WO2016146040A1 - Procédé industriel pour la production de 3,7-di-tert-butyl-s- (trifluorométhyl)dibenzothiophénium trifluorométhanesulfonate - Google Patents

Procédé industriel pour la production de 3,7-di-tert-butyl-s- (trifluorométhyl)dibenzothiophénium trifluorométhanesulfonate Download PDF

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WO2016146040A1
WO2016146040A1 PCT/CN2016/076181 CN2016076181W WO2016146040A1 WO 2016146040 A1 WO2016146040 A1 WO 2016146040A1 CN 2016076181 W CN2016076181 W CN 2016076181W WO 2016146040 A1 WO2016146040 A1 WO 2016146040A1
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tert
formula
butyl
butylbiphenyl
trifluoromethanesulfinate
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PCT/CN2016/076181
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English (en)
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Teruo Umemoto
Tianhao ZHU
Bin Zhang
Yuanqiang Li
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Zhejiang Jiuzhou Pharmaceutical Co.,Ltd
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D333/00—Heterocyclic compounds containing five-membered rings having one sulfur atom as the only ring hetero atom
    • C07D333/50—Heterocyclic compounds containing five-membered rings having one sulfur atom as the only ring hetero atom condensed with carbocyclic rings or ring systems
    • C07D333/76—Dibenzothiophenes

