EP4377294A1 - Procédé de préparation de dérivés de (2,2,2-trifluoroéthyl)sulfanylaniline - Google Patents

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

Info

Publication number
EP4377294A1
EP4377294A1 EP22754090.3A EP22754090A EP4377294A1 EP 4377294 A1 EP4377294 A1 EP 4377294A1 EP 22754090 A EP22754090 A EP 22754090A EP 4377294 A1 EP4377294 A1 EP 4377294A1
Authority
EP
European Patent Office
Prior art keywords
solvent
methyl
ether
carbonate
acetate
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Pending
Application number
EP22754090.3A
Other languages
German (de)
English (en)
Inventor
Alexander ARLT
Dirk Brohm
Thomas Himmler
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Bayer AG
Original Assignee
Bayer AG
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Bayer AG filed Critical Bayer AG
Publication of EP4377294A1 publication Critical patent/EP4377294A1/fr
Pending legal-status Critical Current

Links

Classifications

    • 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
    • C07C323/00—Thiols, sulfides, hydropolysulfides or polysulfides substituted by halogen, oxygen or nitrogen atoms, or by sulfur atoms not being part of thio groups
    • C07C323/23—Thiols, sulfides, hydropolysulfides or polysulfides substituted by halogen, oxygen or nitrogen atoms, or by sulfur atoms not being part of thio groups containing thio groups and nitrogen atoms, not being part of nitro or nitroso groups, bound to the same carbon skeleton
    • C07C323/31—Thiols, sulfides, hydropolysulfides or polysulfides substituted by halogen, oxygen or nitrogen atoms, or by sulfur atoms not being part of thio groups containing thio groups and nitrogen atoms, not being part of nitro or nitroso groups, bound to the same carbon skeleton having the sulfur atom of at least one of the thio groups bound to a carbon atom of a six-membered aromatic ring of the carbon skeleton
    • C07C323/33—Thiols, sulfides, hydropolysulfides or polysulfides substituted by halogen, oxygen or nitrogen atoms, or by sulfur atoms not being part of thio groups containing thio groups and nitrogen atoms, not being part of nitro or nitroso groups, bound to the same carbon skeleton having the sulfur atom of at least one of the thio groups bound to a carbon atom of a six-membered aromatic ring of the carbon skeleton having at least one of the nitrogen atoms bound to a carbon atom of the same non-condensed six-membered aromatic ring
    • C07C323/35—Thiols, sulfides, hydropolysulfides or polysulfides substituted by halogen, oxygen or nitrogen atoms, or by sulfur atoms not being part of thio groups containing thio groups and nitrogen atoms, not being part of nitro or nitroso groups, bound to the same carbon skeleton having the sulfur atom of at least one of the thio groups bound to a carbon atom of a six-membered aromatic ring of the carbon skeleton having at least one of the nitrogen atoms bound to a carbon atom of the same non-condensed six-membered aromatic ring the thio group being a sulfide group
    • C07C323/36—Thiols, sulfides, hydropolysulfides or polysulfides substituted by halogen, oxygen or nitrogen atoms, or by sulfur atoms not being part of thio groups containing thio groups and nitrogen atoms, not being part of nitro or nitroso groups, bound to the same carbon skeleton having the sulfur atom of at least one of the thio groups bound to a carbon atom of a six-membered aromatic ring of the carbon skeleton having at least one of the nitrogen atoms bound to a carbon atom of the same non-condensed six-membered aromatic ring the thio group being a sulfide group the sulfur atom of the sulfide group being further bound to an acyclic carbon atom

