WO2024251913A1 - Synthèse de 2-cyano pyridyl sulfoxydes énantioenrichis - Google Patents

Synthèse de 2-cyano pyridyl sulfoxydes énantioenrichis Download PDF

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WO2024251913A1
WO2024251913A1 PCT/EP2024/065669 EP2024065669W WO2024251913A1 WO 2024251913 A1 WO2024251913 A1 WO 2024251913A1 EP 2024065669 W EP2024065669 W EP 2024065669W WO 2024251913 A1 WO2024251913 A1 WO 2024251913A1
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process according
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halogen
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Simon Williams
Helmars Smits
Sandeep Reddy KANDUKURI
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Syngenta Crop Protection AG Switzerland
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Syngenta Crop Protection AG Switzerland
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Priority to EP24732217.5A priority patent/EP4724425A1/fr
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Priority to MX2025013857A priority patent/MX2025013857A/es
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    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N43/00—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
    • A01N43/90—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having two or more relevant hetero rings, condensed among themselves or with a common carbocyclic ring system
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01P—BIOCIDAL, PEST REPELLANT, PEST ATTRACTANT OR PLANT GROWTH REGULATORY ACTIVITY OF CHEMICAL COMPOUNDS OR PREPARATIONS
    • A01P7/00—Arthropodicides
    • A01P7/04—Insecticides
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D211/00—Heterocyclic compounds containing hydrogenated pyridine rings, not condensed with other rings
    • C07D211/04—Heterocyclic compounds containing hydrogenated pyridine rings, not condensed with other rings with only hydrogen or carbon atoms directly attached to the ring nitrogen atom
    • C07D211/06—Heterocyclic compounds containing hydrogenated pyridine rings, not condensed with other rings with only hydrogen or carbon atoms directly attached to the ring nitrogen atom having no double bonds between ring members or between ring members and non-ring members
    • C07D211/36—Heterocyclic compounds containing hydrogenated pyridine rings, not condensed with other rings with only hydrogen or carbon atoms directly attached to the ring nitrogen atom having no double bonds between ring members or between ring members and non-ring members with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
    • C07D211/54—Sulfur atoms
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D401/00—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, at least one ring being a six-membered ring with only one nitrogen atom
    • C07D401/02—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, at least one ring being a six-membered ring with only one nitrogen atom containing two hetero rings
    • C07D401/12—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, at least one ring being a six-membered ring with only one nitrogen atom containing two hetero rings linked by a chain containing hetero atoms as chain links
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D487/00—Heterocyclic compounds containing nitrogen atoms as the only ring hetero atoms in the condensed system, not provided for by groups C07D451/00 - C07D477/00
    • C07D487/02—Heterocyclic compounds containing nitrogen atoms as the only ring hetero atoms in the condensed system, not provided for by groups C07D451/00 - C07D477/00 in which the condensed system contains two hetero rings
    • C07D487/04—Ortho-condensed systems

Definitions

  • the present invention relates to the synthesis of enantioenriched sulfoxide compounds as intermediates for enantioselective preparation of sulfoximines.
  • a particularly favorable method for a larger scale synthesis is an enantiospecific iron catalyzed imination of enantioenriched sulfoxides with amino 4-nitrobenzoate salts (Angew. Chem. Int. Ed. 2018, 57, 324).
  • Enantioenriched sulfoxides could be prepared from corresponding sulfides by a variety of oxidation methods (reviewed in Chem. Rev. 2020, 120, 4578; Chem. Rev. 2010, 110, 4303; Pitchen Philippe et al, Tetrahedron Letters, 1 January 1984, pages 1049-1052). Notable methods include Kagan’s titanium mediated oxidation using a tartrate ligand (J. Am. Chem. Soc. 1984, 106, 8188). A catalytic version of this protocol has been developed that avoids the use of stoichiometric titanium (Synlett. 1996, 404).
  • Biocatalysis using engineered enzymes offers an efficient and sustainable option for enantioselective sulfide oxidation (Catalysts, 2018, 8, 624) however the efficiency of such enzymes is highly substrate dependent and often requires extensive optimization for a single substrate.