Definitions

  • the present invention relates toan industrial method forthe production of3, 7-di-tert-butyl-S- (trifluoromethyl) dibenzothiophenium trifluoromethanesulfonate which is a useful electrophilic trifluoromethylating agent.
  • a trifluoromethyl group isan importantfunctional group for developing effective medicines, agrochemicals, and other useful materials (for example, see, J. Fluorine Chem. 2006, 127, 1013-1029; Chem. Soc. Rev., 2008, 37, 237-432; “Fluorine and the environment” , Vol. 2, Chapter 4, pp 121-175 (2006) (ISSN 1872-0358) ) .
  • 3, 7-di-tert-butyl-S- (trifluoromethyl) dibenzothiophenium trifluoromethanesulfonate was developed as one of the useful electrophilic trifluoromethylating agents (see, J. Am. Chem.
  • step 1 reaction of 4, 4’ -di-tert-butylbiphenyl with an iodating agent (I 2 /HIO 4 ) including an iodine element which is expensive compared to other halogens (see, J. Org. Chem. 1979, 44, pp.
  • step 2 reaction of the resulting 4, 4’ -di-tert-butyl-2-iodobiphenyl with CF 3 SCu which was prepared by two steps from carbon disulfide and expensive silver fluoride (see, Journal of Fluorine Chemistry, 1990, Vol. 48, pp.
  • step 3 oxidation of the resulting 4, 4’ -di-tert-butyl-2- (trifluoromethylthio) biphenyl with m-chloroperbenzoic acid; and (step 4) , cyclization of the resulting 4, 4’ -di-tert-butyl-2- (trifluoromethylsulfinyl) biphenyl with trifluoromethanesulfonic anhydride.
  • CF 3 SCu used in the step 2 was also prepared from reaction of CF 3 SSCF 3 with Cu. However, CF 3 SSCF 3 is anexpensive and highly toxicliquid of low boiling point (bp 34-35 °C) (see, Heteroatom Chem., 1992, Vol. 3, pp. 189-192) .
  • X - is a conjugated base of Br nsted acid. Br nsted acid is expressed asHX and its conjugated base is X - .
  • HX Br nsted acids
  • strong acids such as trifluoromethanesulfonic acid (CF 3 SO 3 H) , HBF 4 , HPF 6 , H 2 SO 4 , HCl, HBr, and the like are exemplified, and as preferable examples of X - , CF 3 SO 3 - , BF 4 - , PF 6 - , HSO 4 - , Cl - , Br - , and the like are exemplified.
  • 3, 7-Di-tert-butyl-S- (trifluoromethyl) dibenzothiophenium salt (I’ ) having X - other than CF 3 SO 3 - can be prepared by counteranion exchange reaction from 3, 7-di-tert-butyl-S- (trifluoromethyl) dibenzothiophenium trifluoromethanesulfonate.
  • the present invention isto provide a new, highlyeffective and environmentally friendly method for the production of 3, 7-di-tert-butyl-S- (trifluoromethyl) dibenzothiophenium trifluoromethanesulfonate which is useful as an electrophilic trifluoromethylating agent.
  • the inventors have thoroughly studied an idea of making a new method for the industrial production of 3, 7-di-tert-butyl-S- (trifluoromethyl) dibenzothiophenium trifluoromethanesulfonate.
  • the inventors succeeded in making a new method comprising a one-pot and environmentally friendly process and an easy isolation process for the production of 3, 7-di-tert-butyl-S- (trifluoromethyl) dibenzothiophenium trifluoromethanesulfonate, which can overcome the problems discussed above.
  • the present invention relates toan industrial method for the production of 3, 7-di-tert-butyl-S- (trifluoromethyl) dibenzothiophenium trifluoromethanesulfonate ofthe formula (I) that is useful as an electrophilic trifluoromethylating agent.
  • the present invention provides a one-potreaction process for the preparation of 3, 7-di-tert-butyl-S- (trifluoromethyl) dibenzothiophenium trifluoromethanesulfonateof the formula (I) : by reacting 4, 4’ -di-tert-butylbiphenyl of formula (II) with any combination of trifluoromethanesulfinate compound represented by formula CF 3 SO 2 M with trifluoromethanesulfonic anhydride, trifluoromethanesulfonicacid, a carboxylic anhydride represented by formula (RCO) 2 O, and/or a carboxylic acid represented by formula RCOOH; in which M is a hydrogen atom, a metal atom, or an ammonium moiety, and R is an alkyl or haloalkyl group of carbons 1 to 4.
  • R of (RCO) 2 O may be the same as R of RCOOH or different from R of RCOOH.
  • the present invention includes processes which comprise (see, Scheme 4, Process Ia) reacting 4, 4’ -di-tert-butylbiphenyl of formula (II) with trifluoromethanesulfinate compound represented by formula CF 3 SO 2 M and trifluoromethanesulfonic anhydride; (see, Scheme 4, Process Ib) reacting 4, 4’ -di-tert-butylbiphenyl of the formula (II) with trifluoromethanesulfinate compound represented by formula CF 3 SO 2 M and trifluoromethanesulfonic acid; (see, Scheme 4, Process Ic) reacting 4, 4’ -di-tert-butylbiphenyl of formula (II) with trifluoromethanesulfinate compound represented by formula CF 3 SO 2 M, trifluoromethanesulfonic anhydride, and a carboxylic anhydride represented by formula (RCO) 2 O; (see, Scheme 4, Process Id) react
  • the metal atom can be chosen from alkali metal atoms, alkali earth metal atoms, and transition metal atoms.
  • alkali metal atoms such as Li, Na, K, and Cs are exemplified.
  • ammonium moiety ammonium (NH 4 ) and alkylammonium such as CH 3 NH 3 , C 2 H 5 NH 3 , (C 2 H 5 ) 2 NH 2 , (C 2 H 5 ) 3 NH, (CH 3 ) 4 N, (C 2 H 5 ) 4 N, (C 4 H 9 ) 4 N and the like are exemplified.
  • lithium trifluoromethanesulfinate (CF 3 SO 2 Li) , sodium trifluoromethanesulfinate (CF 3 SO 2 Na) , potassium trifluoromethanesulfinate (CF 3 SO 2 K) , and cesium trifluoromethanesulfinate (CF 3 SO 2 Cs) are preferably exemplified.
