WO2020175578A1 - Procédé de production de composé de pyridylpyrazine - Google Patents

Procédé de production de composé de pyridylpyrazine Download PDF

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WO2020175578A1
WO2020175578A1 PCT/JP2020/007856 JP2020007856W WO2020175578A1 WO 2020175578 A1 WO2020175578 A1 WO 2020175578A1 JP 2020007856 W JP2020007856 W JP 2020007856W WO 2020175578 A1 WO2020175578 A1 WO 2020175578A1
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group
compound
formula
atom
pyrazine
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萩谷　弘寿
浩平 折本
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Sumitomo Chemical Co Ltd
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Sumitomo Chemical Co Ltd
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07B—GENERAL METHODS OF ORGANIC CHEMISTRY; APPARATUS THEREFOR
    • C07B61/00—Other general methods
    • 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
    • C07D401/04—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 directly linked by a ring-member-to-ring-member bond

Definitions

  • the present invention relates to a method for producing a pyridylpyrazine compound.
  • Certain pyridylpyrazine compounds are known as active ingredients of pest control agents (Patent Document 1, etc.).
  • Patent Document 1 International Publication No. 2 0 1 7/0 6 5 2 2 8
  • An object of the present invention is to provide a new method for producing the pyridylpyrazine compound described in Patent Document 1.
  • the present inventors have conducted a reaction between 2-halogen-substituted pyrazines and 2-halogen-substituted pyridines under a reducing condition, and as a result, two types of halogen atoms are eliminated so that a coupling coupling reaction proceeds. Then, they found that a pyridylpyrazine compound was produced in a high yield, and completed the present invention.
  • the present invention is as follows.
  • X represents a chlorine atom, a bromine atom or an iodine atom
  • halogen atoms ⁇ 1- ⁇ 10 chain hydrocarbon groups may have one or more halogen atoms ( ⁇ 1 _ ⁇ 5 alkoxy) ⁇ 2 _ ⁇ 5 alkyl group, may have one or more halogen atoms ( ⁇ 1 —
  • alkylsulfanyl 0 2 — 0 5 alkyl group
  • Group ⁇ A group consisting of a halogen atom and a _ 1 _ ⁇ 6 haloalkyl group. ] And a compound of formula (2)
  • [3 ⁇ 4 2 represents cyclopropylmethyl group, cyclopropyl group, or one or more of which may have a halogen atom ⁇ 1 - ⁇ 6 alkyl group,
  • a compound represented by the formula (3) by reacting the compound represented by the formula (3) with at least one metal compound selected from the group consisting of a cobalt compound, a nickel compound and an iron compound, and a reducing agent.
  • the reducing agent contains at least one of a zero-valent metal selected from zinc, iron, manganese, and copper or a monovalent compound of the metal, an organic one-electron reducing agent, and a Grignard reagent.
  • a pyridylpyrazine compound can be efficiently produced by the production method of the present invention. ⁇ 2020/175578 4 ⁇ (: 170? 2020 /007856
  • the phrase “may have one or more halogen atoms” includes the case of having a halogen atom as a substituent and the case of not having a halogen atom as a substituent, and having two or more halogen atoms. When these are present, these halogen atoms may be the same or different from each other.
  • the notation "x10” means that the number of carbon atoms is or.
  • the notation “0 1 — 0 6” means that the number of carbon atoms is 1 to 6.
  • the halogen atom represents a fluorine atom, a chlorine atom, a bromine atom or an iodine atom.
  • the "chain hydrocarbon group” refers to an alkyl group, an alkenyl group and an alkynyl group.
  • the “cyclic hydrocarbon group” represents a cycloalkyl group.
  • alkyl group examples include a methyl group, an ethyl group, a propyl group, an isopropyl group, a 1,1-dimethylpropyl group, a 1,2-dimethylpropyl group,
  • alkenyl group examples include vinyl group, 1-propenyl group, 2-p-openenyl group, 1-methyl-1-propenyl group, 1-methyl-2-propenyl group, 1, 2-- Dimethyl-1-propenyl group, 1, 1-dimethyl-2-propenyl group, 1-ethyl-1-propenyl group, 1-ethyl-2-propenyl group,
  • a 3-butenyl group, a 4-pentenyl group and a 5-hexenyl group can be mentioned.
