WO2024153573A1 - Procédé de préparation de dérivés de (2,2,2-trifluoroéthyl) sulfanylaniline - Google Patents

Procédé de préparation de dérivés de (2,2,2-trifluoroéthyl) sulfanylaniline Download PDF

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Publication number
WO2024153573A1
WO2024153573A1 PCT/EP2024/050760 EP2024050760W WO2024153573A1 WO 2024153573 A1 WO2024153573 A1 WO 2024153573A1 EP 2024050760 W EP2024050760 W EP 2024050760W WO 2024153573 A1 WO2024153573 A1 WO 2024153573A1
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process according
solvent
methyl
sodium
potassium
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PCT/EP2024/050760
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German (de)
English (en)
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Alexander ARLT
Thomas Himmler
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Bayer Aktiengesellschaft
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C319/00—Preparation of thiols, sulfides, hydropolysulfides or polysulfides
    • C07C319/14—Preparation of thiols, sulfides, hydropolysulfides or polysulfides of sulfides
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C319/00—Preparation of thiols, sulfides, hydropolysulfides or polysulfides
    • C07C319/02—Preparation of thiols, sulfides, hydropolysulfides or polysulfides of thiols
    • C07C319/06—Preparation of thiols, sulfides, hydropolysulfides or polysulfides of thiols from sulfides, hydropolysulfides or polysulfides

Definitions

  • the present invention relates to a process for the preparation of (2,2,2-trifluoroethyl)sulfanylaniline derivatives.
  • (2,2,2-Trifluoroethyl)sulfanylaniline derivatives are of great importance in the agrochemical industry as intermediates for the synthesis of active ingredients. There is therefore a continuing need for simplified, technically and economically feasible processes for their synthesis.
  • (2,2,2-trifluoroethyl)sulfanylaniline derivatives can be obtained by the alkylation of a thiophenol with l,l,l-trifluoro-2-iodoethane (e.g. W02014202505) or with bis(2,2,2-trifluoroethyl)sulfate (Chem. Sci., 2019, 10, 10331-10335). It is also possible to replace l,l,l-trifluoro-2-iodoethane with 2,2,2-trifluoroethylmethanesulfonate.
  • Dimethylformamide is a very polar aprotic solvent. It is therefore used in particular as a solvent for nucleophilic substitution reactions. Due to its toxicological properties, it is classified as toxic for reproduction, but its use should be reduced to the absolute minimum.
  • the choice of solvent used in a production process depends on many other factors in addition to these toxicological aspects, such as the solubility of the reactants and products, the influence on the activity of the reactants, the stability of the solvent under the reaction conditions, the influence on the formation of unwanted by-components and the costs and availability at the respective production site. Although there may in principle be various possible options, the choice of a suitable solvent or a suitable solvent mixture is not a trivial task for the reasons mentioned above.
  • a solvent or solvent mixture must be identified that meets the above requirements in two different reactions.
  • Thiophenols are known to be sensitive to oxidation. Under the influence of atmospheric oxygen, disulfides are formed through an oxidative dimerization reaction. These disulfides are no longer available for alkylation by electrophiles and therefore significantly reduce the yield. In addition, these disulfides represent an impurity that may then have to be separated off at great expense. The more electron-rich the thiophenol is, the more sensitive it is to oxidation.
  • the substituted 3-aminobenzenethiols required for the production of (2,2,2-trifluoroethyl)sulfanylaniline derivatives (I) are very sensitive to oxidation due to the electron-rich 3-amino function and therefore have to be handled under an inert gas atmosphere. It would therefore be very advantageous if these substituted 3-aminobenzenethiols did not have to be isolated after their production. This would significantly reduce the risk of oxidation of these intermediate products. The susceptibility to errors in the production process would thus be reduced.