  • sodium trifluoromethanesulfinate and potassium trifluoromethanesulfinate are more preferablefrom a viewpoint of commercial availability.
  • CF 3 SO 2 H may be in situ prepared with an acid in the reaction mixture.
  • CF 3 SO 2 H can be in situ generated by the acidification with trifluoromethanesulfonic acid and/or a carboxylic acid in the reaction mixture.
  • R is an alkyl or haloalkyl group of carbons 1-4
  • alkyl group methyl, ethyl, propyl, isopropyl, butyl, isobutyl, sec-butyl, and tert-butyl are exemplified.
  • a haloalkyl group chloromethyl, dichloromethyl, trichloromethyl, trifluoromethyl, and pentafluoroethyl are exemplified preferably.
  • acetic anhydride As a carboxylic anhydride, acetic anhydride, chloroacetic anhydride, dichloroacetic anhydride, trichloroacetic anhydride, trifluoroacetic anhydride, propionic anhydride, pentafluoropropionic anhydride, butyric anhydride, and isobutyric anhydride are preferably exemplified. Among them, acetic anhydride and trifluoroacetic anhydride are more preferable because of availability, and trifluoroacetic anhydride is furthermore preferable from a viewpoint of productionefficiency andyield.
  • a carboxylic acid represented by formula RCOOH, in which R is an alkyl or haloalkyl group of carbons 1-4, is commercially available.
  • R is an alkyl or haloalkyl group of carbons 1-4
  • alkyl group methyl, ethyl, propyl, isopropy, butyl, isobutyl, sec-butyl, and tert-butyl are exemplified.
  • a haloalkyl group chloromethyl, dichloromethyl, trichloromethyl, trifluoromethyl, and pentafluoroethyl are exemplified preferably.
  • acetic acid As a carboxylic acid, acetic acid, chloroacetic acid, dichloroacetic acid, trichloroacetic acid, trifluoroacetic acid, propionic acid, pentafluoropropionic acid, butyric acid, and isobutyric acid are preferably exemplified. Among them, acetic acid and trifluoroacetic acid are more preferable because of availability, and trifluoroacetic acid is furthermore preferable from a viewpoint of production efficiencyand yield.
  • the amount of the trifluoromethanesulfinate compound used for this process can be suitably decided in a range of about 0.5 mol to about 5 mol, or preferably about 1 mol to about 4 mol for 1 mol of 4, 4’ -di-tert-butylbiphenyl.
  • the amount of trifluoromethanesulfonic anhydride can be suitably decided in a range of about 0.5 mol to about 3 mol for 1 mol of the trifluoromethanesulfinate compound.
  • the amount of the trifluoromethanesulfinate compound for this process can be suitably decided in a range of about 0.5 mol to about 5 mol, or preferably about 1 mol to about 4 mol for 1 mol of 4, 4’ -di-tert-butylbiphenyl.
  • the amount of trifluoromethanesulfonic acid can be suitably decided in a range of about 2 mol to about 20 mol for 1 mol of the trifluoromethanesulfinate compound.
  • the amount of the trifluoromethanesulfinate compound used for this process can be suitably decided in a range of about 0.5 mol to about 4 mol, or preferably about 1 mol to about 3 mol for 1 mol of 4, 4’ -di-tert-butylbiphenyl.
  • the amount of trifluoromethanesulfonic anhydride can be suitably decided in a range of about 0.5 mol to about 3 mol for 1 mol of the trifluoromethanesulfinate compound.
  • the amount of a carboxylic anhydride can be suitably decided in a range of about 0.5 mol to about 3 mol for 1 mol of 4, 4’ -di-tert-butylbiphenyl.
  • the amount of the trifluoromethanesulfinate compound used for this process can be suitably decided in a range of about 0.5 mol to about 4 mol, or preferably about 1 mol to about 3 mol for 1 mol of 4, 4’ -di-tert-butylbiphenyl.
  • the amount of trifluoromethanesulfonic acid can be suitably decided in a range of about 1 mol to about 5 mol for 1 mol of the trifluoromethanesulfinate compound.
  • the amount of a carboxylic anhydride can be suitably decided in a range of about 0.5 mol to about 3 mol for 1 mol of the trifluoromethanesulfinate compound.
  • the amount of the trifluoromethanesulfinate compound used for this process can be suitably decided in a range of about 0.5 mol to about 4mol, or preferably about 1 mol to about 3 mol for 1 mol of 4, 4’ -di-tert-butylbiphenyl.
  • the amount of trifluoromethanesulfonic anhydride can be suitably decided in a range of about 0.5 mol to 3 mol for 1 mol of the trifluoromethanesulfinate compound.
  • the amount of a carboxylic anhydride can be suitably decided in a range of about 0.5 mol to about 3 mol for 1 mol of 4, 4’ -tert-butylbiphenyl.
  • the amount of a carboxylic acid can be suitably decided in a range of a catalytic amount (about 0.01 mol) to about 3 mol for 1 mol of the trifluoromethanesulfinate compound.
  • the amount of the trifluoromethanesulfinate compound used for this process can be suitably decided in a range of about 0.5 mol to about 4 mol, or preferably about 1 mol to about 3 mol for 1 mol of 4, 4’ -di-tert-butylbiphenyl.
  • the amount of trifluoromethanesulfonic acid can be suitably decided in a range of about 1 mol to 5 mol of the trifluoromethanesulfinate compound.
  • the amount of a carboxylic anhydride can be suitably decided in a range of about 0.5 mol to about 3 mol for 1 mol of the trifluoromethanesufinate compound.
  • the amount of a carboxylic acid can be suitably decided in a range of a catalytic amount (about 0.01 mol) to about 3 mol for1 mol of the trifluoromethanesulfinate compound.