  • alkynyl group examples include ethynyl group, 1-propynyl group, 2-propynyl group, 1-methyl-2-propynyl group, 1,1-dimethyl-2-propynyl group, 1-ethyl-2-propynyl group, 2- Examples include butynyl group, 4-pentynyl group and 5-hexynyl group. ⁇ 2020/175578 5 (: 170? 2020/007856
  • a chain hydrocarbon group optionally having one or more halogen atoms
  • the “02-010 haloalkyl group” refers to a group in which the hydrogen atom of the 02-010 alkyl group is substituted with a halogen atom, and examples thereof include a 02-01° fluoroalkyl group.
  • Examples of the “ ⁇ 2— ⁇ 10 haloalkyl group” include a chloroethyl group, 2,2,2-trifluoroethyl group, 2-bromo-1,1,2,2-tetrafluoroethyl group, 2, 2, 3, Examples thereof include 3-tetrafluoropropyl group, 1-methyl-2,2,3,3-tetrafluoropropyl group, perfluorohexyl group and perfluorodecyl group.
  • Examples of the “ ⁇ 2- ⁇ 10 fluoroalkyl group” include, for example, 2,2,2-difluoroethyl group, 2,2,3,3-tetrafluoropropyl group, 1-methyl-2,2,3 , 3-tetrafluoropropyl group, perfluorohexyl group and perfluorodecyl group.
  • cycloalkyl group examples include a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group and a cycloheptyl group.
  • alkoxy refers to a group in which an oxygen atom (o) is bonded to an alkyl group (that is, when 8 is an alkyl group, it is described as [3 ⁇ 4o_]).
  • the alkylsulfanyl group, alkylsulfinyl group, and alkylsulphonyl group represent an alkyl group having a moiety represented by 3(0).
  • examples of the alkylsulfanyl group having 0 are a methylsulfanyl group, an ethylsulfanyl group, a propylsulfanyl group, an isopropylsulfanyl group, and the like.
  • examples of the alkylsulfinyl group having 1 are a methylsulfinyl group, an ethylsulfinyl group, a propylsulfinyl group, an isopropylsulfinyl group, and the like. ⁇ 2020/175578 6 ⁇ (: 170? 2020 /007856
  • examples of the alkylsulfonyl group having a group of 2 include a methylsulfonyl group, an ethylsulfonyl group, a propylsulfonyl group, and an isopropylsulfonyl group.
  • the “2--05 alkyl group” means a group in which ( ⁇ 3 1 — 05 alkoxy) and/or ( ⁇ 2 _05 alkyl) may have one or more halogen atoms, and for example, 2-(trifluoromethoxy)ethyl group, 2,2-difluoro-3-methoxypropyl group, 2,2-difluoro-3-(2,2,2-trifluoroethoxy)propyl group, and 3--(2-chloroethoxy) ) Propyl groups are listed.
  • the term "(may be one or more halogen atom) ( ⁇ 1 _ ⁇ 5 alkylsulfanyl) ⁇ 2- ⁇ 5 alkyl group” means ( ⁇ 1- ⁇ 5 alkylsulfanyl) and/or ( ⁇ 2_05 alkyl) represents a group which may have one or more halogen atoms, and examples thereof include a 2,2-difluoro-2-(trifluoromethylthio)ethyl group.
  • (1)-(5) alkylsulfinyl which may have one or more halogen atoms (2)-(05) alkylsulfinyl) means ((1)-(05) alkylsulfinyl) and/or ( ⁇ 2 _ ⁇ 5 alkyl) represents a group which may have one or more halogen atoms, and examples thereof include a 2,2-difluoro-2-(trifluoromethansulfinyl)ethyl group.
  • the "may have one or more halogen atoms ( ⁇ 1 _ ⁇ 5 alkylsulfonyl) 0 2 — 05 alkyl group” means Alkylsulfonyl) and/or ( ⁇ 2 _ ⁇ 5 alkyl) represents a group which may have one or more halogen atoms, and for example, a 2,2-difluoro-2-(trifluoromethanesulfonyl)ethyl group is Can be mentioned.