  • the present invention describes such a strategy starting from thio derivatives of formula (II) which after stereoselective oxidation yield sulfoxides of formula (I) which could later be elaborated to enantioenriched sulfoxides of formula (III). These can then be converted to enantioenriched sulfoximines as described above.
  • Scheme 2 Ri is hydrogen, halogen, Ci-Ce-haloalkyl, Ci-Ce-cyanoalkyl, Ci-Ce-cyanoalkoxy, Cs-Ce-cyanocycloalkyl or optionally substituted aryl;
  • R2 is C1-C4 alkyl
  • R3 is C1-C4 alkyl
  • G1 and G2 are independently CH or N
  • the present invention provides a process for the preparation of enantiomerically enriched sulfoxides of formula (I) wherein
  • R1 is hydrogen, halogen, Ci-Ce-haloalkyl, Ci-Ce-cyanoalkyl, Ci-Ce-cyanoalkoxy, Cs-Ce-cyanocycloalkyl or optionally substituted aryl;
  • R2 is C1-C4 alkyl by stereoselective oxidation of a sulfanyl compound of formula (II) wherein Ri and R2 are as defined for compounds of formula (I); in the presence of an oxidant, in the presence of a chiral reagent or catalyst, optionally in the presence of a suitable acid additive, in an appropriate solvent (or diluent); to produce a sulfinyl compound of formula (I)
  • R1, R2 and S* are as defined previously.
  • a sulfanyl compound of formula (II) in the presence of an oxidant, in the presence of a metal derivative, in the presence of a chiral ligand (such as a reagent or catalyst), in an appropriate solvent (or diluent) and optionally in the presence of a suitable acid additive.
  • Suitable and preferred oxidants are inorganic peroxides, such as hydrogen peroxide or organic peroxides, such as tert-butyl hydroperoxide.
  • the oxidant is hydrogen peroxide.
  • the ratio of the oxidant used, compared to the sulfanyl compound of formula (II), is in the range from 8:1 to 0.8:1 , preferably between 5:1 and 1 :1 , more preferably between 3:1 and 1 :1.
  • Example of suitable and preferred metal derivatives are salts of vanadium and iron.
  • iron salts are used.
  • Suitable examples include but are not limited to VOCI2, VO(acac)2, Fe(acac)3, Fe(acac)2.
  • the amount of metal catalyst used, compared to the sulfanyl compounds of formula (II) is in the range from 0.1 mol% to 50 mol%; preferably in the range between 0.5 mol % and 10 mol%.
  • Suitable and preferred chiral ligands are selected from Schiff bases formed from salicylaldehyde derivatives and chiral amines.
  • the metal derivative is iron and the chiral ligand is a Schiff base formed from salicylaldehyde derivatives and chiral amino-alcohols represented by a compound of formula (IV),
  • R4 is halogen and * represents (where appropriate) an enantioenriched chiral center in either R or
  • R s chloro, iodo or bromo
  • the chiral ligand is used as an enantioenriched compound.
  • the enantiomeric ratio of the ligand is from 80:20 to 100:0 [R]:[S] or [S]:[R], preferably the enantiomeric ratio of the ligand is from 90:10 to 100:0 [R]:[S] or [S]:[R],
  • the amount of the ligand used, compared to the sulfanyl compound of formula (II), is in the range from 0.1 to 30 mol %, preferably from 1 to 15 mol%, most preferably from 2 to 10 mol%.
  • the ligand can be formed in situ in the reaction by adding the appropriate salicylaldehyde derivative and an appropriate amino alcohol.
  • the ligand can be prepared in a separate step.
  • Example of suitable and preferred additives are carboxylic acids.
  • the additive is a benzoic acid, optionally mono-, di- or tri-substituted by methyl, ethyl, isopropyl, methoxy or dimethylamino, optionally in form of a lithium, sodium or potassium salt.
  • the additive is a methoxybenzoic acid or a dimethylaminobenzoic acid (optionally in form of a lithium, sodium or potassium salt), even more preferably 4-methoxybenzoic acid.