Definitions

  • the present invention relates to a process for preparing (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 substances. 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 alkylating a thiophenol with l,l,l-trifluoro-2-iodoethane (e.g. WO2014202505) or with bis(2,2,2-trifluoroethyl) sulfate (Chem. Sei., 2019, 10, 10331-10335). It is also possible to replace l,l,l-trifluoro-2-iodoethane with 2,2,2-trifluoroethyl methanesulfonate.
  • dimethylformamide is a very polar aprotic solvent. Therefore, it is used in particular as a solvent for nucleophilic substitution reactions. Due to its toxicological properties, it is classified as toxic to reproduction, but its use should be reduced to what is absolutely necessary.
  • the choice of the solvent used in a production process depends on many other factors, such as the solubility of the starting materials and products, the influence on the activity of the reactants, the stability of the solvent under the reaction conditions, the influence on the arise unwanted secondary components and the costs as well as the availability at the respective production site.
  • the choice of a suitable solvent or a suitable solvent mixture is not a trivial task for the reasons given above.
  • a solvent or a 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 as a result of an oxidative dimerization reaction. These disulfides are no longer available for alkylation by electrophiles and therefore significantly reduce the yield. In addition, these disulphides represent an impurity which may subsequently have to be removed in a laborious process. The more electron-rich the thiophenol is, the more sensitive it is to oxidation.
  • substituted 3-aminobenzenethiols required for the preparation of (2,2,2-trifluoroethyl)sulfanylaniline derivatives (I) are very sensitive to oxidation due to the electron-rich 3-amino function and must therefore be handled under an inert gas atmosphere. It would therefore be very advantageous if these substituted 3-aminobenzene thiols did not have to be isolated after their preparation. This would significantly reduce the risk of oxidation of these intermediates. 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 from 1,1-disulfanediylbis(3-nitrobenzene) derivatives by a transition metal-catalyzed reduction with hydrogen. It has been found that this reduction is advantageously carried out in the solvents THF or ethyl acetate (WO2014/090913). However, an alkylation to (2,2,2-trifluoroethyl)sulfanylaniline with l,l,l-trifluoro-2-chloroethane has only been described for dimethylformamide as the solvent.
  • the subject matter of the present invention is therefore 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-aminobenzene thiol of the formula (II) in which R 1 and R 2 have the meanings given above, with l, l, l-trifluoro-2-chloroethane in the presence of a base in a solvent mixture, wherein the solvent mixture
  • 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), terf-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, toluene, xylenes and ethylbenzene, includes.
  • the solvent mixture comprises
  • a second (less polar aprotic) solvent selected from tetrahydrofuran (THF), 1,2-dimethoxyethane (DME), 1,4-dioxane, diethyl ether,
  • MTBE methyl tert-butyl ether
  • TAME tert-A m y 1 - methyl 1 ether
  • 2-methyl-THF 2-methyl-THF
  • cyclopentyl methyl ether bis(2-methoxyethyl) ether, anisole, ethyl acetate, isopropyl acetate, butyl acetate, pentyl acetate, 3,3-dimethylbutanone, toluene, xylenes and ethylbenzene.
  • R 1 and R 2 are preferably each independently fluorine, chlorine or methyl.
  • R 1 and R 2 are particularly preferably independently fluorine or methyl.
  • R 1 stands for methyl and R 2 for fluorine.
  • 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 which is suitable for the industrial scale.
  • R 1 and R 2 have the meanings given above.
  • the required substituted 3-aminobenzenethiols of the formula (II) can be obtained, for example, analogously to the processes described in WO2014/090913.
  • the process can also be carried out with derivatives of 3-aminobenzenethiols in which one or both protons of the amino group have been substituted by -CO(Ci-C 6 )alkyl (alkanoyl) or -SOdCVGjalkyl (alkylsulfonyl).
  • halogens includes such elements 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 are preferably used.
  • Optionally substituted groups can be substituted once or several times, where in the case of multiple substitutions the substituents can be identical or different.
  • the substituents are selected from halogen, (CVGjalkyl, (C3-Cio)cycloalkyl, cyano, nitro, hydroxy, (CVOjalkoxy, (C 1 -G >) haloalkyl and (Ci-Ojhaloalkoxy, in particular from Fluorine, chlorine, (Ci-C3)alkyl, (C3-C6)cycloalkyl, cyclopropyl, cyano, (Ci-C3)alkoxy, (Ci-C3)haloalkyl and (Ci-C3)haloalkoxy.
  • Alkyl groups substituted with one or more halogen atoms are selected, for example, from trifluoromethyl (CF 3 ), difluoromethyl (CHF 2 ), CF 3 CH 2 , CICH 2 , CF 3 CCI 2 .
  • alkyl groups are linear, branched or cyclic saturated hydrocarbon groups.
  • Ci-C3-alkyl includes the largest range defined herein for an alkyl group. Specifically, this definition includes, for example, the meanings methyl, ethyl, n-, 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), 1,3-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, toluene, xylenes and ethylbenzene.
  • THF tetrahydrofuran
  • DME 1,2-dimethoxyethane
  • MTBE methyl tert-butyl ether
  • TAME tert
  • Preferred first and thus polar aprotic solvents are: N-methylpyrrolidone, N-methylformamide, dimethylformamide, N,N-dimethylacetamide (DMAc), sulfolane, dimethyl sulfoxide and polyethylene glycols with a molecular weight of 200-800 g/mol (polyethylene glycol 200-800).
  • first and thus polar aprotic solvents are: N-methylpyrrolidone, N-methylformamide, dimethylformamide, N,N-dimethylacetamide (DMAc), sulfolane and dimethyl sulfoxide.
  • 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.
  • first and thus polar aprotic solvents are: N-methylpyrrolidone, dimethylformamide and N,N-dimethylacetamide (DMAc).