  • (3 to 0 6 cycloalkyl) ⁇ 3 1 to 0 3 alkyl group which may have one or more halogen atoms means (0 3 to 0 6 cycloalkyl) and/or ( ⁇ 1 - ⁇ 3alkyl) is a group which may have one or more halogen atoms. ⁇ 2020/175 578 7 (: 170? 2020 /007856
  • alkyl group means (0 3 — 0 7 cycloalkyl) and/or Represents a group having one or more substituents selected from the group ⁇ , and includes, for example, (2,2-difluorocyclopropyl)methyl group, [1-(trifluoromethyl)cyclopropyl]methyl group, [2- (Trifluoromethyl)cyclopropyl]methyl group, 2-cyclopropyl-1,1,2,2-tetrafluoroethyl group, 2—(2,2-difluorocyclopropyl)-1
  • Group ⁇ is a group consisting of a halogen atom, and a _ 1 _ ⁇ 6 haloalkyl group.
  • Examples of the embodiment of the compound represented by the formula (3) include the following compounds.
  • a compound in which is hydrogen is hydrogen.
  • the compound represented by the formula (1) and the compound represented by the formula (2) are treated with at least one metal compound selected from the group consisting of a cobalt compound, a nickel compound and an iron compound, and a reduction compound.
  • the compound represented by the formula (3) can be obtained.
  • the cobalt compound is a compound in which an atom other than cobalt is bound to cobalt (herein, the term "bond” is a general term for coordination bond, covalent bond, ionic bond, etc.), and preferably cobalt (0 ) Compounds and cobalt ( ⁇ ) Compounds are listed.
  • cobalt (0) compound examples include bis(1,5-cyclooctadiene)cobalt (0).
  • cobalt (II) compounds include cobalt (II) acetate, trifluorocobalt acetate ( ⁇ ), cobalt ( ⁇ ), cobalt carboxylates such as acetylacetonate; cobalt chloride ( ⁇ ), cobalt bromide ( ⁇ ) ⁇ ), Iodine ⁇ 0 2020/175 578 9 (: 17 2020/007856
  • cobalt halides such as Balt ( ⁇ ).
  • Cobalt chloride ( ⁇ ), cobalt bromide ( ⁇ ) and cobalt acetate ( ⁇ ) are preferred.
  • the nickel compound is a compound in which an atom other than nickel is bonded to nickel (herein, the term “bonding” refers to a coordination bond, a covalent bond, an ionic bond, etc.), and preferably nickel (0 ) Compounds and nickel ( ⁇ ) Compounds are listed.
  • nickel (0) compound examples include bis(1,5-cyclooctadiene) nickel (0).
  • Nickel ( ⁇ ) compounds include nickel acetate ( ⁇ ), nickel trifluoroacetate ( ⁇ ), nickel ( ⁇ ) nickel carboxylic acid salts such as acetylacetonate; nickel chloride ( ⁇ ), nickel bromide Nickel halides such as ( ⁇ ) and nickel iodide ( ⁇ ); bis(triphenylphosphine) nickel ( ⁇ ) dichloride, (2, 2'-bipyridine) nickel ( ⁇ I) dichloride, dichloro (1 ⁇ 1, 1 ⁇ 1, 1 ⁇ 1', 1 ⁇ 1'-tetramethylethylenediamine) Nickel compounds to which organic compounds such as nickel (II) are bound (coordinated) can be mentioned. Of these, nickel chloride ( ⁇ ), nickel bromide ( ⁇ I) and nickel acetate ( ⁇ ) are preferable.
  • the iron compound is a compound in which an atom other than iron is bound to iron (here, the term bond is a generic term for a coordination bond, a covalent bond, an ionic bond, etc.), and preferably iron (0) Compounds and iron ( ⁇ ) compounds.
  • iron (o) compound examples include bis (1,5-cyclooctadiene) iron (o).