  • the amount of the trifluoromethanesulfinate compound used for this process can be suitably decided in a range of about 0.5 mol to about 4 mol, or preferably about 1 mol to about 3 mol for 1 mol of 4, 4’ -di-tert-butylbiphenyl.
  • the amount of trifluoromethanesulfonic anhydride can be suitably decided in a range of about 0.5 mol to about 3 mol for 1 mol of trifluoromethanesulfinate compound.
  • the amount of trifluoromethanesulfonic acid can be suitably decided in a range of a catalytic amount (about 0.01 mol) to about 3 mol for 1 mol of the trifluoromethanesulfinate compound.
  • the amount of a carboxylic anhydride can be suitably decided in a range of about 0.5 mol to about 3 mol for 1 mol of 4, 4’ -di-tert-butylbipyenyl.
  • the amount of the trifluoromethanesulfinate compoundused for this process can be suitably decided in a range of about 0.5 mol to about 4mol, or preferably about 1 mol to about 3 mol for 1 mol of 4, 4’ -di-tert-butylbiphenyl.
  • the amount of trifluoromethanesulfonic anhydride can be suitably decided in a range of about 0.5 mol to about 3 mol for 1 mol of the trifluoromethanesulfinate compound.
  • the total amount of trifluoromethanesulfonic acid and a carboxylic acid can be suitably decided in a range of a catalytic amount (about 0.01 mol) to about 3 mol for 1 mol for the trifluoromethanesulfinate compound.
  • the amount of a carboxylic anhydride can be suitably decided in a range of about 0.5 mol to about 3 mol for 1 mol of 4, 4’ -di-tert-butylbiphenyl.
  • solvent can preferably be used in the case that the reaction mixture is solid or is hard to stir.
  • solvent used for the reaction polar solvents such as nitromethane, nitroethane, 1-nitropropane, 2-nitropropane, nitrobenzene, sulfolane, 2-methylsulfolane, ethyl methyl sulfone, and so on; halocarbons such as dichloromethane, chloroform, carbon tetrachloride, dichloroethane, trichloroethane, and so on; carboxylic acids such as acetic acid, propionic acid, trifluoroacetic acid, perfluoropropionic acid, and so on; and mixtures of these solvents, can be preferably exemplified.
  • the polar solvents such as nitromethane and sulfolane and the carboxylic acids such as trifluoroacetic acid and halocarbons such as dichloromethane are more preferable because of good yield of the product.
  • the carboxylic acids can be used as both the solvent and the reagent for Processes 1e, 1f, and 1h.
  • the reaction temperatureof Processes I and Ia-h can be suitably selected from a range of about -50 °C to about+100 °C.
  • the reaction time can be suitably selected so that the reaction is completed. It can be from about 0.5 hrs to several days, preferably with a few days.
  • Processes 1a, 1c, 1d, and 1f are preferable from a viewpoint of high yield or production cost.
  • This invention also relates to the reuse of 3, 7-di-tert-butyldibenzothiophene of formula (III) which is obtained after the usage of 3, 7-di-tert-butyl-S- (trifluorometyl) dibenzothiophenum salt of formula (I’ ) as a trifluoromethylating agent.
  • 3, 7-Di-tert-butyldibenzothiophene of the formula (III) and 3, 7-di-tert-butyl-S- (trifluorometyl) dibenzothiophenum salt of the formula (I’ ) are shown below:
  • X - is a conjugated base of Br nsted acid (HX) , which is exemplified as above.
  • the reduction (desulfurization) of 3, 7-di-tert-butyldibenzothiophene can be done by the conventional methods for desulfurization of organosulfur compoundsusing reducing agents (see, Example 5) .
  • reducing agents are exemplified by, but not limited to, Raney nickel; metals such as Li, Na, K and so on; and dehydrogenation with H 2 in the presence of a catalyst such as Raney Ni, Pd and its salt, and other metals and their salts.
  • 4, 4’ -Di-tert-butylbiphenyl obtained by the desulfurization can be reused as a starting material for the production of 3, 7-di-tert-butyl-S- (trifluoromethyl) dibenzothiophenium trifluoromethanesulfonate of this invention.
  • the present invention also relates to the production of 3, 7-di-tert-butyl-S- (trifluoromethyl) dibenzothiophenium trifluoromethanesulfonate of formula (I) using 4, 4’ -di-tert-butylbiphenyl of formula (II) that is recovered by the reduction (desulfurization) of 3, 7-di-tert-butyldibenzothiophene of formula (III) obtained by the usage of 3, 7-di-tert-butyl-S- (trifluoromethyl) dibenzothiophenium salt (I’ ) .
  • Trifluoromethanesulfonic acid used for the present invention can be recovered from the reaction mixture containing trifluoromethanesulfonic acid or its salt.
  • Trifluoromethanesulfonic anhydride used for the present invention can be prepared from the recovered trifluoromethanesulfonic acid or its salt by the conventional synthetic methods such as dehydration reaction with P 2 O 5 (see, J. Chem. Soc., 1957, 4069-4079) : CF 3 SO 3 H + P 2 O 5 ⁇ (CF 3 SO 2 ) 2 O.
  • the present invention also relates to the isolation process for 3, 7-di-tert-butyl-S- (trifluoromethyl) dibenzothiophenium trifluoromethanesulfonate of formula (I) .
  • the method comprises washing the reaction mixture, which results from the reactions of 4, 4’ -di-tert-butylbiphenyl with the reactant (s) as mentioned above, with water and an organic solvent (s) which does not dissolve or scarcely dissolve the product, 3, 7-di-tert-butyl-S- (trifluoromethyl) dibenzothiophenium trifluoromethanesulfonate.
  • the reaction mixture maybe the reaction residue which isobtained by the evaporation of the solvent after the reaction in order to recover the solvent or to get a better yield of the product.