  • Particularly preferred second and thus less polar aprotic solvents are: tetrahydrofuran (THF), ethyl acetate and isopropyl acetate.
  • Very particularly preferred first and thus polar solvents are: dimethylformamide, N,N-dimethylacetamide (DMAc), dimethyl sulfoxide and polyethylene glycol 400.
  • first and thus polar aprotic solvents are: dimethylformamide and N,N-dimethylacetamide (DMAc).
  • Very particularly preferred second and thus less polar aprotic solvents are: tetrahydrofuran (THF) and ethyl acetate.
  • the ratio of first (polar aprotic) solvent to second (less polar aprotic) solvent is in the range from 20:1 to 1:20, preferably in the range from 2:1 to 1:10, particularly preferably in the range from 1:2 to 1:5 and most preferably in the range 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 1:1 to 1:2, or in the range 2:1 to 1:5 or in the range 2:1 to 1:3 or in the range 2:1 to 1:2 or in the range from 1:2 to 1:10 or in the range from 1:2 to 1:20.
  • the bases which can be used for this reaction are not particularly limited.
  • Monovalent or divalent organic bases are suitable as bases for preparing the thiolates or inorganic bases, preferably in equimolar amounts, such as.
  • 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 in anhydrous form or as aqueous solutions.
  • the molar ratio of base to thiol of the formula (II) is in the range from 0.9:1 to 5:1, preferably between 1.1:1 and 2:1.
  • the reaction is generally carried out at a temperature between 0°C and 100°C, preferably between 20°C and 100°C, very particularly preferably between 40°C and 80°C.
  • the reaction is typically carried out under atmospheric pressure up to moderately elevated pressure, but can also be carried out under higher elevated pressure.
  • 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 excess pressure can be caused by the inherent pressure of the l,l,l-trifluoro-2-chloroethane used or by forcing in 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 in this regard are known to the person 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 desired compounds of the formula (I) can be isolated, for example, by subsequent extraction and distillation.
  • Reported yields were calculated by weighing the amount of product obtained and correcting this weight for the HPLC determined area percent purity.
  • the HPLC area percent of the desired product was evaluated at a wavelength of 210 nm.
  • the amount of product was determined by weighing a solution of the product and correcting the weight for the HPLC purity 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 an external standard.
  • Example 1 Synthesis of 2-fluoro-4-methyl-5-r(2.2.2-trifluoroethyl-sulfanyl-aniline in a solvent composed of dimethylformamide and ethyl acetate (ratio 1:21
  • the autoclave was sealed and the internal pressure increased to 10 bar by introducing argon. It was heated to 60° C. and stirred at this temperature for 16 h (stirring speed: 600 rpm). The autoclave was vented and the contents poured into 200 mL of ice water with stirring. It was stirred for 30 min and then the phases were separated. The aqueous phase was extracted a total of three times with 150 mL methyl fcrf-butyl ether each time. The combined organic phases were washed twice with 30 ml of water each time and then with 30 ml of saturated sodium chloride solution. The organic phase was dried with a drying agent (sodium sulfate or magnesium sulfate).
  • a drying agent sodium sulfate or magnesium sulfate
  • Example 3 Synthesis of 2-fluoro-4-methyl-5T(2.2.2-trifluoroethyl)sulfanylaniline in a solvent composed of dimethylformamide and ethyl acetate (ratio 1:2) under autogenous pressure
  • Hastelloy alloy autoclave were placed 23.58 g (150.0 mmol) 5-amino-4-fluoro-2-methylbenzenethiol, 29.0 g (210 mmol) potassium carbonate, 2.42 g (7.51 mmol) tetra-n-butylammonium bromide, 150 mL Submitted ethyl acetate and 75 mL dimethylformamide.
  • the autoclave was sealed, flushed several times with nitrogen, cooled to -10° C. and 23.30 g (196.6 mmol) of 1,1,1-trifluoro-2-chloroethane were introduced at this temperature. The autoclave was then heated to 60° C.
  • Hastelloy alloy autoclave In a 500 mL Hastelloy alloy autoclave were placed 23.58 g (150.0 mmol) 5-amino-4-fluoro-2-methylbenzenethiol, 29.0 g (210 mmol) potassium carbonate, 2.42 g (7.51 mmol) tetra-n-butylammonium bromide, 150 mL Ethyl acetate and 75 mL polyethylene glycol 400 submitted. The autoclave was sealed, flushed several times with nitrogen, cooled to -10° C. and 24.70 g (208.5 mmol) of 1,1,1-trifluoro-2-chloroethane were introduced at this temperature.
  • the internal pressure was then increased to 4 bar by introducing nitrogen, the autoclave was heated to 60° C. and stirred at this temperature for 63 h (stirring speed: 300 rpm). The internal pressure rose to 5.6 bar. It was then cooled to 18° C. and the autoclave was vented. The reaction mixture was mixed with 100 mL water, stirred for a further 2 h, transferred to a separating funnel and the phases were separated. 163.7 g of an upper phase, 171.9 g of a middle phase and 47.6 g of a lower phase were obtained.
  • Hastelloy alloy autoclave were placed 23.58 g (150.0 mmol) 5-amino-4-fluoro-2-methylbenzenethiol, 29.0 g (210 mmol) potassium carbonate, 2.42 g (7.51 mmol) tetra-n-butylammonium bromide, 150 mL Submitted ethyl acetate and 73 mL of dimethyl sulfoxide.
  • the autoclave was sealed, flushed several times with nitrogen, cooled to -10° C. and 24.0 g (203 mmol) of 1,1,1-trifluoro-2-chloroethane were introduced at this temperature. The autoclave was then heated to 60° C.
  • the autoclave was then cooled with dry ice and 7.7 g (65 mmol) of 1,1,1-trifluoro-2-chloroethane were introduced.
  • the autoclave was sealed and the internal pressure increased to 10 bar by introducing argon. It was heated to 60° C. and stirred at this temperature for 16 h (stirring speed: 600 rpm).
  • the autoclave was vented and the contents poured into 200 mL of ice water with stirring. It was stirred for 30 min and then the phases were separated. The aqueous phase was extracted a total of three times with 150 mL of methyl to -butyl ether each time.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)

