791-50-4

Usage

Uses

Used in Chemical Synthesis Industry:
2,2,4,4-tetrakis(trifluoromethyl)-1,3-dithietane is used as a synthetic intermediate for the production of various organic compounds, particularly vinyl ethers. Its reactivity and unique structure make it a valuable component in the synthesis of specialty chemicals and materials with specific properties.

InChI:InChI=1/C6F12S2/c7-3(8,9)1(4(10,11)12)19-2(20-1,5(13,14)15)6(16,17)18

Upstream product

• 116-15-4 perfluoropropylene 
• 1490-33-1 hexafluorothioacetone 
• 87108-79-0 sulfoxid 
• 2782-91-4 1,1,3,3-tetramethyl-2-thiourea 
• 684-16-2 Hexafluoroacetone 
• 99648-45-0 2-(Chlorcarbonylthio)-1,1,1,3,3,3-hexafluor-2-propansulfenylchlorid 
• 126-33-0 sulfolane 
• 756-88-7 bis-(1,2,2,2-tetrafluoro-1-trifluoromethyl-ethyl)-mercury 
• 7704-34-9 sulfur 
• 754-62-1 bis(perfluoroisopropyl) disulfide 
• 1588-32-5 bis(perfluoro-2-propyl) trisulfide 
• 1588-31-4 bis(perfluoroisopropyl) tetrasulfide 
• 603-35-0 triphenylphosphine 
• 64997-94-0 trithiolane 

Downstream Products

• 73607-11-1 4-CH₃C₆H₄CHC(CF₃)2 
• 50849-61-1 3-CF₃C₆H₄CN(CF₃)2 
• 50713-44-5 2,4-Dinitro-1-(2,2,2-trifluoro-1-methoxy-1-trifluoromethyl-ethylsulfanyl)-benzene 
• 50713-50-3 1-(1-Ethoxy-2,2,2-trifluoro-1-trifluoromethyl-ethylsulfanyl)-2,4-dinitro-benzene 
• 41879-17-8 3,3,3-Trifluoro-1-phenyl-2-(trifluoromethyl)-1-propene 
• 34025-20-2 4-chloro-N-[2,2,2-trifluoro-1-(trifluoromethyl)ethylidene]aniline 
• 73607-12-2 1-methoxy-4-(3,3,3-trifluoro-2-(trifluoromethyl)prop-1-en-1-yl)benzene 
• 34025-21-3 4-methoxy-N-<2,2,2-trifluoro-1-(trifluoromethyl)ethylidene>benzeneamine 
• 400-16-8 Hexafluor-aceton-semicarbazon 
• 50713-47-8 {2,2,2-Trifluoro-1-trifluoromethyl-1-[2,2,2-trifluoro-1-trifluoromethyl-1-(2,2,2-trifluoro-1-trifluoromethyl-ethylsulfanyl)-ethylsulfanyl]-ethyldisulfanyl}-benzene 
• 2002-95-1 N-(hexafluoroisopropylidene)aniline 
• 50713-48-9 1-Methyl-4-(2,2,2-trifluoro-1-trifluoromethyl-1-{2,2,2-trifluoro-1-trifluoromethyl-1-[2,2,2-trifluoro-1-trifluoromethyl-1-(2,2,2-trifluoro-1-trifluoromethyl-ethylsulfanyl)-ethylsulfanyl]-ethylsulfanyl}-ethyldisulfanyl)-benzene 
• 36052-90-1 3-ClC₆H₄CN(CF₃)2 
• 36052-89-8 3-CH₃C₆H₄CN(CF₃)2 

Relevant academic research and scientific papers

Reaction of hexafluorothioacetone dimer with azoles. Practical synthesis of N-(hexafluoro-iso-propyl)azoles

The reaction of azoles with 2,2,4,4-tetrakis-(trifluoromethyl)-1,3- dithietane led to the unexpected formation of N-(hexafluoro-isopropyl)azoles and sulfur, providing access to a group of compounds bearing a (CF 3)2CH-group at nitrog

Reaction of hexafluorothioacetone dimer with ketene dimethylacetal and dimethyl thioacetal

It was demonstrated that the fluoride anion catalyzed reaction of 2,2,4,4-terakis(trifluoromethyl)dithienane-1,3 (1, cyclic dimer of hexafluorothioacetone) with ketene dimethylacetal (2, 1,1-dimethoxy ethylene) leads to the formation of 2,2-bis(trifluoromethyl)-3,3-bis(methoxy)thietane (3), rather than expected 2,2-bis(trifluoromethyl)-4,4-bis(methoxy)thietane isomer (4). Compound 3 is a kinetic product and upon storage at ambient temperature undergoes quantitative isomerization into 4. The isomerization proceeds through the formation of free hexafluorothioacetone, which was trapped as cycloadduct with quadricyclane. It was also demonstrated that the ethylene 2 is able to react with dimer 1 in the absence of the catalyst. The reaction results in unusual ring opening process producing (2,2-dimethoxyvinyl)(1,1,1,3,3,3- hexafluoro-2-(1,1,1,3,3,3-hexafluoropropan-2-yl)thio)propan-2-yl)sulfane (11).