  • the reaction mixture may be the reaction mixture after the reaction.
  • the reaction solvents are exemplified above.
  • the organic solvent for washing the reaction mixture does not dissolve or scarcely dissolve the product.
  • ethers such as diethyl ether, dipropyl ether, di (isopropyl) ether, dibutyl ether, di (isobutyl) ether, di (sec-butyl) ether, di (tert-butyl) ether, tert-butyl methyl ether, and so on; esters such as ethyl acetate, propyl acetate, isopropyl acetate, ethyl propionate, and so on; halocarbons such as methylene chloride, chloroform, carbon tetrachloride, dichloroethane, and so on; aromatics such as benzene, toluene, xylene, chlorobenzene, dichlorobenzene, fluorobenzene, benzotrifluoride, and so on; alkanes such as n-pentane, n-hexane, n-h
  • the reaction mixture may be washed with a mixture of water and the organic solvent.
  • the reaction mixture may also be washed in a step-wise manner; it is washed with water and then with the organic solvent, or with the organic solvent and then with water. Washing with a mixture of water and the organic solvent is preferable because of high effectiveness for the production.
  • water can remove byproducts which are trifluoromethanesulfonic acid and its salt, alkanecarboxylic acid and its salt, and the starting materials and reactants remained, which aretrifluoromethanesulfinic acid and its salt, trifluoromethanesufonic anhydride, trifluoromethanesulfonic acid, the carboxylic anhydride, and the carboxylic acid and its salt.
  • Water can remove other compounds which dissolve in water.
  • the organic solvents can remove 4, 4’ -di-tert-butylbiphenyl remained and byproducts which are dissolved in the organic solvent (s) .
  • the organic solvents can remove other compounds which dissolve in the organic solvents.
  • the product, 3, 7-di-tert-butyl-S- (trifluoromethyl) dibenzothiophenium trifluoromethanesulfonate can easily be isolated only by washing the reaction mixture with water and the organic solvent (s) mentioned above without the column chromatography separation process.
  • 3 7-Di-tert-butyl-S- (trifluoromethyl) dibenzothiophenium trifluoromethanesulfonate of formula (I) is known as auseful electrophilic trifluoromethylating agentto prepare useful trifluoromethylated organic compounds.
  • the present invention can be used for the industrial production of the useful trifluoromethylating agent (I) , because the invented method comprisesa very short one-pot process and a simple isolation process of filtration of the products precipitated from the reaction mixture by washing water and the specified organic solvent (s) (see Examples 1-3below) . These are highly usefulfor cost-effective production of the trifluoromethylating agent (I) in industry.
  • trifluoromethanesulfonic anhydride and trifluoromethanesulfonic acid may also be recovered from trifluoromethanesulfonic acid or salt obtained from the usage of the 3, 7-di-tert-butyl-S- (trifluoromethyl) dibenzothiopheniumtrifluoromethanesulfonate (I) .
  • a reactor (a round-bottomed flask) was charged with 6.44g (41.3 mmol) of dried sodium trifluoromethanesulfinate, 5.0 g (18.8mmol) of 4, 4’ -di-tert-butylbiphenyl, and 25 mL of dry nitromethane.
  • the reactor was purged with N 2 gas and cooled on an ice bath.
  • 12.7 g (45.0 mmol) of trifluoromethanesulfonic anhydride was drop-wise addedfor 20 min. The reaction mixture was gradually warmed to room temperature and stirred at room temperature for 19 hours.
  • the production method of this invention provided a high yield of the product by a one-pot reaction and a simple filtration. This is particularly useful for the economical industrial large scale production.
  • a reactor (a round-bottomed flask) was charged with 7.61 g (48.4 mmol) of dried sodium trifluoromethanesulfinate, 10.0 g (37.5 mmol) of 4, 4’ -di-tert-butylbiphenyl, and 50 mL of dry nitromethane.
  • the reactor was purged with N 2 gas and put on a water bath.
  • 15.1 g (53.5 mmol) of trifluoromethanesulfonic anhydride was drop-wise addedfor 20 min, and then the reaction mixture was stirred for 10 min. After the water bath was removed, 8.66 g (41.3 mmol) of trifluoroacetic anhydride was added by one portion.
  • a reactor (a round-bottomed flask) was charged with 3.8g (24.4mol) of dried sodium trifluoromethanesulfinate, 5.0 g (18.8mmol) of 4, 4’ -di-tert-butylbiphenyl, and 25 mL of dry nitromethane.
  • the reactor was purged with N 2 gas.
  • 9.9 g (47.0 mmol) of trifluoroacetic anhydride was drop-wise addedfor 10 min, and the mixture was stirred for 1.5 hours.
  • Trifluoromethanesulfonic acid (7.1 g, 47.0 mmol) was then added slowly in a period of about 15 min so that the temperature of the reaction mixture did not exceed 25 °C under cooling with an ice bath. After the addition, the reaction mixture was stirred for 30 min on an ice bath and then the bath was removed. The mixture was then stirred at room temperature for 22 hours. 19 FNMR analysis of the reaction solution using benzotrifluoride as a standard showed that the product, 3, 7-di-tert-butyl-S- (trifluoromethyl) dibenzothiophenium trifluoromethanesulfonate, was produced in 51%yield.
  • the yield of the di-tert-butyldibenzothiophene was 82%on the basis of3, 7-di-tert-butyl-S- (trifluoromethyl) dibenzothiophenium trifluoromethanesulfonate used.