  • the 3-aminobenzenethiols required for the preparation of (2,2,2-trifluoroethyl)sulfanylaniline derivatives (I) can be obtained, for example, by a transition metal-catalyzed reduction with hydrogen from suitable disulfides, in particular l,l'-disulfanediylbis(3-nitrobenzene) derivatives. It has been found that this reduction is advantageously carried out in the solvents THF or ethyl acetate (W02014/090913). However, alkylation to (2,2,2-trifluoroethyl)sulfanylaniline with l,l,l-trifluoro-2-chloroethane is only described for dimethylformamide as solvent.
  • the desired process should enable the desired target compounds to be obtained starting from solutions of the substituted 3-aminobenzenethiols in non-polar solvents, in particular in isopropyl acetate or ethyl acetate, and avoid or at least significantly reduce the use of polar solvents such as dimethylformamide.
  • the (2,2,2-trifluoroethyl)sulfanylaniline derivatives obtainable with this desired process should preferably be obtained in high yield and in high chemical purity.
  • the content of disulfides, which may already be present at the start of the reaction and/or may form during the reaction should be as low as possible in the end product of the process.
  • disulfides in the end product of the reaction can be significantly reduced if at least one reducing agent such as sodium hydroxymethanesulfinate or sodium dithionite is added to the reaction.
  • Disulfides can form during the reaction according to the invention and/or be present at the start of the reaction. They reduce the yield of the desired end product, so that the lowest possible content of disulfides in the end product is desirable.
  • the present invention therefore relates to a process for the preparation of (2,2,2-trifluoroethyl)sulfanylaniline derivatives of the formula (I) in which R 1 and R 2 independently represent (Ci C3)alkyl or halogen, which is characterized in that a 3-aminobenzenethiol of the formula (II) in which R 1 and R 2 have the meanings given above, with 1,1,1 -trifluoro-2-chloroethane in the presence of a base and at least one reducing agent in a
  • a first (polar aprotic) solvent selected from N-methylpyrrolidone, N-ethylpyrrolidone, N-methylformamide, dimethylformamide, N,N-dimethylacetamide (DMAc), l,3-dimethyl-2-imidazolidinone, tetramethylurea, sulfolane, Dimethyl sulfoxide, acetonitrile, propionitrile, butyronitrile, polyethylene glycols,
  • a first (polar aprotic) solvent selected from N-methylpyrrolidone, N-ethylpyrrolidone, N-methylformamide, dimethylformamide, N,N-dimethylacetamide (DMAc), l,3-dimethyl-2-imidazolidinone, tetramethylurea, sulfolane, Dimethyl sulfoxide, acetonitrile, propionitrile, butyronitrile, polyethylene glycols,
  • a second (less polar aprotic) solvent selected from tetrahydrofuran (THF), 1,2-dimethoxyethane (DME), 1,4-dioxane, diethyl ether, methyl tert-butyl ether (MTBE), tert-amyl methyl ether (TAME), 2-methyl THF, cyclopentyl methyl ether, bis(2-methoxyethyl) ether, anisole, ethyl acetate, isopropyl acetate, butyl acetate, pentyl acetate, 3,3-dimethylbutanone, diethyl carbonate, dimethyl carbonate, benzene, toluene, xylenes and ethylbenzene.
  • THF tetrahydrofuran
  • DME 1,2-dimethoxyethane
  • MTBE methyl tert-butyl ether
  • TAME tert-amyl
  • R 1 and R 2 independently represent fluorine, chlorine or methyl.
  • R 1 and R 2 independently represent fluorine or methyl.
  • R 1 stands for methyl and R 2 for fluorine.
  • the compound of formula (II) is formed from a disulfide of formula (III) in which R 1 and R 2 have the meanings given above.
  • This disulfide is reduced in the presence of the reducing agent according to the invention to the compound of formula (II).
  • the compounds of formula (II) and (III) can already be present side by side at the beginning of the reaction.
  • disulfides of formula (III) can be formed from compounds of formula (II) in the course of the reaction.
  • the (2,2,2-trifluoroethyl)sulfanylaniline derivatives of the formula (I) can be prepared in good yields using the process according to the invention. Furthermore, the process according to the invention allows the use of solvent mixtures of a polar solvent with a significantly less polar solvent suitable for industrial scale. In addition, the content of disulfides in the final product of the reaction can be significantly reduced by the addition of at least one reducing agent.
