29514-94-1

Synthetic route

5-iodooctafluoro-3-oxapentanesulfonyl fluoride (66137-74-4) → 1,1,2,2-tetrafluoro-2-(trifluoroethenyloxy)ethanesulfonyl fluoride (29514-94-1)

Conditions	Yield
With 1-methyl-pyrrolidin-2-one; iron(III) chloride In tetrahydrofuran at 80℃; for 6h; Temperature; Reagent/catalyst; Solvent;	96%

1,1,2,2-tetrafluoro-2-(trifluoroethenyloxy)ethanesulfonyl chloride (27009-57-0) → 1,1,2,2-tetrafluoro-2-(trifluoroethenyloxy)ethanesulfonyl fluoride (29514-94-1)

Conditions	Yield
With potassium fluoride In acetonitrile at 20 - 34℃; for 24h; Product distribution / selectivity;	92.7%
With potassium fluoride In sulfolane at 60℃; for 3h; Product distribution / selectivity;	91.5%
With sodium fluoride In sulfolane at 73℃; Product distribution / selectivity;	51.4%

sodium 1,1,2,2-tetrafluoro-2-(trifluoroethenyloxy)ethanesulfonate → 1,1,2,2-tetrafluoro-2-(trifluoroethenyloxy)ethanesulfonyl fluoride (29514-94-1)

Conditions	Yield
With Tetraethylene glycol dimethyl ether; hexafluoropropene-diethylamine adduct at 20 - 80℃; for 4h; Reagent/catalyst;	86%
With sulfur tetrafluoride; hydrogen fluoride at 0 - 20℃; for 16h;	85%

2-(1,2-dichloro-1,2,2-trifluoroethoxy)perfluorethanesulfonyl fluoride (144728-59-6) → 1,1,2,2-tetrafluoro-2-(trifluoroethenyloxy)ethanesulfonyl fluoride (29514-94-1)

Conditions	Yield
With 1-methyl-pyrrolidin-2-one; bromine; zinc at 35 - 85℃; for 2h; Inert atmosphere; Cooling with ice;	82%
With 1-methyl-pyrrolidin-2-one; bromine; zinc at 35 - 85℃; for 2.5h; Autoclave; Inert atmosphere;	82%

1,1,2,2-tetrafluoro-2-(trifluoroethenyloxy)ethanesulfonic acid (111173-24-1) → 1,1,2,2-tetrafluoro-2-(trifluoroethenyloxy)ethanesulfonyl fluoride (29514-94-1)

Conditions	Yield
With Tetraethylene glycol dimethyl ether; hexafluoropropene-diethylamine adduct at 20 - 80℃; for 4h;	81%

5-iodooctafluoro-3-oxapentanesulfonyl fluoride (66137-74-4) + methylmagnesium bromide (75-16-1) → 1,1,2,2-tetrafluoro-2-(trifluoroethenyloxy)ethanesulfonyl fluoride (29514-94-1)

Conditions	Yield
In tetrahydrofuran 155°C, 2 h;	60%
In tetrahydrofuran 155°C, 2 h;	60%

C7H3F7N2O3S (446312-63-6) → 1,1,2,2-tetrafluoro-2-(trifluoroethenyloxy)ethanesulfonyl fluoride (29514-94-1)

Conditions	Yield
With hydrogen fluoride at 60℃; for 0.5h;	71 % Spectr.

1,1,2,2-tetrafluoro-2-(trifluoroethenyloxy)ethanesulfonyl chloride (27009-57-0) + sodium fluoride → 1,1,2,2-tetrafluoro-2-(trifluoroethenyloxy)ethanesulfonyl fluoride (29514-94-1)

FSO2CF2CF2OCF(CF2Cl)COONa (1246760-89-3) → 1,1,2,2-tetrafluoro-2-(trifluoroethenyloxy)ethanesulfonyl fluoride (29514-94-1)

Conditions	Yield
In diethylene glycol dimethyl ether at 140℃;

1,1,2,2-tetrafluoro-2-(trifluoroethenyloxy)ethanesulfonyl fluoride (29514-94-1) + potassium tetrafluoro(2-fluorosulfonyl)-1-ethanolate (81439-24-9) → C6F13IO6S2

Conditions	Yield
With iodine In diethylene glycol dimethyl ether at 20℃; for 24h;	96%

