for Organic Synthesis Valentine G. Nenajdenko,*,†,§ Vasiliy M. Muzalevskiy,† and Aleksey V. Shastin†,‡ †Department of Chemistry, Moscow State University, Leninskie Gory, Moscow 119992, Russia ‡The Institute of Problems of Chemical Physics of the Russian Academy of Sciences (IPCP RAS), Chernogolovka, Moscow Region 142432, Russia A.N. Nesmeyanov Institute of Organoelement Compounds of Russian Academy of Sciences (INEOS RAS), 119991, GSP-1, Moscow, V-334, Vavilova St. 28, Russia

Polyfluorinated ethanes as versatile fluorinated C2-building blocks for organic synthesis.

Syntheses and properties of aliphatic and aromatic polythioesters (PTEs) were reviewed including polythiocarbonates and polythiourethanes. The content is subdivided into the following sections: PTEs of aliphatic α‐mercapto carboxylic acid, PTEs of ω‐mercapto carboxylic acids, PTEs derived from α,ω‐dimercapto alkanes, aromatic poly(thioester)s, aliphatic poly(thiocarbonate)s, aliphatic poly(thiourethane)s and aromatic polythiocarbonates. The synthetic strategies reviewed in this article include anionic and cationic ring‐opening polymerizations, polycondensations in bulk, polycondensations in solutions, interfacial polycondensations and in vitro enzymatic polycondensations.

Poly(thioester)s

Described is a reaction of a fluorinated alkoxide with an alkyl fluorovinylalkyl ether, the alkyl fluorovinylalkyl ether having alpha-beta carbon-carbon unsaturation relative to the ether oxygen, to produce a hydrofluoroether.

Process for preparing hydrofluoroethers

Perfluoroisobutene-MeOH adduct (2H-octafluoroisobutyl methyl ether) converted to hexafluoropropane by reaction with trialkyl amine (e.g., triethylamine) and H₂O. 1,1,1,3,3-Pentafluoropropene also produced in lesser amounts. Electrolysis of reaction product in anhydrous HF (at 10° - 50°C, 0 - 140 kPa, and 50 - 300 amps/m² anode area) yields C₃F₈ and some CF₃CFHCF₃ condensed out of gas stream from electrolysis cell.

Process for making hexafluoropropane and perfluoropropane

Synthesis and surface properties of semi-fluorinated gemini surfactants with two reactive bromo pendant groups.

1.

In competition for conjugation with an olefinic bond the phosphono group has a mote powerful electronwithdrawing effect than the trifluoromethyl group. The reaction of diethyl perfluoropropenylphosphonate with various nucleophilic reagents leads to products in which a fluorine atom in theβ -position relative to the phosphono group is replaced.




2.

It was found that the electron-withdrawing effect of two trifluoromethyl groups is more powerful than the effect due to one phosphono group: in the reaction of diethyl perfluoroisobutenylphosphonate with nucleophilic reagents it is theα-fluorine atom that is replaced; in the case of diethyl α-hydrohexafluoroisobutenylphosphonate, addition products are formed with nucleophilic reagents, i.e. α-substituted-α, β-dihydrohexafluoroisobutylphosphonic esters.

Reactions of fluoro olefins

Reactions of mercapto amino acids: Communication 9. Synthesis of ?-acylamino ?-thiolactones

1.

It was shown that 3, 3, 3-trifluoropropene, trifluoroethylene, and 1,1-diflnoroethylene readily undergo addition of bromine in glacial acetic acid.




2.

For the first time, fluoroolefins were caused to undergo conjugated addition. By the action of bromine on some fluoroolefins in glacial acetic acid, some acetic esters of β -bromo α,α -difluoro alcohols were prepared.




3.

It was shown that compounds of this new type have the character of mixed acid anhydrides.




4.

By conjugated addition of bromine in water, the bromohydrin of 3,3,3-trifluoropropene was obtained, and this was converted into 2,3-epoxy- 1,1,1-trifluoropropane.




5.

By conjugated addition of bromine to trifluoroethylene in water, bromofluoroacetic acid was obtained.




6.

The addition of mercuric acetate to 1,1-difluoroethylene was effected in acetic acid and in alcohol, the products being the unstable 2-acetoxy-2,2-difluoroethylmercury and 2-ethoxy-2,2-difluoroethylmercury acetates, which are readily transformed into a (halomercuri)acetic acid and its esters.

https://link.springer.com/content/pdf/10.1007/BF01169991.pdf

Addition reactions of perfluoroolefins communication 5. Conjugated addition of halogens

1.

Concerted addition of halogens to polyfluoroolefins in perhalogenated acid solutions have been carried out. A series of new haloacetates of α,α-difluoro-Β-bromo(chloro) substituted alcohols has been prepared.




2.

Concerted additions of highly dissociated mercuric salts to polyfluoroolefins have been carried out in acetic acid and alcohol to form unsymmetrical organomercury compounds with either hydroxy or acetoxy groups in the polyfluoroinated radical.

Addition reactions of fluoroolefins

1.

The alkylation of the perfluoro-tert-butyl carbanion with acrylonitrile and the esters of acrylic acid is a convenient method for the preparation ofβ-(perfluoro-tert-butyl)propionic acid derivatives.




2.

The alkylation of the perfluoro-tert-butyl carbanion with ethylene oxide gaveβ-(perfluoro-tert-butyl) ethanol.




3.

The alkylation of the perfluoro-tert-butyl carbanion with ethylene thiooxide gaveβ-(perfluoro-tert-butyl)ethyl perfluoroisobutenyl sulfide and the bis-[β-(perfluoro-tert-butyl)ethyl] dithioacetal of hexa-fluorodimethylketone.




4.

The reaction of perfluoroisobutylene with halo derivatives in the presence of metal fluorides gave (perfluoro-tert-butyl)methane, 1-(perfluoro-tert-butyl)butane, 1-(perfluoro-tert-butyl)-2-propene, and ω-(perfluoro-tert-butyl)toluene in 70–90% yield.

Reaction of perfluoro-tert-butyl carbanion with olefins, containing an activated double bond, and with three-membered heterocycles and various halo derivatives

E. Ya. Pervova

Papers

Reactions of fluoro olefins

Reactions of mercapto amino acids: Communication 9. Synthesis of ?-acylamino ?-thiolactones

Addition reactions of perfluoroolefins communication 5. Conjugated addition of halogens

Addition reactions of fluoroolefins

Reaction of perfluoro-tert-butyl carbanion with olefins, containing an activated double bond, and with three-membered heterocycles and various halo derivatives