  • the amount of the additive used, compared to the sulfanyl compound of formula (II) is in the range from 0.1 to 10 mol %, most preferably from 0.5 to 5 mol %.
  • the oxidizing agent is hydrogen peroxide
  • the metal salt is Fe(acac)3
  • the ligand is selected from:
  • Suitable and preferred solvents are esters, nitriles, alcohols, ethers, and aliphatic, aromatic or halogenated hydrocarbons.
  • suitable and preferred solvents include but are not limited to: ethyl acetate, isopropyl acetate, acetonitrile, butyronitrile, ethanol, methanol, isopropanol, n-propanol, tetra hydrofuran, 2-methyl tetra hydrofuran, cyclopentylmethyl ether, t-butylmethyl ether, diethyl ether, 1 ,4-dioxane pentane, hexane, cyclohexane, heptane, dichloromethane, 1 ,2-dichloroethane, chloroform, benzene, toluene, xylene, chlorobenzene, fluorobenzene, dichlorobenzene, methoxybenzene
  • the solvent is an aromatic or halogenated hydrocarbon, for example: dichloromethane, 1 ,2- dichloroethane, chloroform, benzene, toluene, xylene, chlorobenzene, fluorobenzene, dichlorobenzene, methoxybenzene, trifluoromethylbenzene, p-cymene, mesitylene, ethylbenzene, isopropylbenzene, or mixtures thereof.
  • an aromatic or halogenated hydrocarbon for example: dichloromethane, 1 ,2- dichloroethane, chloroform, benzene, toluene, xylene, chlorobenzene, fluorobenzene, dichlorobenzene, methoxybenzene, trifluoromethylbenzene, p-cymene, mesitylene, ethylbenzene, isopropylbenzene, or mixtures thereof.
  • the solvent is selected from: dichloromethane, toluene, xylene, chlorobenzene, methoxybenzene or mixtures thereof.
  • the ratio of enantiomers produced is from 50.5:49.5 to 100:0 [R]:[S] or [S]:[R], Preferably the enantiomeric ratio of the product is from 70:30 to 100:0 [R]:[S] or [S]:[R], even more preferably 90:10 to 100:0 [R]:[S] or [S]:[R]
  • the enantiomeric ratio of the product can be either lower or higher than the enantiomeric ratio of the chiral ligand used in the reaction.
  • the ratio of enantiomers produced can be increased by crystallization if required.
  • Such methods are known to those skilled in the art and include crystallization from an organic solvent, a mixture of organic solvents or a mixture of organic solvents with water.
  • alkyl as used herein, in isolation or as part of a chemical group, represents straight-chain orbranched hydrocarbons, preferably with 1 to 6 carbon atoms, for example methyl, ethyl, n- propyl, isopropyl, n-butyl, isobutyl, s-butyl, t-butyl, pentyl, 1- methylbutyl, 2-methylbutyl, 3-methylbutyl, 1 ,2- dimethylpropyl, 1 ,1 -dimethylpropyl, 2,2- dimethylpropyl, 1 -ethylpropyl, hexyl, 1 -methylpentyl, 2- methylpentyl, 3-methylpentyl, 4- methylpentyl, 1 ,2-dimethylpropyl, 1 ,3-dimethylbutyl, 1 ,4-dimethylbutyl,2,3- dimethylbutyl, 1 ,1- dimethylbutyl,
  • Alkyl groups with 1 to 4 carbon atoms are preferred, forexample methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, s-butyl or t-butyl.
  • aryl represents a mono-, bi- or polycyclical aromatic system with preferably 6 to 14, more preferably 6 to 10 ring-carbon atoms, for example phenyl, naphthyl, anthryl, phenanthrenyl, preferably phenyl.
  • Aryl also represents polycyclic systems, for example tetrahydronaphtyl, indenyl, indanyl, fluorenyl, biphenyl.
  • Arylalkyls are examples of substituted aryls, which may be further substituted with the same or different substituents both at the aryl or alkyl part. Benzyl and 1 — phenylethyl are examples of such arylalkyls.
  • halogen represents fluoro, chloro, bromo or iodo, particularly fluoro, chloro or bromo.
