# US 11,897,853 B2 · Synthesis of 1,1,2-trifluoro-4-(substituted sufonyl)-but-1-ene > Agents: this data is available as JSON from the patentgrep API and MCP server — see https://patentgrep.com/llms.txt - Number: US 11,897,853 B2 - Document ID: US11897853B2 - Status: Granted - Kind: B2 - Application number: 17/419,417 - Filed: 2019-12-30 - Published: 2021-12-16 - Granted: 2024-02-13 - Earliest claimed: 2018-12-31 - Assignees: Adama Makhteshim Ltd. - Applicants: Adama Makhteshim Ltd. - Inventors: Thomas Zell; Shlomi Cohen - Web page: https://patentgrep.com/patent/US11897853B2 ## CPC - C07D 277/36: Sulfur atoms - B01J 23/30: Tungsten - C07D: HETEROCYCLIC COMPOUNDS (macromolecular compounds C08) - B01J: CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS ## Abstract The present invention provides a process for preparing a compound of formula [I] from a compound of formula [II] using an oxidizing agent and a catalyst, the process is carried out at a low temperature. ## Claims ### Claim 1 A process for preparing a compound of formula [I], the process comprises: (a) reacting a compound of formula [II] with an oxidizing agent and a catalyst, wherein the process is carried out at a temperature of about −5° C.-25° C. wherein, R1 is an optionally substituted heterocyclic aromatic ring, wherein the catalyst is selected from the group consisting of TaCl5, Ta(OEt)5, NbCl5, Nb2O5, TiO2/H3PO4, Ti(OiPr)4, V2O3, V2O5, VO(acac)2, Na2WO4, WO2, WO3, WO, WF6, wrought tungsten and two tungsten-copper pseudoalloys, W metal, W metal in combination with Al2O3, WF6, mixed oxo-flurocomplexes of W(VI), WO5·HMPT·H2O wherein HMPT is hexamethyl phosophoric acid triamide, mixed oxo-flurocomplexes of W(IV), WO2F2, WOF4, mixed oxo-chlorocomplexes of W(IV), WO2Cl2, WOCl4, W(CO)6, H2WO4(aq,), MoO3, Na2MoO4, and H4PMo11VO40; and (b) obtaining the compound of formula (I). ### Claim 2 (depends on 1) The process according to claim 1, wherein the temperature is about 0° C. -20° C. ### Claim 3 (depends on 1) The process according to claim 1, wherein the temperature is about 5° C. -15° C. ### Claim 4 (depends on 1) The process according to claim 1, wherein the temperature is about 8° C. -10° C. ### Claim 5 (depends on 1) The process according to claim 1, wherein the oxidizing agent is selected from a group consisting of hydrogen peroxide, m-chloroperoxybenzoic acid, peroxyacetic acid, peroxy-benzoic acid, magnesium monoperoxyphthalate, potassium peroxymonosulfate, bis(trimethylsilyl) peroxide, methylsilyl peroxide, nickel peroxide, trifluoroperacetic acid, 2,4-dinitroperbenzoic acids, peroxysulfuric acid, carbonoperoxoic acid, sodium perborate monohydrate, and tertbutyl hydroperoxide. ### Claim 6 (depends on 5) The process according to claim 5, wherein the oxidizing agent is hydrogen peroxide. ### Claim 7 (depends on 6) The process according to claim 6, wherein the concentration of hydrogen peroxide in water is at least 30%. ### Claim 8 (depends on 7) The process according to claim 7, wherein the concentration of hydrogen peroxide in water is 50%. ### Claim 9 (depends on 1) The process according to claim 1, wherein the catalyst is selected from the group consisting of TaCl5, Ta(OEt)5, NbCl5, Nb2O5, TiO2/H3PO4, Ti(OiPr)4, V2O3, V2O5, VO(acac)2, Na2WO4, WO2, MoO3, Na2MoO4, and H4PMo11VO40. ### Claim 10 (depends on 9) The process according to claim 9, wherein the catalyst is selected from the group consisting of NbCl5, TaCl5, Na2WO4 and Na2MoO4. ### Claim 11 (depends on 10) The process according to claim 10, wherein the catalyst is Na2WO4. ### Claim 12 (depends on 1) The process according to claim 1, wherein the process is carried out in a solvent selected from a group consisting of alcohols, nitriles, ethers, chlorinated solvents, optionally substituted aliphatic, alicyclic and aromatic solvents or a combination thereof. ### Claim 13 (depends on 12) The process according to claim 12, wherein the process is carried out in a solvent selected from a group consisting of methanol, acetonitrile, toluene or a combination thereof. ### Claim 14 (depends on 12) The process according to claim 12, wherein the solvent is methanol. ### Claim 15 (depends on 1) The process according to claim 1, wherein the molar ratio between the compound of formula [II] and the catalyst is from 1:1 to 100:1. ### Claim 16 (depends on 15) The process according to claim 15, wherein the molar ratio between the compound of formula [II] and the catalyst is from 10:1 to 20:1. ### Claim 17 (depends on 15) The process according to claim 15, wherein the molar ratio between the compound of formula [II] and the catalyst is 15:1. ### Claim 18 (depends on 1) The process according to claim 1, wherein the molar ratio between the compound of formula [II] and the oxidizing agent is from 1:1 to 1:10. ### Claim 19 (depends on 18) The process according to claim 18, wherein the molar ratio between the compound of formula [II] and the oxidizing agent is from 1:1 to 1:5. ### Claim 20 (depends on 18) The process according to claim 18, wherein the molar ratio between the compound of formula [II] and the oxidizing agent is about 1:4. ### Claim 21 (depends on 1) The process according to claim 1, wherein the process is carried out for less than 24h. ### Claim 22 (depends on 21) The process according to claim 21, wherein the process is carried out for less than 12h. ### Claim 23 (depends on 22) The process according to claim 22, wherein the process is carried out for less than 10h. ### Claim 24 (depends on 1) The process according to claim 1, wherein the conversion of a compound of formula [II] to a compound of formula [I] is higher than 90%. ### Claim 25 (depends on 1) The process according to claim 1, wherein the chemical yield is higher than 85%. ### Claim 26 (depends on 1) The process according to claim 1, wherein the compound of formula [I] is further purified by recrystallization. ### Claim 27 (depends on 26) The process according to claim 26, wherein the recrystallization is by cooling a hot saturated solution. ### Claim 28 (depends on 26) The process according to claim 26, wherein the recrystallization is by cooling a hot saturated solution of a non-polar solvent. ### Claim 29 (depends on 28) The process according to claim 28, wherein the non-polar solvent is methyl cyclohexane or heptane or a combination thereof. ### Claim 30 (depends on 26) The process according to claim 26, wherein the purification is carried out at a temperature range of about 0-70° C. ### Claim 31 (depends on 26) The process according to claim 26, wherein the yield of the purified product is higher than 80%. ### Claim 32 (depends on 1) The process according to claim 1, wherein R1 is selected from a group consisting of optionally substituted thiophene, optionally substituted thiazole and optionally substituted thiadiazole. ### Claim 33 (depends on 1) The process according to claim 1, wherein the compound of formula [I] is fluensulfone. ### Claim 34 (depends on 1) The process according to claim 1, wherein the compound of formula [II] is chloro-2-[(3,4,4-trifluoro-3-buten-1-yl)thio]-thiazole.