Abstract

La présente invention concerne un procédé de préparation de (2,2,2-trifluoroéthyl)sulfanylaniline représentée par la formule (I), dans laquelle R1 et R2 ont les significations données dans la description.
EP22754090.3A 2021-07-27 2022-07-22 Procédé de préparation de dérivés de (2,2,2-trifluoroéthyl)sulfanylaniline Pending EP4377294A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
EP21187944 2021-07-27
PCT/EP2022/070624 WO2023006607A1 (fr) 2021-07-27 2022-07-22 Procédé de préparation de dérivés de (2,2,2-trifluoroéthyl)sulfanylaniline

Publications (1)

Publication Number Publication Date
EP4377294A1 true EP4377294A1 (fr) 2024-06-05

Family

ID=77103841

Family Applications (1)

Application Number Title Priority Date Filing Date
EP22754090.3A Pending EP4377294A1 (fr) 2021-07-27 2022-07-22 Procédé de préparation de dérivés de (2,2,2-trifluoroéthyl)sulfanylaniline

Country Status (8)

Country Link
EP (1) EP4377294A1 (fr)
JP (1) JP2024528718A (fr)
KR (1) KR20240038029A (fr)
CN (1) CN117715888A (fr)
IL (1) IL310365A (fr)
MX (1) MX2024001312A (fr)
TW (1) TW202321195A (fr)
WO (1) WO2023006607A1 (fr)

Family Cites Families (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE4333058A1 (de) 1993-09-29 1995-03-30 Hoechst Ag Verfahren zur Herstellung von Trifluorethylschwefelverbindungen aus Thiolaten und 1-Chlor-2,2,2-trifluorethan
EP2606726A1 (fr) * 2011-12-21 2013-06-26 Bayer CropScience AG Dérivés de trifluoroéthylsulfure substitués par du N-arylamidine en tant qu'acaricides et insecticides
TWI623520B (zh) 2012-12-12 2018-05-11 德商拜耳作物科學股份有限公司 製備雙（３－胺基苯基）二硫化物及３－胺基硫醇之方法
EP3010889B1 (fr) 2013-06-20 2018-10-03 Bayer CropScience Aktiengesellschaft Dérivés d'arylsulfure et d'arylsulfoxyde comme acaricides et insecticides