  • the chemical groups which are substituted with halogen for example haloalkyl, halocycloalkyl, haloalkyloxy, haloalkylsulfanyl, haloalkylsulfinyl or haloalkylsulfonyl are substituted one or up to the maximum number of substituents with halogen. If “alkyl”, “alkenyl” or “alkynyl” are substituted with halogen, the halogen atoms can be the same or different and can be bound at the same carbon atom or different carbon atoms.
  • the term “optionally substituted” means that the group in question can be substituted with zero up to the maximum number of substituents with groups independently selected from: halogen, methyl, ethyl, propyl, isopropyl, t-butyl, cyclopropyl, cyclobutyl, cyclopropyl, cyclohexyl, trifluoromethyl, difluoromethyl, chlorodifluoromethyl, trichloromethyl, methoxy, ethoxy, trifluoromethoxy, difluoromethoxy, nitro, cyano, hydroxy, sulfhydryl, acetyl, acetoxy, COOH, COOMe, COOEt, CONH2, CONHMe, CONMe2, amino, methylamino, dimethylamino, phenyl.
  • enantiomerically enriched means that one of the enantiomers of the compound is present in excess in comparison to the other enantiomer. This excess will hereafter be referred to as enantiomeric excess or ee.
  • the ee may be determined by chiral GC, HPLC or SFC analysis. The ee is equal to the difference between amounts of enantiomers divided by the sum of the amounts of the enantiomers, which quotient can be expressed as a percentage after multiplication by 100.
  • R1 is CF3
  • R2 is ethyl: as described in WO2014104407
  • R1 is cyanocyclopropyl
  • R2 is ethyl: as described in WO2022074214
  • R1 is cyanoisopropoxy
  • R2 is ethyl: as shown in Scheme 4
  • Ri is 3-fluorophenyl
  • R2 is methyl: as shown in Scheme 5
  • R1 is cyanoisopropyl
  • R2 is ethyl: as shown in Scheme 6
  • coupling with ethyl cyanoacetate in the presence of a base yielded coupling product which was decarboxylated using sodium chloride in acetic acid.
  • double methylation with either methyl iodide or dimethyl sulfate provided a compound of formula (II) with this substitution pattern.
  • Embodiment 1 provides a process for the preparation of enantiomerically enriched sulfoxides of formula (I) as defined above.
  • Embodiment 2 provides a process for the preparation of a compound of formula (I) which process comprises: stereoselective oxidation of a sulfanyl compound of formula (II) in the presence of an oxidant, in the presence of a chiral reagent or catalyst, optionally in the presence of a suitable additive, in an appropriate solvent (or diluent), to produce a compound of formula (I) as defined above.
  • Embodiment 3 provides preferred alternatives of the oxidant, metal derivative, chiral ligand, solvent (or diluent) and acid additive that are used in the process of embodiments 1 - 2 and which are, in any combination thereof, as set out above.
  • Ri and R2 are, in any combination thereof, as set out below:
  • R1 is hydrogen, halogen, Ci-Ce-haloalkyl, Ci-Ce-cyanoalkyl, Ci-Ce-cyanoalkoxy, C3-C6- cyanocycloalkyl or optionally substituted aryl.
  • R1 is hydrogen, halogen, Ci-C4-haloalkyl, Ci-C4-cyanoalkyl, Ci-C4-cyanoalkoxy, C3-C4- cyanocycloalkyl or optionally substituted aryl.
  • R1 is hydrogen, halogen, trifluoromethyl, cyanoisopropoxy, cyanoisopropyl, cyanocyclopropyl or optionally substituted phenyl.
  • optionally substituted phenyl is phenyl or halo-phenyl.
  • R2 is C1-C4 alkyl; more preferably, R2 is methyl or ethyl; most preferably, R2 is ethyl.
  • the crude material was purified by silica gel chromatography using ethyl acetate and cyclohexane as an eluent to yield the title compound (2.60 g, 94% purity, 71 % yield) as a brown solid.
  • Results A single crystal grown from di-isopropyl ether was selected for X-ray data analysis.