  • Iron ( ⁇ ) compounds include iron acetate ( ⁇ ), iron trifluoroacetate ( ⁇ I), iron ( ⁇ ) iron carboxylates such as acetylacetonate; iron chloride (II)
  • Iron bromide ( ⁇ ), iron iodide ( ⁇ ) and other iron halides Iron bromide ( ⁇ ), iron iodide ( ⁇ ) and other iron halides. Among them, iron (II) chloride, iron (II) bromide and iron (II) acetate are preferable. ⁇ 2020/175 578 10 (: 170? 2020 /007856
  • the amount of the cobalt compound, nickel compound or iron compound used is not limited to this, but is usually 0.001 mol to 0.8 mol per mol of the compound represented by the formula (1). , Preferably 0.01 mol to 0.2 mol.
  • a monovalent, divalent or trivalent state of a cobalt compound, a nickel compound or an iron compound can be used as a reducing agent (a valence of the compound before the reaction is 1 valence, As long as it is divalent or trivalent) or monovalent (when the valence of the compound before the reaction is divalent or trivalent), it can be used without particular limitation.
  • the amount of the reducing agent used is not limited to this, but is usually 0.9 mol to 3.0 mol, preferably 1.0 mol to 2 mol per mol of the compound represented by the formula (1). 0.0 mol.
  • Examples of the reducing agent include a metal-free reducing compound, and a reducing metal or a compound thereof.
  • Examples of the reducing compound include organic one-electron reducing agents, and examples thereof include olefins such as tetrakis(dimethylamino)ethylene and tetrathiafulvalene.
  • Examples of the reducing metal or its compound include a zero-valent metal selected from zinc, iron, manganese and copper, or a monovalent compound of the metal, and a Grignard reagent.
  • Specific examples of the reducing metal or its compound include zero-valent zinc, zero-valent manganese, zero-valent iron, zero-valent copper, and a monovalent copper compound, with zinc being preferred.
  • the zinc is preferably activated.
  • a known method is used as a method for activating zinc.
  • zinc in an unactivated state can be used by simultaneously adding an activator to the coupling reaction system.
  • the amount of zinc used is not limited to this, but is usually 0.9 mol to 3.0 mol, preferably 1.0 mol to 2.0 mol per mol of the compound represented by the formula (1). Is.
  • Examples of the zinc activator used in the present invention include lithium chloride and organic carbohydrate. ⁇ 2020/175578 1 1 ⁇ (: 170? 2020/007856
  • Acids or organic halogen compounds may be mentioned.
  • Organic carboxylic acids include, for example, aliphatic carboxylic acids such as acetic acid, propionic acid, butanoic acid, pivalic acid; benzoic acid, 4-methoxybenzoic acid, 4-methylbenzoic acid, 4 _ nitrobenzoic acid and the like. Aromatic carboxylic acids are mentioned.
  • the amount of the organic carboxylic acid used is not limited to this, but is usually 0.1 to 50 mol per mol of the metal compound such as nickel compound. Alternatively, the amount of the organic carboxylic acid used is not limited to this, but is usually 0.1 to 50 mol per mol of zinc.
  • organic halogen compound examples include allyl chloride, 1,2-dibromoethane, 1-iodobutane, trimethylsilyl chloride and the like. Two or more zinc activators may be used.
  • the amount of the organic halogen compound used is not limited to this, but is usually 0.1 to 50 mol per mol of the metal compound such as nickel compound.
  • the amount of the organohalogen compound used is not limited to this, but is usually 0.1 to 50 mol per mol of zinc.
  • reaction can be carried out in the presence of a solvent.
  • the solvent is preferably an aprotic organic solvent.
  • An aprotic organic solvent has a group containing a proton (that is, a donating proton) such as a hydroxyl group (101 to 1), an amino group, a carboxyl group (1001 to 1) in the molecule. And an organic solvent capable of dissolving the compound represented by the formula (1) and the compound represented by the formula (2).
  • aprotic organic solvent examples include amid solvents such as non-cyclic amide solvents or cyclic amide solvents, ether solvents such as non-cyclic ether solvents or cyclic ether solvents, aromatic hydrocarbon solvents and aliphatic hydrocarbons.
