N. I. Delyagina

Catalytic synthesis of polyfluoroolefins

A catalytic synthesis of polyfluoroolefins was developed proceeding from polyfluorochlorocarbons with the use of industrially produced nickel-chromium catalyst. Three ways of the catalytic synthesis of fluoroolefins were implemented: the cleavage of vicinal chlorine atoms from polyfluorochlorocarbons, the replacement of vinyl chlorine atoms by hydrogen in fluorochloroolrfins, and the reductive dimerization of polyfluorochlorocarbons containing a trichloromethyl group. The condition of a prolonged operation of the nickel-chromium catalyst was found consisting in the application of quartz for absorption of the hydrogen fluoride formed as a side product.

Fluoroaliphatic esters of fluorosulfonic acid. 5. Conjugate radical fluorosulfatohalogenation of higher fluoroolefins

A study has been made of the electrochemical fluorosulfation of perfluoro-2-alkenes in the presence of halogens, leading to the formation of fluoroaliphatic vicinal fluorosulfatohalides. The reaction proceeds as a conjugate radical addition of peroxydisulfuryl difluoride and the halogen at the double bond of the olefin; the ratio of the resulting regioisomers is determined by steric factors.

Fluoroaliphatic esters of fluorosulfonic acid. 2. Reaction of bis(fluorosulfato)perfluoroalkanes with cesium fluoride

Abstract2,3-Bis(fluorosulfato)perfluoroalkanes split under the action of CsF in the absence of solvents, giving a mixture of α-fluorosulfatoperfluoro ketones, perfluoroalkene sulfates, and perfluoro α-diketones. The occurrence of these reactions in solutions results mainly in the formation of oxides of the corresponding fluoroolefins or products of their conversions. The reactions carried out are the first examples of nucleophilic substitution at a secondary carbon atom in a perfluorinated saturated chain.

ELECTROCHEMICAL PERFLUOROALKOXYLATION OF AROMATIC COMPOUNDS

New approaches to the electrochemical synthesis of aryl perfluoroalkyl ethers based on a) the electrooxidation of perfluorocarboxylic acid on a consumable PbO2 anode and b) the simultaneous anodic oxidation of the “aromatic compound-alkaline perfluoroalkoholate” system on a platinum electrode were proposed.

Interaction of perfluorinated α-fluorosulfatocarbonyl compounds with nucleophilic reagents

Abstract α-Perfluorosulfatoperfluorocarbonyl compounds interact with alkaline metals halogenides to form the corresponding α-halo derivatives as a result of the direct nucleophilic substitution of the FSO 3 group. Through the action of halogenide anions on perfluorinated α,β-bis-fluorosulfatocarbonyl compounds, substitution by halogen of the FSO 3 group in the α-position to the carbonyl takes place. However, the FSO 3 group in the β-position is cleaved, which allows α-substituted β-dicarbonyl derivatives to be obtained.

Fluoroaliphatic esters of fluorosulfonic acid. 6. Interaction of fluorine-containing α,β-bis-fluorosulfatocarbonyl compounds with nucleophilic reagents

Fluorine-containing α,β-fluorosulfatocarbonyl compounds interact with halides of alkali metals with the formation of α-halogeno-β-dicarbonyl derivatives.

SYNTHESIS AND REACTIVITY OF POLYFLUORINATED FLUOROSULFATOCARBINOLS IN THE PRESENCE OF BASES

Compounds CF3CR(OH)CF2OSO2F (I) (R=MeO, Ph) were synthesized by the reaction of α-(fluorosulfato)pentafluoroacetone with MeOH or C6H6/A1Cl3. In the presence of bases compound (I), depending on the reaction conditions, forms either cyclic sulfates or products of their isomerization — substituted α-fluorosulfato-trifluoropropionic acid fluorides which are capable of nucleophilic substitution of FSO3 groups in reaction with the nucleophiles.

Conjugate fluorosulfatohalogenation of fluoroolefines.

Abstract Halogen fluorosulfates XOSO2F (XCl, Br) were added to perfluoro- 4-methylpentene-2 (I) to form a mixture of isomeric fluorosulfatohalogenides (IIa–b, IIIa–b) in 1:1 ratio. (IIa, b) are the main products in electrolysis of HOSO2F in presence of (I) and Cl2, or Br2. The predominant formation of these regioisomers can be considered as a result of conjugate addition of (FSO3)2 and halogen to (I).

Fluoroaliphatic esters of fluorosulfonic acid. 3. Decomposition of poly(fluorosulfato)perfluoroalkanes under the action of antimony pentafluoride

Vicinal bis(fluorosulfato)perfluoroalkanes containing FSO3 groups in the middle of a fluorocarbon chain eliminate one or two molecules of sulfuryl fluoride under the action of SbF5, forming a mixture of isomeric α-fluorosulfato ketones and α-diketones.

Fluoroaliphatic esters of fluorosulfonic acid. 4. Reactions of α-fluorosulfatoperfluoro ketones with nucleophilic reagents

Abstractα-Fluorosulfatoperfluoroethyl isopropyl ketone I and fluorosulfatopentafluoroacetone II react with alkali metal chlorides and bromides to form the corresponding α-haloperfluoro ketones as a result of direct nucleophilic substitution.