1,1,2,2-tetrafluoro-2-(trifluoroethenyloxy)ethanesulfonyl fluoride (29514-94-1) + Silver 1-fluorosulfuryltetrafluoroethoxide → C6HF13O6S2

Conditions	Yield
With sulfuric acid In diethylene glycol dimethyl ether at 20℃; for 120h;	73%

1,1,2,2-tetrafluoro-2-(trifluoroethenyloxy)ethanesulfonyl fluoride (29514-94-1) → C4Br2F8O3S

Conditions	Yield
With bromine at 0 - 20℃;	65.6%
With bromine at 0℃;

1,1,2,2-tetrafluoro-2-(trifluoroethenyloxy)ethanesulfonyl fluoride (29514-94-1) → perfluorovinyl perfluoroiodoethyl ether (6037-91-8)

Conditions	Yield
With sodium iodide In dimethyl sulfoxide at 20 - 110℃; for 2h; Product distribution / selectivity;	60%

1,1,2,2-tetrafluoro-2-(trifluoroethenyloxy)ethanesulfonyl fluoride (29514-94-1) → 1-(2-fluorosulfonylperfluoroethoxy)-1,2-bis(fluorosulfonyloxy)-1,2,2-trifluoroethane + fluorosulfuric acid 1,2,2,3,4,4-hexafluoro-4-fluorosulfonyloxy-1,3-bis-(1,1,2,2-tetrafluoro-2-fluorosulfonyl-ethoxy)-butyl ester + 2,3-bis(2-fluorosulfonylperfluoroethoxy)-1,4-bis(fluorosulfonyloxy)perfluorobutane + 1,6-bis(fluorosulfonyloxy)-2,3,5-tris(2-fluorosulfonylperfluoroethoxy)perfluorohexane

Conditions	Yield
With potassium fluorosulfonate; bis(fluorosulfuryl) peroxide; fluorosulphonic acid at 28℃; Electrochemical reaction;

1,1,2,2-tetrafluoro-2-(trifluoroethenyloxy)ethanesulfonyl fluoride (29514-94-1) → 2,3-bis(2-fluorosulfonylperfluoroethoxy)-2,3-difluorosuccinyl difluoride + 1,1,2,2-tetrafluoro-2-[2,2,3,4-tetrafluoro-5-oxo-4-(1,1,2,2-tetrafluoro-2-fluorosulfonyl-ethoxy)-tetrahydro-furan-3-yloxy]-ethanesulfonyl fluoride

Conditions	Yield
Stage #1: 1,1,2,2-tetrafluoro-2-(trifluoroethenyloxy)ethanesulfonyl fluoride With potassium fluorosulfonate; bis(fluorosulfuryl) peroxide; fluorosulphonic acid at 28℃; Electrochemical reaction; Stage #2: With cesium fluoride In various solvent(s) Title compound not separated from byproducts;

1,1,2,2-tetrafluoro-2-(trifluoroethenyloxy)ethanesulfonyl fluoride (29514-94-1) → 2-(1,2-dichloro-1,2,2-trifluoroethoxy)perfluorethanesulfonyl fluoride (144728-59-6)

Conditions	Yield
With chlorine In HFC43-10mee at 20℃;

1,1,2,2-tetrafluoro-2-(trifluoroethenyloxy)ethanesulfonyl fluoride (29514-94-1) → C4F7N3O3S + C4HF7N6O3S

Conditions	Yield
With sodium azide; phosphorus pentoxide In acetonitrile at 20 - 40℃; for 51.3167h; Molecular sieve; Inert atmosphere;

1,1,2,2-tetrafluoro-2-(trifluoroethenyloxy)ethanesulfonyl fluoride (29514-94-1) → C4F7O4S(1-)*K(1+) + C4HF5O6S(2-)*2K(1+)

Conditions	Yield
With potassium hydroxide In water; tert-butyl alcohol at 26 - 39℃; for 1.5h; Temperature; Solvent;

Upstream product

• 446312-63-6 C₇H₃F₇N₂O₃S 
• 27009-57-0 1,1,2,2-tetrafluoro-2-(trifluoroethenyloxy)ethanesulfonyl chloride 
• 7681-49-4 sodium fluoride 
• 66137-74-4 5-iodooctafluoro-3-oxapentanesulfonyl fluoride 
• 75-16-1 methylmagnesium bromide 
• 1246760-89-3 FSO₂CF₂CF₂OCF(CF₂Cl)COONa 
• 144728-59-6 2-(1,2-dichloro-1,2,2-trifluoroethoxy)perfluorethanesulfonyl fluoride 
• 111173-24-1 1,1,2,2-tetrafluoro-2-(trifluoroethenyloxy)ethanesulfonic acid 