  • the compounds of formula (II) can be obtained, for example, from disulfides of formula (III) or analogously to the processes described in W02014/090913.
  • the process can also be carried out with derivatives of the 3-aminobenzenethiols in which one or both protons of the amino group have been substituted by -CO(Ci-C6)alkyl (alkanoyl) or -SC(Ci-Ce)alkyl (alkylsulfonyl).
  • halogens includes those elements which are selected from the group consisting of fluorine, chlorine, bromine and iodine, with fluorine, chlorine and bromine being preferred and fluorine and chlorine being particularly preferred.
  • Optionally substituted groups can be mono- or polysubstituted, where in the case of multiple substitutions the substituents can be the same or different.
  • the substituents are selected from halogen, (Ci-Gjalkyl, (C3-Cw)cycloalkyl, cyano, nitro, hydroxy, (Ci-Cejalkoxy, (Ci-Cejhaloalkyl and (Ci-Crjhaloalkoxy, in particular from fluorine, chlorine, (C 1-C3) alkyl, (Cs-Cejcycloalkyl, cyclopropyl, cyano, (Ci-Csjalkoxy, (Ci-Csjhaloalkyl and (Ci-Csjhaloalkoxy.
  • Alkyl groups substituted with one or more halogen atoms are, for example, selected from trifluoromethyl (CF3), difluoromethyl (CHF2), CF3CH2, CICH2, CF3CCI2.
  • alkyl groups are, unless otherwise defined, linear, branched or ring-shaped saturated hydrocarbon groups.
  • Ci-C alkyl covers the largest range defined herein for an alkyl group.
  • this definition includes, for example, the meanings methyl, ethyl, n-, and iso-propyl.
  • This solvent mixture comprises a first and a second solvent.
  • this solvent mixture consists of the first and the second solvent.
  • the first solvent is a polar aprotic solvent and the second solvent is a less polar aprotic solvent.
  • Such solvents are mentioned below.
  • polar aprotic solvents within the meaning of the present application are: N-methylpyrrolidone, N-ethylpyrrolidone, N-methylformamide, dimethylformamide, N,N-dimethylacetamide (DMAc), l,3-dimethyl-2-imidazolidinone, tetramethylurea, sulfolane, dimethyl sulfoxide, acetonitrile, propionitrile, butyronitrile, polyethylene glycols, ethylene carbonate and propylene carbonate.
  • Second and therefore less polar aprotic solvents within the meaning of the application are: tetrahydrofuran (THF), 1,2-dimethoxyethane (DME), 1,4-dioxane, diethyl ether, methyl tert-butyl ether (MTBE), tert-amyl methyl ether (TAME), 2-methyl-THF, cyclopentyl methyl ether, bis(2-methoxyethyl) ether, anisole, ethyl acetate, isopropyl acetate, butyl acetate, pentyl acetate, 3,3-dimethylbutanone, diethyl carbonate, dimethyl carbonate, benzene, toluene, xylenes and ethylbenzene.
  • THF tetrahydrofuran
  • DME 1,2-dimethoxyethane
  • MTBE methyl tert-butyl ether
  • TAME ter
  • Preferred first and thus polar aprotic solvents are: N-methylpyrrolidone, N-methylformamide, dimethylformamide, N,N-dimethylacetamide (DMAc), sulfolane, dimethyl sulfoxide and polyethylene glycols with molecular weights of 200 - 800 g/mol (polyethylene glycol 200 - 800).
  • Preferred second and thus less polar aprotic solvents are: tetrahydrofuran (THF), dimethyl ether (DME), 1,4-dioxane, 2-methyl-THF, ethyl acetate, isopropyl acetate, butyl acetate and pentyl acetate.
  • first and thus polar aprotic solvents are: N-methylpyrrolidone, dimethylformamide, N,N-dimethylacetamide (DMAc), dimethyl sulfoxide and polyethylene glycol 400.
  • Particularly preferred second and thus less polar aprotic solvents are: tetrahydrofuran (THF), ethyl acetate and isopropyl acetate.
