytic activity of complex catalysts based on Li, Na, K, and Cs chlorides and polydentate ligands, viz., dibenzo-18-crown-6, mono-, di-, and tetraglymes, and poly(ethylene glycols) PEG-600 and PEG-1000 was examined in the phosphorylation of heptafluorobutanol with phosphorus oxychloride. The introduction of an organic ligand into a catalytic system leads to improvement in solubility of the salt used as a catalyst and to an increase in the reaction rate by a factor of 1.3-2.8. The catalytic systems based on LiCl and poly(ethylene glycols) proved to be most efficient.
- Kudryavtsev,Zakharov
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- CATALYTIC PROCESS FOR PHOSPHO-HALOGENATION OF FLUORINATED ALCOHOLS
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A process for manufacturing a polyfluroalkanoyl phosphorodichloridate comprising reacting a polyfluoroalkanol having the general formula Rf—CH2—OH, wherein Rf is a linear or branched C1-C8 perfluoroalkyl group optionally interrupted by O, with at least 4 moles of POCl3 per mole of Rf—CH2—OH in the presence of 0.1 to 0.2 moles of LiCl catalyst per mole of Rf—CH2—OH at a temperature between 95° C. and 110° C. to form a phosphorodichloridate of the general formula Rf—CH2—O—P(O)Cl2.
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Paragraph 0034-0036
(2013/04/13)
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- Fluorinated phosphorus compounds: Part 3. the synthesis of symmetrical and unsymmetrical fluoroalkyl phosphates
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Treatment of phosphorus pentachloride with four molar equivalents of fluoroalcohol gave symmetrical phosphates (RFO)3P=O in isolated yields between 10-92% [RF=CF3CH2, C2F5CH2, HCF2CF2CH2, C3F7CH2, (FCH2)2CH, (CF3)2CH, C2F5(CH3)CH]. The reaction proceeded best for fluoroalcohols having many fluorine atoms. 2,2-Difluoroethanol HCF2CH2OH and 1,3-difluoroisopropanol (FCH2)2CHOH did not react cleanly and gave product mixtures. Hexafluoroisopropanol produced a 3:7 mixture of symmetrical phosphate [(CF3)2CHO]3P=O and chlorophosphorane [(CF3)2CHO]4PCl. The latter reacted readily with water and alcohols. Heating the chloridates CF3CH2OP(O)Cl2, (CF3CH2O)2P(O)Cl and (C2F5CH2O)2P(O)Cl with various fluoroalcohols in the presence of calcium chloride catalyst gave unsymmetrical phosphates in isolated yields between 46-83%. The mixed phosphate (CF3CH2O)2P(O)OCH2C 2F5 did not react with butanol or propylamine in dichloromethane at room temperature.
- Timperley, Christopher M.,Holden, Ian,Morton, Ian J.,Waters, Matthew J.
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p. 153 - 161
(2007/10/03)
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- NEW HOMOGENEOUS ORGANIC CATALYTIC SYSTEMS FOR SYNTHESIZING POLYFLUOROALKYL ESTERS OF PHOSPHORUS ACIDS
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Catalytic activity of a series of ammonium and phosphonium salts, as well as some carboxylic and phosphorus acid amides, was studied.Dipolar compounds of R2S=O or R3P=O types were also found to be precursors of homogeneous catalytic systems.
- Kabachnik, M. I.,Zakharov, L. S.,Kudryavtsev, I. Yu.
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p. 1733 - 1734
(2007/10/03)
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- CATALYTIC PHOSPHORYLATION OF POLYFLUOROALKANOLS. 13. SOME AMMONIUM AND PHOSPHONIUM SALTS AS PHOSPHYRYLATION CATALYSTS
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It was shown that it is possible to use a series of ammonium and phosphonium salts as effective catalysts for the preparative synthesis of tris(polyfluoroalkyl)phosphates.The effect of the structure of substituted ammonium salts on their catalytic activity was studied in the phosphorylation of 1,1-dihydroperfluorobutanol by phosphorus oxychloride.It was determined that the reaction rate is effected not only by the solubility of the salt, but also by the nature of the ion pair and the steric access of the onium center for solvation by phosphoryl compounds.
- Kabachnik, M. I.,Zakharov, L. S.,Kudryatsev, I. Yu.
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p. 2553 - 2556
(2007/10/02)
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