Downstream Products

• 6037-91-8 2-iodo-1,1,2,2-tetrafluoroethyl trifluorovinyl ether 

Relevant academic research and scientific papers

New preparation of 1,1,2,2-tetrafluoro-2-(trifluoroethenyloxy)-ethanesulfonyl fluoride

A new preparation method of 1,1,2,2-tetrafluoro-2-(trifluoroethenyloxy)-ethanesulfonyl fluoride (8) has been developed utilizing the unique performance of the imidazole protective group. Namely, the electrodonating character of the imidazole protective group on the sulfonyl group enables the formation of the novel intermediate monomer, which can be easily converted to 8 by the reaction with HF.

VINYLSULFONIC ANHYDRIDE, METHOD FOR PRODUCING SAME, AND METHOD FOR PRODUCING VINYLSULFONYL FLUORIDE

The present disclosure is directed to provide a vinylsulfonic anhydride which is useful as a synthetic intermediate for synthesis of a fluorinated monomer. It is also directed to efficiently produce the vinylsulfonic anhydride. It is further directed to efficiently produce a fluorinated monomer using the vinylsulfonic anhydride. A vinylsulfonic anhydride of the present disclosure is expressed by the general formula (1). Further, a process for producing a vinylsulfonic anhydride of the present disclosure includes making a vinylsulfonic acid compound represented by the general formula (2) come in contact and be mixed with an anhydridization agent. Further, a process for producing a vinylsulfonyl fluoride of the present disclosure includes a step (b) of making a vinylsulfonic anhydride represented by the general formula (1) come in contact and be mixed with a fluorinating agent to prepare a reaction mixture including a vinylsulfonyl fluoride represented by the general formula (3) and a vinylsulfonic acid compound represented by the general formula (2).

Preparation method of resin monomer for ion exchange membrane

The invention discloses a preparation method of a resin monomer for an ion exchange membrane. The preparation method comprises the following steps: reacting fluorosulfonyl tetrafluoroethyl oxa-tetrafluoroiodoethane (ICF2CF2OCF2CF2SO2F) with a dehalogenating agent in a solvent; wherein the molar ratio of the fluorosulfonyl tetrafluoroethyl oxa-tetrafluoroiodoethane(ICF2CF2OCF2CF2SO2F) to the dehalogenating agent is (0.1-1): 1, the reacting temperature is between 20 and 200 DEG C, the reacting time is 2 to 8 hours; and cooling, discharging and distilling after the reaction is finished to obtaina resin monomer fluorosulfonyl tetrafluoroethyl oxatrifluoroethylene (CF2 is CFOCF2CF2SO2F) product for the ion exchange membrane; and the method has the advantages of simple process, readily available raw materials, low cost, environmental friendliness and easiness in industrialization.

Preparation method of perfluorovinyl ether sulfonyl fluoride

The invention belongs to the technical field of perfluorinated resin, and particularly relates to a preparation method of Perfluorovinyl ether sulfonyl fluoride. A CF2=CF(OCF2CFX)mO(CF2)nSO2F productis directly generated from perfluorovinyl ether sulfonate CF2=CF(OCF2CFX)mO(CF2)nSO2OM by a one-step reaction under the action of a fluorinating reagent CHClFCF2N(C2H5)2,CF3CHFCF2N(C2H5)2. The preparation method has the advantages of simple process, easiness in operation, low reagent cost, avoidance of the production of waste acid gas and waste liquid as well as the increase of multi-step wastageand by-products; reaction steps are reduced, and the use of high-toxicity and high-risk reagents is avoided at the same time, and the yield can be up to 80 percent or more.