  • Particularly preferred first and therefore polar solvents are: dimethylformamide and N,N-dimethylacetamide (DMAc).
  • Particularly preferred second and therefore less polar aprotic solvents are: isopropyl acetate and ethyl acetate.
  • the ratio of first (polar aprotic) solvent to second (less polar aprotic) solvent is in the range of 20:1 to 1:20, preferably in the range of 2:1 to 1:10, particularly preferably in the range of 1:2 to 1:5 and most preferably in the range of 1:2 to 1:4, ideally 1:2 to 1:3.
  • the ratio of first (polar aprotic) solvent to second (less polar aprotic) solvent is in the range of 1:1 to 1:10, or in the range of 1:1 to 1:5, or in the range of 1:1 to 1:3, or in the range of 1:1 to 1:2, or in the range of 2:1 to 1:5, or in the range of 2:1 to 1:3, or in the range of 2:1 to 1:2, or in the range of 1:2 to 1:10, or in the range of 1:2 to 1:20.
  • Suitable bases for preparing the thiolates are mono- or divalent organic or inorganic bases, preferably in equimolar amounts, such as alkali metal, alkaline earth metal, ammonium or alkylammonium hydroxide, sodium hydride, calcium hydride, alkali metal or alkaline earth metal alcoholate, alkali metal or alkaline earth metal carbonates, ammonia, primary, secondary or tertiary alkyl, aryl or aralkylamines, amidines or pyridine.
  • Preferred bases are sodium and potassium hydroxide and sodium and potassium carbonate.
  • Sodium and potassium carbonate are particularly preferred. Potassium carbonate is particularly preferred.
  • the bases can be used either anhydrous or as aqueous solutions.
  • the molar ratio of base to thiol of formula (II) is in the range of 0.9:1 to 5:1 and preferably in the range of 1:1 to 2:1.
  • reducing agents are formamidine sulfinic acid, sodium hydroxymethanesulfinate, potassium hydroxymethanesulfinate, magnesium hydroxymethanesulfinate, calcium hydroxymethanesulfinate, zinc hydroxymethanesulfinate, sodium dithionite, potassium dithionite, magnesium dithionite, calcium dithionite, zinc dithionite, sodium sulfite, potassium sulfite, calcium sulfite, magnesium sulfite, potassium disulfite, sodium disulfite, potassium hydrogen sulfite, sodium hydrogen sulfite, calcium hydrogen sulfite and magnesium hydrogen sulfite.
  • sodium hydroxymethanesulfinate potassium hydroxymethanesulfinate
  • potassium dithionite sodium dithionite.
  • Sodium hydroxymethanesulfinate and sodium dithionite are particularly preferred.
  • the molar ratio of reducing agent to thiol of formula (II) is in the range from 0.05:1 to 2:1, preferably in the range from 0.1:1 to 1.5:1 and most preferably in the range from 0.1:1 to 1:1.
  • the molar ratio of reducing agent to disulfide of the formula (III) is in the range from 1:1 to 4:1, preferably in the range from 1:1 to 3:1 and very particularly preferably in the range from 1:1 to 2.5:1.
  • the reaction is generally carried out at a temperature between 0 °C and 100 °C, preferably between 20 °C and 100 °C, most preferably between 40 °C and 80 °C.
  • the reaction is typically carried out under normal pressure up to moderate overpressure, but can also be carried out under higher overpressure.
  • Preferred pressure ranges are between 0 bar and 20 bar overpressure, in particular between 0 bar and 18 bar overpressure, preferably between 0 bar and 15 bar overpressure, very particularly preferably between 0 bar and 10 bar overpressure.
  • the overpressure can arise from the inherent pressure of the 1,1,1-trifluoro-2-chloroethane used or from the injection of an additional inert gas, such as argon or nitrogen.
  • the reaction can take place in a pressure autoclave, for example, but does not necessarily have to take place in a pressure autoclave. Various alternatives are known to those skilled in the art.
  • the reaction can be carried out in the presence of a phase transfer catalyst, such as tetra-n-butylammonium bromide.