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Abstract

L'invention concerne un procédé industriel comprenant un procédé de réaction monotope et un procédé d'isolement aisé pour la production de 3, 7-di-tert-butyl-S- (trifluorométhyl)dibenzothiphénium trifluorométhanesulfonate de formule (I) qui est un agent de trifluorométhylation utile. Le procédé comprend également l'utilisation de matériaux de départ récupérés après trifluorométhylation.
PCT/CN2016/076181 2015-03-13 2016-03-12 Procédé industriel pour la production de 3,7-di-tert-butyl-s- (trifluorométhyl)dibenzothiophénium trifluorométhanesulfonate WO2016146040A1 (fr)

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Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH05339260A (ja) * 1992-06-03 1993-12-21 Daikin Ind Ltd アルキル置換（ハロアルキル）ジベンゾオニウム塩及びアルキル置換（ハロアルキル）ビフェニル化合物

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* Cited by examiner, † Cited by third party
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JPH05339261A (ja) * 1992-06-03 1993-12-21 Daikin Ind Ltd （ハロアルキル）ジベンゾチオ又はセレノフェニウムハロアルカンスルホナートの製造方法

Patent Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH05339260A (ja) * 1992-06-03 1993-12-21 Daikin Ind Ltd アルキル置換（ハロアルキル）ジベンゾオニウム塩及びアルキル置換（ハロアルキル）ビフェニル化合物

Non-Patent Citations (2)

* Cited by examiner, † Cited by third party
Title
TAKAO OKAZAKI ET AL.: "The 2, 4-dimethyl-7-pentafluorosulfanyl-5- (trifluoromethyl)dibenzo[b, d]thiophenium trifluoromethanesulfonate: The SF5-analog of Umemoto salt.", JOURNAL OF FLUORINE CHEMISTRY., 2 July 2014 (2014-07-02), pages 91 - 95, XP029014973 *
TERUO UMEMOTO ET AL.: "Power -Variable Electrophilic Trifluoromethylating Agents. S-, Se-, and Te-(Trifluoromethyl)dibenzothio-, -seleno-, and -tellurophenium Salt System.", J. AM. CHEM. SOC., vol. 6, no. 115, 31 December 1993 (1993-12-31), pages 2156 - 2164, XP002055068 *

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