  • the solvent examples include an amid solvent such as a non-cyclic amide solvent or a cyclic amide solvent, and an aromatic hydrocarbon solvent.
  • Amid solvents such as non-cyclic amide solvents or cyclic amide solvents include, for example, dimethylformamide (0 ! ⁇ /!), dimethylacetamide,! ⁇ 1 _ Methyl ⁇ 2020/175 578 12 (: 170? 2020 /007856
  • 2-pyrrolidone can be mentioned.
  • acyclic ether solvent examples include diethyl ether, diisopropyl ether, ethylene glycol dimethyl ether and diethylene glycol dimethyl ether.
  • cyclic ether solvents examples include 1,4-dioxane and tetrahydrofuran.
  • Aromatic hydrocarbon solvents include, for example, benzene, toluene, xylene and mesitylene.
  • Aliphatic hydrocarbon solvents include, for example, hexane, heptane and cyclohexane.
  • toluene, xylene, mesitylene, dimethylformamide, dimethylacetamide and 1 ⁇ 1 _methyl-2-pyrrolidone are preferable. ..
  • two or more kinds of aprotic organic solvents may be used in combination. Specifically, for example, a mixed solvent of 1 ⁇ 1-methyl-2-pyrrolidone and toluene, and dimethylform A mixed solvent of amide and toluene can be used.
  • the amount of the solvent used is not limited to this, but is usually 1 to 50 parts by weight, preferably 1 to 20 parts by weight per 1 part by weight of the compound represented by the formula (1).
  • the coupling reaction can be more efficiently carried out.
  • the coordinating organic compound used in the reaction is preferably a compound capable of coordinating to those metals in the presence of one kind or a mixture of two or more kinds of cobalt compound, nickel compound and iron compound. Any organic compound having such a coordinating property can be used without particular limitation. Generally, an organic compound containing one or more heteroatoms such as nitrogen, phosphorus, oxygen or sulfur is preferable from the viewpoint of coordination ability.
  • organic compound containing a nitrogen atom examples include trialkylamines such as trimethylamine, triethylamine and diisopropylethylamine; arylamines such as triphenylamine, dimethylaniline and diethylaniline; nitrogen-containing heterocyclic compounds such as pyridine, picoline and quinoline. Ring compounds; 1 ⁇ 1, 1 ⁇ 1, ! ⁇ 1, ,! ⁇ 1'-Tetramethylethylenediamine,! ⁇ 1 ,! ⁇ 1 ,! ⁇ 1' ,! ⁇ 1'-Tetra 20/175578 13 ⁇ (: 170? 2020 /007856
  • Methyl-1,3-propanediamine 1 ⁇ 1, 1 ⁇ 1, 1 ⁇ 1, ,1 ⁇ 1, Tetraethylethylenediamine, 1 ⁇ 1, 1 ⁇ 1, 1 ⁇ 1', 1 ⁇ 1' Tetramethyl-1,4 —Bitandiamine and other two-coordinate (that is, bidentate) alkyldiamines; 2,2'-bipyridine, 1,9-phenanthroline, 1,10-phenanthroline, 6, 6 '-Dimethyl-2,2'-bipyridine, 4,4'-bis(trifluoromethyl)-1,2'-bipyridine, dimethyl-2,2'-bipyridine-4,
  • Examples thereof include dicoordinated (ie, bidentate) nitrogen-containing heterocyclic compounds such as dimethyl 4-dicarboxylate and 2,2'-biquinoline.
  • organic compound containing a phosphorus atom examples include alkyl phosphines such as trimethylphosphine, triethylphosphine, 3-methyl-2-butenyl (di _ 1: _butyl) phosphine; 1, 2-bis (di I -Butylphosphino
  • Ethane 1,3-bis (di 1:-butylphosphino) propane, 1, 4-bis (di-I-butylphosphino) butane and other alkyldiphosphines; trimethylphosphite, triethylphosphite, etc.
  • Arylphosphines 1,2-bis(diphenylphosphino)ethane, 1,3-bis(diphenylphosphino)propane, 1,4-bis(diphenylphosphino)butane and other aryldiphosphines; trimethyl Trialkyl phosphates such as phosphates and triethyl phosphates; compounds containing a plurality of phosphorus atoms such as 4,5,-bis(diphenylphosphino)_9,9'-dimethylxanthene and the like.