  • a phase transfer catalyst such as tetra-n-butylammonium bromide.
  • the isolation of the desired compounds of formula (I) can be carried out, for example, by subsequent extraction and distillation.
  • the reported yields were calculated by weighing the amount of product obtained and correcting this weight for the purity in area percent determined by HPLC.
  • the amount of the desired product in HPLC area percent was evaluated at a wavelength of 210 nm.
  • the amount of product was determined by weighing a solution of the product and correcting this weight by the purity determined by HPLC in percent by weight. The proportion of the target product in the product solution was determined against an external standard. A sample of 2-fluoro-4-methyl-5-[(2,2,2-trifluoroethyl)sulfanyl]aniline of known purity served as the external standard. Analysis of 2-fluoro-4-methyl-5-((2,2,2-trifluoroethyl)sulfanyl)aniline in a from dimethylformamide and with the addition of sodium dithionite
  • a 250 mL glass reactor equipped with an overhead stirrer, a gas inlet and a reflux condenser was used.
  • 30 g of isopropyl acetate, 33 g of dimethylformamide, 1.13 g (3.51 mmol) of tetra-n-butylammonium bromide, 14.51 g (105.0 mmol) of potassium carbonate and 1.72 g (8.40 mmol) of sodium dithionite were mixed.
  • the reaction mixture was degassed by passing a stream of nitrogen.
  • reaction mixture was stirred at 60 °C for 19 h.
  • the reaction mixture was cooled to 20 °C, 70 g of water were added and stirred for 25 min.
  • the phases were then separated.
  • the organic phase was washed twice with 20 g of 10% aqueous NaCl solution. 71.26 g of an organic upper phase were obtained.
  • the proportion of 2-fluoro-4-methyl-5-[(2,2,2-trifluoroethyl)sulfanyl]aniline in the upper phase was determined by quantitative HPLC (against external standard) to be 22.2%. This corresponds to a yield of 88% starting from 5-amino-4-fluoro-2-methylbenzenethiol.
  • the disulfide 5-[(5-amino-4-fluoro-2-methyl-phenyl)disulfanyl]-2-fluoro-4-methyl-aniline was not found in the organic phase (evaluation carried out at a wavelength of 230 nm).
  • a 250 ml glass reactor equipped with an overhead stirrer, a gas inlet and a reflux condenser was used.
  • the ratio of 2-fluoro-4-methyl-5-[(2,2,2-trifluoroethyl)sulfanyl]aniline to the disulfide 5-[(5-amino-4-fluoro-2-methyl-phenyl)disulfanyl]-2-fluoro-4-methyl-aniline was 2313:1 according to HPLC (evaluation carried out at a wavelength of 230 nm).
  • Example 3 Synthesis of 2-fluoro-4-methyl-5-r(2,2,2-trifluoroethyl)sulfanyl1aniline in a solvent mixture of dimethylformamide and ethyl acetate with the addition of 1 equivalent of sodium hydroxymethanesulfinate
  • a 250 mL glass reactor equipped with an overhead stirrer, a gas inlet and a reflux condenser was used. 30 g of ethyl acetate, 33 g of dimethylformamide, 1.13 g (3.51 mmol) of tetra-n-butylammonium bromide, 9.67 g (70.0 mmol) of potassium carbonate and 8.27 g (70.0 mmol) of sodium hydroxymethanesulfinate were mixed in the 250 mL reactor. To degas the reaction mixture, the pressure was reduced to 45 mbar while stirring, the mixture was briefly refluxed and the apparatus was then slowly refilled with nitrogen. This cycle was carried out three times in total.
  • the ratio of 2-fluoro-4-methyl-5-[(2,2,2-trifluoroethyl)sulfanyl]aniline to the disulfide 5-[(5-amino-4-fluoro-2-methyl-phenyl)disulfanyl]-2-fluoro-4-methyl-aniline was 1028:1 according to HPLC area percent (evaluation carried out at a wavelength of 230 nm).