Reaction of 2,2,4,4-tetrakis(trifluoromethyl)-1,3-dithiethane with N-vinyl compounds

The reaction of hexafluorothioacetone dimer (2,2,4,4- tetrakis(trifluoromethyl)-1,3-dithiethane, 1) with vinylamides leads to the rapid formation of [2 + 2] cycloadducts: 4-amino-2,2-bis(trifluoromethyl) thietanes. The reaction proceeds in polar solvents (DMF, DMSO) in the absence of a catalyst at elevated temperature producing the corresponding cycloadducts in 47-86% yield. The reaction of N-vinylimidazole unexpectedly led to the formation of the corresponding 1-(hexafluoroisopropyl)-3-vinyl-1,3-dihydro-2Himidazole-2- thione (5). The structure of this compound, along with the structures of two new thietanes was confirmed by single crystal X-ray diffraction.

Simple synthesis of 1,1-bis(trifluoromethyl)cyclopropanes

A new, simple synthesis of 1,1-bis(trifluoromethyl)cyclopropanes has been discovered. It is based on the reaction of readily available 2,2-bis(trifluoromethyl)thietanes with tertiary phosphines in a polar solvent, which leads to an unusual desulfurization

Reactions of polyfluorinated thietanes. Selective synthesis of 4-R-2,2-bis(trifluoromethyl)thietane-1-S-oxides and 2-substituted 5-fluoro-4-(trifluoromethyl)-2,3-dihydrothiophenes

Oxidation of 4-substituted 2,2-bis(trifluoromethyl)thietanes by m-chloroperoxybenzoic acid results in selective formation of the corresponding S-oxides in 65-86% yield. Oxidation of 4-C2H5S-2,2-bis(trifluoromethyl)thietane under mild conditions led to selective formation of 4-C2H5SO2-2,2-bis(trifluoromethyl)thietane, which under more rigorous conditions was selectively converted into trans-4-C2H5SO2-2,2-bis(trifluoromethyl)thietane-1-S-oxide. Reaction of 4-substituted 2,2-bis(trifluoromethyl)thietanes with activated aluminum powder results in a highly selective ring expansion process, producing the corresponding 5-fluoro-4-(trifluoromethyl)-2,3-dihydro-2-alkoxythiophenes in 58-93% yield. These compounds were also prepared in 61-85% yield using a "one-pot" procedure, starting from sulfur, hexafluoropropene and the corresponding vinyl ether without isolation of any intermediates. Both 2-i-C3H7O- and 2-t-C4H9O- 5-fluoro-4-(trifluoromethyl)-2,3-dihydrothiophenes were converted into 2-fluoro-3-trifluormethylthiophene by reaction with P2O5.

On the exchange reaction,, using hexafluoroacetone

The reaction of λ3-phospha-diazetidin-thione, 1 with hexafluoroacetone (HFA) furnished not only the expected addition product, the λ5P-perfluoropinacolyl phosphorane, 2. In addition, HFA was observed to cause {A figure is presented} exchange in 2, and exclusive formation of a urea derivative, 3, was noted upon prolonged interaction of HFA with 2. Likewise, N,N,N′,N′,-tetramethylthiourea, 1, was found to be converted to N,N,N′,N′-tetrarmethylurea, 5, by HFA. The reactions were followed by 1H-, 13C-, 19F- and 31P-n.m.r. spectroscopy.

Bis(trifluoromethyl)sulfine, (CF3)2C=SO: New Syntheses and Some Reactions

New methods for the synthesis of bis(trifluoromethyl)sulfine (sulfoxide) (9) are reported.Pyrolysis, photolysis, and hydrolysis of the compound were investigated as well as the typical behaviour in reactions with the thiocarbonyl group (thiophosgene), with anthracene (Diels-Alder addition) and halogens.

Synthesis and Properties of Tetrakis(trifluoromethyl)-1,3-dithietane S-Oxides and Bis(trifluoromethyl)sulfine

The corresponding S-oxides 2-6 could be obtained by oxidation of 2,2,4,4-tetrakis(trifluoromethyl)-1,3-dithietane (1).Similar oxidation of 2,2,4,4-tetrakis(trifluoromethyl)thiirane (8) yields the episulfoxide 12, but not the episulfone 14.Pyrolysis of 2, 3, 5, and 6 have been investigated and bis(trifluoromethyl)sulfine (7) could be isolated as the first member of perfluoroalkylsulfines as well as the sulfonylfluoride 13 being the product of isomerization of bis(trifluoromethyl)sulfene (9). 7 could also be obtained by ring opening from 3 with bases and by oxidation of hexafluorothioacetone (11), respectively.Solvolytic ring opening in 5 and 6 yields the sulfones 16 and 17.

Process of preparing hexafluorothioacetone dimer

An improved process for the reaction of hexafluoropropene with elemental sulfur and alkali metal fluoride such as KF, in an aprotic solvent selected from the group consisting of acetonitrile dimethylacetamide, dimethylformamide, dimethyl sulfoxide and N-methyl pyrrolidone under substantially one atmosphere pressure and at tempertures of between about 25° and 100° C. is disclosed. The preferred alkali metal fluoride is KF and the preferred aprotic solvent is dimethylformamide.