Also Published As

Publication number Publication date
TW202321195A (zh) 2023-06-01
CN117715888A (zh) 2024-03-15
MX2024001312A (es) 2024-02-14
IL310365A (en) 2024-03-01
JP2024528718A (ja) 2024-07-30
KR20240038029A (ko) 2024-03-22
WO2023006607A1 (fr) 2023-02-02

Similar Documents

Publication Publication Date Title
EP0143384B1 (fr) Procédé de préparation de dérivés de bêta-hydroxyéthyl-1,2,4-triazole
EP2200978A1 (fr) Procede de production de diamides sulfoniques
DE10129057A1 (de) Verbessertes Verfahren zur Herstellung kernfluorierter Aromaten
EP0200051B1 (fr) Procédé de préparation d'imidates
EP1616863A1 (fr) Procédé pour la préparation des composés aromatiques fluorés
DD202022A5 (de) Verfahren zur sulfenylierung von n-alkylcarbamaten
EP0168344B1 (fr) Procédé pour la préparation de dérivés d'éthers alpha, alpha-difluoro-alcoyl-phényl
EP4377294A1 (fr) Procédé de préparation de dérivés de (2,2,2-trifluoroéthyl)sulfanylaniline
CH632501A5 (de) Verfahren zur herstellung von 1-azolyl-3,3-dimethyl-1-phenoxy-butan-2-onen.
DE2425979A1 (de) Verfahren zur herstellung von pyrazolen
WO2024153573A1 (fr) Procédé de préparation de dérivés de (2,2,2-trifluoroéthyl) sulfanylaniline
DE3123878A1 (de) Neue sulfobetaine und verfahren zu ihrer herstellung
EP0693466B1 (fr) Procédé pour la préparation de composés aromatiques fluorés et diamides
EP0059241A1 (fr) Procédé de préparation des halogénures aromatiques de sulfonyle
DE69837852T2 (de) Derivate von o-(perfluor)dibenzofuranium-salzen, zwischenprodukte zu ihrer herstellung, verfahren zur herstellung der zwischenprodukte, perfluoralkylierungsmittel und perfluoralkylierungsverfahren
DE69911737T2 (de) Verfahren zur herstellung von aromatischen schwefelverbindungen
DE112020000596T5 (de) Herstellungsverfahren für chlorbenzolverbindung
DE4007049A1 (de) Verfahren zur herstellung von 3'-aminopropyl-2-sulfatoethylsulfon
EP0518882B1 (fr) N-acyl-aminoalkyl-2-hydroxyethylsulfure et un procede de preparation
DE602004008845T2 (de) Verfahren zu Fluorierung von Äthern
DE19904310A1 (de) Verfahren zur Herstellung heterocyclischer Verbindungen
EP0358018A2 (fr) Procédé de préparation d'oxyguanidines
WO2024200331A2 (fr) Procédé de production du méthyl-4-isocyanatosulfonyl-5-méthyl-thiophène-3-carboxylate
EP0983982B1 (fr) Procédé pour la préparation de chlorures de sulfonyle aromatiques ou hétéroaromatiques
DE69819504T2 (de) Verfahren zur herstellung von 2-alkylthiobenzonitril-derivaten

Legal Events

Date Code Title Description
STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: UNKNOWN

STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: THE INTERNATIONAL PUBLICATION HAS BEEN MADE

PUAI Public reference made under article 153(3) epc to a published international application that has entered the european phase

Free format text: ORIGINAL CODE: 0009012

STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: REQUEST FOR EXAMINATION WAS MADE

17P Request for examination filed

Effective date: 20240227

AK Designated contracting states

Kind code of ref document: A1

Designated state(s): AL AT BE BG CH CY CZ DE DK EE ES FI FR GB GR HR HU IE IS IT LI LT LU LV MC MK MT NL NO PL PT RO RS SE SI SK SM TR

DAV Request for validation of the european patent (deleted)
DAX Request for extension of the european patent (deleted)