  • Comparative Example 1 Synthesis of 2-fluoro-4-methyl-5-r(2.2,2-trifluoroethyl)sulfanyl1aniline in a solvent mixture of dimethylformamide and ethyl acetate without addition of a reducing agent
  • a 250 mL glass reactor equipped with an overhead stirrer, a gas inlet and a reflux condenser was used.
  • 30 g of ethyl acetate, 33.2 g of dimethylformamide, 1.13 g (3.51 mmol) of tetra-n-butylammonium bromide and 9.67 g (70.0 mmol) of potassium carbonate were mixed.
  • the reaction mixture was degassed by introducing a stream of nitrogen.
  • the ratio of 2-fluoro-4-methyl-5-[(2,2,2-trifluoroethyl)sulfanyl]aniline to the disulfide 5-[(5-amino-4-fluoro-2-methyl-phenyl)disulfanyl]-2-fluoro-4-methyl-aniline was 17:1 according to HPLC area percent (evaluation carried out at a wavelength of 230 nm).
  • the ratio of 2-fluoro-4-methyl-5-[(2,2,2-trifluoroethyl)sulfanyl]aniline to the disulfide 5-[(5-amino-4-fluoro-2-methyl-phenyl)disulfanyl]-2-fluoro-4-methyl-aniline was 14:1 according to HPLC area percent (evaluation carried out at a wavelength of 210 nm).
  • the ratio of 2-fluoro-4-methyl-5-[(2,2,2-trifluoroethyl)sulfanyl]aniline to the disulfide 5-[(5-amino-4-fluoro-2-methyl-phenyl)disulfanyl]-2-fluoro-4-methyl-aniline was 1.4:1 (evaluation carried out at a wavelength of 210 nm).

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  • Organic Chemistry (AREA)
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Abstract

La présente invention concerne un procédé de préparation de dérivés de (2,2,2-trifluoroéthyl) sulfanylaniline de formule (I), dans laquelle R1 et R2 ont les significations indiquées dans la description.
PCT/EP2024/050760 2023-01-19 2024-01-15 Procédé de préparation de dérivés de (2,2,2-trifluoroéthyl) sulfanylaniline WO2024153573A1 (fr)

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Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0645355A1 (fr) 1993-09-29 1995-03-29 Hoechst Aktiengesellschaft Procédé de préparation de composés trifluorosoufrés au départ de thiolates et de 1-chloro-2,2,2-trifluoroéthane
WO2013030262A1 (fr) * 2011-09-02 2013-03-07 Basf Se Mélanges insecticides actifs comprenant des composés d'arylquinazolinone
WO2014090913A1 (fr) 2012-12-12 2014-06-19 Bayer Cropscience Ag Procédé de préparation de bis(3-aminophényl)-disulfures et de 2-aminothiols
WO2014202505A1 (fr) 2013-06-20 2014-12-24 Bayer Cropscience Ag Dérivés d'arylsulfure et d'arylsulfoxyde utilisés comme acaricides et insecticides
JP2015036377A (ja) * 2013-08-15 2015-02-23 北興化学工業株式会社 置換フェニルピペラジン化合物および有害生物防除剤

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0645355A1 (fr) 1993-09-29 1995-03-29 Hoechst Aktiengesellschaft Procédé de préparation de composés trifluorosoufrés au départ de thiolates et de 1-chloro-2,2,2-trifluoroéthane
WO2013030262A1 (fr) * 2011-09-02 2013-03-07 Basf Se Mélanges insecticides actifs comprenant des composés d'arylquinazolinone
WO2014090913A1 (fr) 2012-12-12 2014-06-19 Bayer Cropscience Ag Procédé de préparation de bis(3-aminophényl)-disulfures et de 2-aminothiols
WO2014202505A1 (fr) 2013-06-20 2014-12-24 Bayer Cropscience Ag Dérivés d'arylsulfure et d'arylsulfoxyde utilisés comme acaricides et insecticides
JP2015036377A (ja) * 2013-08-15 2015-02-23 北興化学工業株式会社 置換フェニルピペラジン化合物および有害生物防除剤

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