  • an organic compound containing a phosphorus atom is susceptible to oxidation, it can be used as a mineral acid salt, and by adding a base at the same time, a coordinating organic compound containing a phosphorus atom can be generated in the reaction system. ..
  • Examples of the organic compound containing a sulfur atom include dimethyl sulfoxide, dimethyl sulfone, and sulfolane. ⁇ 2020/175 578 14 (: 170? 2020 /007856
  • Examples of the organic compound containing an oxygen atom include phenol, catechol, and acetylacetonate.
  • Organic compounds containing a nitrogen atom and an oxygen atom can also be used, and examples thereof include proline and 8-quinolinol.
  • Two or more coordinating organic compounds may be used in combination.
  • the coordinating organic compound containing a phosphorus atom and the coordinating organic compound containing a nitrogen atom are used together.
  • the amount of the compound used is not limited to this, but may be a cobalt compound, a nickel compound or an iron compound.
  • the amount is usually 0.1 mol to 50 mol, preferably 0.5 mol to 20 mol per mol.
  • the amount of the compound used is not limited to this, but per mol of cobalt compound, nickel compound or iron compound.
  • the amount is usually 0.05 mol to 30 mol, preferably 0.3 mol to 20 mol.
  • a compound containing a phosphorus atom and a compound containing a nitrogen atom are preferably used.
  • the compound containing a phosphorus atom include trimethylphosphine, triethylphosphine, triphenylphosphine, 1,4-bis(di _ _ptylphosphino).
  • Butane, trimethylphosphite, or triphenylphosphite is preferred.
  • Compounds containing nitrogen atoms include 1 ⁇ ], 1 ⁇ 1 ,1 ⁇ 1', 1 ⁇ 1'-tetramethylethylenediamine, 1 ⁇ 1 ,1 ⁇ 1 ,1 ⁇ 1, ,1 ⁇ 1, tetramethyl- 1,3—Propanedamine, 1,10-phenanthroline, 6,6'-dimethyl-2,2'-bipyridine, 4,4'-bis(trifluoromethyl)-1,2'-bipyridine, dimethyl-2,2' Bipyridine-4,4-dicarboxylate dimethyl, or 2,2'-biquinoline is preferred.
  • the coordinating organic compound is a cobalt compound or a nickel compound in advance. ⁇ 2020/175 578 15 (: 170? 2020 /007856
  • a metal compound coordinated with an iron compound can be used.
  • metal compounds include bis(triphenylphosphine)nickel(II) dichloride, (2,2'-bipyridine)nickel( ⁇ ) dichloride, dichloro (1 ⁇ 1, 1 ⁇ 1, 1 ⁇ 1', 1 ⁇ 1'-Tetramethylethylenediamine) Nickel
  • Specific examples of the compound represented by the formula (1) include 2-chloro-5-(carbolifluoromethoxy)pyrazine, 2-chloro-5-(2,2,2-trifluoroethoxy)pyrazine, 2 -Chloro-5-(1,1,1,2,2-tetrafluoroethoxy)pyrazine, 2-chloro-5-(2,2,3,3,3-pentafluoropropoxy)pyrazine,2-chloro-5-(2,2 , 3, 3-Tetrafluoropropoxy) pyrazine, 2-chloro-5-(3,3,3-trifluoropropoxy)pyrazine, 2-chloro-5-(1, 1, 1, 1, 3, 3, 3-hexafluoroiso Propoxy) Pyrazine, 2-Bromo _ 5— (Trifluororometoxy) Pyrazine, 2-Bromo-5— (2, 2, 2-Trifluoroethoxy) Pyrazine, 2-Bromo-5— (1, 1, 1, 2, 2—Tetra Fluor
  • Examples include xylpyrazine and the like.