Preparation method of direct-chain perfluoro vinyl ether by using sulfuryl fluoride group as end group

The invention belongs to the field of fine chemicals, and particularly relates to a preparation method of direct-chain perfluoro vinyl ether by using a sulfuryl fluoride group as an end group. The preparation method comprises the following steps of using the chlorinated alkyl vinyl ether as the raw material, performing the sulfonation reaction and chlorination reaction to obtain a product, and performing the addition reaction on the product with chloride gas, so as to obtain the chlorinated alkyl ether by using sulfuryl fluoride as the end group; performing the fluorination reaction on the chlorinated alkyl ether by using the sulfuryl fluoride as the end group, so as to obtain the perfluoro alkyl ether; performing the reduction reaction on the perfluoro alkyl ether, so as to obtain the direct-chain perfluoro vinyl ether by using the sulfuryl fluoride group as the end group, namely CF2=CFOCF2(CF2)nSO2F, wherein n is equal to 1 to 6. The preparation method has the advantages that by using the chlorinated alkyl vinyl ether as the raw material, the commercialized effect of the raw material is realized, the obtaining is easy, the cost is low and is lower than the cost of the fluoride-containing compound, the high-temperature cracking route and non-conventional monomer are avoided, the product is obtained via the high-yield reaction, the production of excessive fluoride-containing waste liquid is avoided, and the cost is reduced; the operation is simple and convenient, the implementing is easy, the yield rate is higher, the waste of the fluoride resource is avoided, and the production amount of the fluoride-containing waste is reduced.

Preparation method for perfluoro vinyl ether with sulfuryl fluoride group as terminal group

The invention belongs to the field of fine chemicals and specifically relates to a preparation method for perfluoro vinyl ether with a sulfuryl fluoride group as a terminal group. The perfluoro vinyl ether with the sulfuryl fluoride group as the terminal group is prepared in the manner of taking fluorosulfonyl perfluoroalkyl fluoride as a raw material and performing salt forming reaction, fluoridation and reduction reaction. The perfluoro vinyl ether with the sulfuryl fluoride group as the terminal group is CF2=CFOCF2(CF2)nSO2F, wherein n is equal to 1-3. According to the invention, the fluorosulfonyl perfluoroalkyl fluoride is taken as the raw material, the raw material is commercialized and easily acquired, the cost is low, the high-temperature pyrolyzing route and the unconventional monomer are avoided, the product is acquired through high-yield reaction, much fluorine-containing effluent is prevented from generation and the cost is lowered. The yield is higher, the waste of fluorine resource is avoided and the generation of fluorine-containing waste is reduced.

TRICHLORO-TRIFLUORO-PROPYLENE OXIDE AND METHOD FOR PRODUCING TRICHLORO-TRIFLUORO-PROPYLENE OXIDE

The present invention provides a novel propylene oxide and a method for producing the same as well as a production method using the novel propylene oxide. The present invention is 1,1,3-trichloro-2,3,3-trifluoropropylene oxide. The present invention is a method for producing 1,1,3-trichloro-2,3,3-trifluoropropylene oxide which comprises the step of oxidizing a vinyl compound of CF2Cl-CF=CCl2.

METHOD FOR PRODUCING FLUORINE-CONTAINING FLUOROSULFONYL ALKYLVINYL ETHER

Disclosed is a method for producing a fluorine-containing fluorosulfonyl alkylvinyl ether represented by the following chemical formula: CF2=CFOCF2CF2SO2F which is characterized in that a fluorine-containing chlorosulfonyl alkylvinyl ether represented by the following chemical formula: CF2=CFOCF2CF2SO2Cl is reacted with a fluorinating agent represented by the following chemical formula: KF·(HF)n (wherein n represents a number of 0-5) in a polar organic solvent at a temperature not more than 70 C. With this method, a fluorine-containing fluorosulfonyl alkylvinyl ether can be commercially advantageously produced at low cost with high yield by a simple process.

PROCESS FOR PRODUCING FLUORINATED FLUOROSULFONYLALKYL VINYL ETHER

The present invention provides a process for producing a fluorinated fluorosulfonylalkyl vinyl ether represented by general formula (2):CF2=CFO(CF2CF(CF3)O)nCF2CF2SO2F wherein n is an integer from 0 to 10, comprising fluorinating a perfluorovinylether sulfonate with SF4 and HF, the perfluorovinylether sulfonate being represented by general formula (1):CF2=CFO(CF2CF(CF3)O)nCF2CF2SO3M wherein M is Ma or Mb1/2, provided that Ma is an alkali metal and Mb is an alkaline earth metal; and n is as defined above. According to the process of the invention, the fluorinated fluorosulfonylalkyl vinyl ether can be produced in high yield in an industrially advantageous manner.