  • the crystal sample mounted had dimensions of 0.4 mm x 0.3 mm x 0.3 mm and was a colorless prism.
  • Data collection was performed on a Rigaku Oxford Diffraction Supernova diffractometer at 293 K.
  • the unit cell was determined to be orthorhombic (space group P212121), and the structure contained one molecule in the crystal asymmetric unit ( Figure 1 , a thin stick representation labelled by chirality. Figure 1 generated in Flare software package).
  • the stereochemistry was unambiguously determined to be the R isomer, with a Flack parameter of 0.02 +/- 0.03. Crystallographic data is summarized in Table 1 and selected geometric parameters are listed in Table 2.
  • the resulting reaction mixture was stirred for further 20 h at the same temperature.
  • the reaction mixture was poured into EtOAc (23 ml) and quenched by addition of 1 .0M NaHSOs (2.4 ml). Phases were separated and the organic phase was washed with 1 .0M HCI (2.3 ml) and aq NaHCOs.
  • the organic phase was dried over anhydrous Na2SO4 and evaporated under reduced pressure.
  • the crude material was purified by a reverse phase HPLC (water/MeCN/0.1 % formic acid mobile phase) to yield the title compound (230 mg, >99.5%ee, 93% yield) as a white powder.
  • the resulting reaction mixture was stirred vigorously for further 22 h at the same temperature.
  • the reaction was quenched by addition of 40% aq NaHSO3 (10.6 ml) and diluted with anisole (53 ml). Phase were separated and the organic phase was washed with 1 M H2SO4 (21 ml), aq saturated NaHCOs (21 ml) and brine (21 ml).
  • the combined organic phase was dried over anhydrous Na2SO4 and concentrated under reduced pressure.
  • the crude material was purified by a reverse phase HPLC (water/MeCN as a mobile phase) to yield the title compound (10.44 g, >99.5% ee, 93% yield) as a white powder.
  • the reaction mixture was stirred for further 5 h and then quenched by adding aq saturated sodium thiosulphate at 0 °C.
  • the organic layer was separated, and aqueous layer extracted with ethyl acetate.
  • the combined organic layers were washed with brine, dried over Na2SO4, concentrated under reduced pressure to get the crude compound.
  • the crude material was purified by silica gel chromatography using cyclohexane and ethyl acetate as an eluent to yield the title compound (1 .55 g, 89% purity, >99.5% ee, 79% yield).
  • the reaction mixture was stirred for 2 h at 24°C and then quenched by adding saturated Na2S20s at 0 °C.
  • the organic layer was separated, and aqueous layer extracted with ethyl acetate.
  • the combined organic layers were washed with brine, dried over Na2SO4 and concentrated under reduced pressure to obtain the crude product.
  • the crude material was purified by column chromatography using cyclohexane and ethyl acetate as an eluent to yield the title compound (5.48 g, 91 % purity, 97% ee, 81 % yield).
  • the resulting biphasic mixture was stirred at 10°C for 22h.
  • the reaction was quenched by cooling to 0°C and the addition of 40% aq. NaHSOs (0.315 ml, 1.60 mmol).
  • the mixture was diluted with EtOAc (10 ml) and cone.
  • H2SO4 50 pl was added to acidify the mixture.
  • the aqueous layer was again extracted with EtOAc (15 ml).
  • the combined organic layer was washed with sat. aq. NaHCOs (8 ml) and brine (8 ml).
  • the organic layer was dried over anhydrous MgSO4 concentrated under reduced pressure.
  • N2-methyl-5-(trifluoromethyl) pyridine-2,3-diamine (344 mg, 1.71 mmol) was then added, and the reaction mixture was stirred at 70 °C for 2 h. The reaction mixture was then cooled to ambient temperature and diluted with cold water. The resulting mixture was extracted with EtOAc, the combined organic layer was dried over anhydrous Na2SO4, filtered, and evaporated under reduced pressure. The crude residue was purified by silica gel chromatography using ethyl acetate/cyclohexane as an eluent to yield the title compound (220 mg, 91 % purity, 32% yield) as a light brown solid.