  • Specific examples of the compound represented by the formula (2) include 2-chloro-3-ethylsulfonylpyridine, 2-bromo_3-ethylsulfonylpyridine, 2-chloro-3-ethylsulfonyl-5- Examples include methylpyridine, 2-chloro-3-ethylsulfonyl-5-cyclopropylpyridine, 2-chloro-3-ethylsulfonyl-6-ethylpyridine, 2-chloro-3-methylsulfonylpyridin, 2-chloro-3-propylsulfonylpyridine, and the like.
  • 2-chloro-3-ethylsulfonylpyridine 2-bromo_3-ethylsulfonylpyridine
  • 2-chloro-3-ethylsulfonyl-5- Examples include methylpyridine, 2-chloro-3-ethylsulfonyl-5-cyclopropyl
  • the amount of the compound represented by the formula (2) is not limited to this, but is usually 0.8 to 3 mol, preferably 1 to 3 mol per 1 mol of the compound represented by the formula (1). 2 mol.
  • the reaction temperature is usually ⁇ to 1800°, and preferably 50 to 150°.
  • the reaction time is usually 0.1 to 48 hours.
  • the embodiment of the reaction is not particularly limited, but usually, after mixing a cobalt compound, a nickel compound or an iron compound with a solvent, a coordinating organic compound is added, if necessary.
  • the method is carried out by adding the compound represented by 1) and the compound represented by the formula (2), and finally adding a reducing agent and, if necessary, an activating agent for the reducing agent.
  • the obtained mixture is filtered to remove solids such as inorganic salts, and then the solvent is distilled off; or water is added to the obtained mixture to obtain solids such as inorganic salts. And dilute by adding a solvent if necessary, separate the aqueous layer, wash the obtained organic layer with water, and then distill off the solvent.
  • the compound of formula (3) Can be obtained.
  • the obtained compound can be further purified by crystallization, column chromatography or the like.
  • the door is 2, 3 , [3 ⁇ 4 and [3 ⁇ 4 3 .
  • the compound of the present invention which is any combination described in [Table 5] (hereinafter referred to as compound group 3 XI).
  • n is 1, and 3 .
  • the door is 2, and [3 ⁇ 4 33 and [3 ⁇ 4 3] .
  • the compound of the present invention which is any combination described in [Table 5] (hereinafter, referred to as compound group 3X5).
  • Equation (3) the door is 2, and [3 ⁇ 4 315 and [3 ⁇ 4 3 . Is a hydrogen atom
  • the compound represented by the formula (1) is 2,5-dichloropyrazine, 2,5-dibromopyrazine or 2,5-diiodopyrazine, and the compound represented by the formula (8):
  • the reaction may be carried out in a solvent or without a solvent.
  • the solvent include tetrahydrofuran, methyl 1: _butyl ether, ethers such as ethylene glycol dimethyl ether; aromatic hydrocarbons such as toluene and xylene; nitriles such as acetnitrile and propionitrile; and mixtures of two or more of these.
  • a compound is mentioned.
  • Examples of the base include alkali metal hydrides such as lithium hydride and sodium hydride; organic salt groups such as triethylamine and diisopropylethylamine; alkali metal carbonates such as sodium carbonate and potassium carbonate.
  • the amount of the compound represented by the formula (8) is 2, 5-dichloropyrazine, 2,
  • the amount of base used can be, but is not limited to, 2,5-dichloropyrone. ⁇ 2020/175 578 23 ⁇ (: 170? 2020 /007856
  • the amount is usually 1 to 5 mol per mol of ladine, 2,5-dibromopyrazine or 2,5-diiodopyrazine.
  • reaction temperature is usually one 2 0 ° ⁇ ⁇ 1 5 0 ° ⁇ .
  • Reaction time is usually 0.5 to 2
  • 2,5-dichloropyrazine, 2,5-dibromopyrazine, 2,5-diiodopyrazine and the compound represented by the formula (8) are commercially available compounds or may be produced by a known method. it can.