  • Example 18 Preparation of 2-[5-[(R)-ethylsulfinyl]-6- [3-methyl-6-(trifluoro methyl) imidazo[4,5-b] pyridin-2-
  • a solution of 5-(1-cyano-1-methyl-ethyl)-3-[(R)-ethylsulfinyl]-N-[2-(methylamino)-5-(trifluoromethyl)-3- pyridyl] pyridine-2-carboxamide (200 mg, 91 % purity, 0.414 mmol) in acetic acid (1.4 mL) was heated at 110 °C for 2 h. After full consumption of starting material, the reaction mixture was evaporated under reduced pressure. The crude material was purified by silica gel chromatography using ethyl acetate/cyclohexane as an eluent to afford the title compound (130 mg, 97% purity, 72% yield) as a brown solid.

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Abstract

L'invention concerne un procédé de préparation de composés de pyridine énantioenrichis de formule (I), dans laquelle R1 et R2 sont tels que définis dans la description.
PCT/EP2024/065669 2023-06-06 2024-06-06 Synthèse de 2-cyano pyridyl sulfoxydes énantioenrichis Ceased WO2024251913A1 (fr)

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Application Number Priority Date Filing Date Title
IL324550A IL324550A (en) 2023-06-06 2024-06-06 Synthesis of enantioenriched 2-cyano pyridyl sulfoxides
CN202480035203.6A CN121219266A (zh) 2023-06-06 2024-06-06 对映异构体富集的2-氰基吡啶基亚砜的合成
EP24732217.5A EP4724425A1 (fr) 2023-06-06 2024-06-06 Synthèse de 2-cyano pyridyl sulfoxydes énantioenrichis
MX2025013857A MX2025013857A (es) 2023-06-06 2025-11-20 Sintesis de sulfoxidos de 2-ciano piridilo enantioenriquecidos

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WO2018095795A1 (fr) 2016-11-23 2018-05-31 Syngenta Participations Ag Dérivés polycycliques à activité pesticide comportant des substituants contenant du soufre
WO2021175959A1 (fr) 2020-03-04 2021-09-10 Syngenta Crop Protection Ag Procédé de préparation de carboxylates et d'amides d'acide 5-chloro-3-alkylsulfanyl-pyridine-2-carboxylique
WO2022074214A1 (fr) 2020-10-09 2022-04-14 Syngenta Crop Protection Ag Procédé de préparation d'esters amides et de nitriles d'acide 5-(1-cyanocyclopropyl)-pyridine-2-carboxylique
WO2022253841A1 (fr) 2021-06-02 2022-12-08 Syngenta Crop Protection Ag Dérivés hétérocycliques à action pesticide avec des substituants contenant de la sulfoximine

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Publication number Priority date Publication date Assignee Title
WO2014104407A1 (fr) 2012-12-27 2014-07-03 Sumitomo Chemical Company, Limited Composés d'oxazole fusionnés et leur utilisation dans la lutte contre les organismes nuisibles
WO2016118858A1 (fr) 2015-01-23 2016-07-28 Akebia Therapeutics, Inc. Formes solides d'acide 2-(5-(3-fluorophényl)-3-hydroxypicolinamido)acétique, compositions et utilisation dudit acide
WO2018095795A1 (fr) 2016-11-23 2018-05-31 Syngenta Participations Ag Dérivés polycycliques à activité pesticide comportant des substituants contenant du soufre
WO2021175959A1 (fr) 2020-03-04 2021-09-10 Syngenta Crop Protection Ag Procédé de préparation de carboxylates et d'amides d'acide 5-chloro-3-alkylsulfanyl-pyridine-2-carboxylique
WO2022074214A1 (fr) 2020-10-09 2022-04-14 Syngenta Crop Protection Ag Procédé de préparation d'esters amides et de nitriles d'acide 5-(1-cyanocyclopropyl)-pyridine-2-carboxylique
WO2022253841A1 (fr) 2021-06-02 2022-12-08 Syngenta Crop Protection Ag Dérivés hétérocycliques à action pesticide avec des substituants contenant de la sulfoximine

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