  • Helium gas flow velocity 1.0 01 1_ / 01 1 -Internal standard: 4-dimethylamino toluene
  • nickel chloride ( ⁇ ) 6. 1 ,1 ⁇ — phenanthroline 1 8. Mix toluene 0.41_ and stir at 1 20° for 30 minutes ⁇ 2020/175 578 27 ⁇ (: 170? 2020 /007856
  • the resulting mixture contained 2-chloro-3-ethylsulfonylpyridine 1 2 3. 3 ⁇ 19, 2-chloro-5-(2,2,3,3,3-pentafluoropropoxy)pyrazine 1 3 1. 1 ⁇ 1-Methylpyrrolidone ⁇ 0.31_, zinc powder 59. Toluene 0.51_ was added, and the mixture was stirred at 120°C for 3 hours. The obtained reaction mixture was cooled to room temperature, acetonitrile was added, and the mixture was filtered through Celite, and the obtained solution was analyzed by liquid chromatography.
  • Nickel chloride 12 Triphenylphosphine 25. 1 ⁇ 1, 1 ⁇ 1, 1 ⁇ 1, ,1 ⁇ 1, -Tetramethylethylenediamine 68019, 2-Chloro-3-ethylsulfonylpyridine 20 ⁇ .38 019, 2-Chloro-5- (2, 2, 3 , 3, 3-Pentafluoropropoxy) pyrazine 263. Pyridine 0 IV! 1.0 1_, zinc
  • the obtained reaction mixture was cooled to room temperature, acetonitrile was added, and the mixture was filtered through Celite, and the obtained solution was analyzed by liquid chromatography method 3 and found to be 2 ⁇ [3 ⁇ (ethylsulfonyl) — The yield of 2-pyridinyl]-5-(2,2,3,3,3-pentafluoropropoxy)pyrazine was 57%.
  • Example 1 2-chloro-3-ethylsulfonylpyridine 94 Replace with 9, 2,3-dichloropyridine 68 The reaction was carried out in the same manner as in Example 1 except that 9 was used.
  • a pyridylpyrazine compound which is an active ingredient of a pest control agent can be obtained.

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  • Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
  • Plural Heterocyclic Compounds (AREA)
  • Pharmaceuticals Containing Other Organic And Inorganic Compounds (AREA)

Abstract

La présente invention concerne un nouveau procédé de production d'un type de composé de pyridylpyrazine. Plus particulièrement, la présente invention concerne un procédé de production d'un composé représenté par la formule (3) (dans laquelle R1, R2, R3a, R3b, R3c et n sont tels que définis ci-après), qui comprend une étape selon laquelle un composé représenté par la formule (1) (dans laquelle X représente un atome de chlore ou similaire ; et R1 représente un groupe hydrocarboné à chaîne en C1-C10 qui peut avoir un ou plusieurs atomes d'halogène, un groupe cycloalkyle en C3-C7 ayant un ou plusieurs substituants choisis dans le groupe G qui est constitué d'atomes d'halogène et de groupes haloalkyle en C1-C6, ou analogues) et un composé représenté par la formule (2) (dans laquelle Y représente un atome de chlore ou similaire ; R2 représente un groupe cyclopropyle méthyle ou similaire ; R3a représente un atome d'hydrogène ou similaire ; R3b représente un atome d'hydrogène ou similaire ; R3c représente un atome d'hydrogène ou similaire ; et n représente 1 ou 2) sont mis à réagir l'un avec l'autre en présence d'un agent réducteur et d'au moins un composé métallique choisi dans le groupe constitué par des composés de cobalt, des composés de nickel et des composés de fer, ce qui permet d'obtenir un composé représenté par la formule (3).
PCT/JP2020/007856 2019-02-27 2020-02-26 Procédé de production de composé de pyridylpyrazine Ceased WO2020175578A1 (fr)

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Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2006114666A1 (fr) * 2005-03-17 2006-11-02 Pfizer Products Inc. Derives d'aryl-1,4-pyrazine
WO2017065228A1 (fr) * 2015-10-16 2017-04-20 住友化学株式会社 Composé pyrazine et agent de lutte contre les arthropodes nuisibles contenant celui-ci
WO2017150209A1 (fr) * 2016-02-29 2017-09-08 住友化学株式会社 Composé hétérocyclique
WO2019111869A1 (fr) * 2017-12-05 2019-06-13 住友化学株式会社 Procédé de production d'un composé pyridine 3-éthylsulfonyle à substitution en position 2 et analogues

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2006114666A1 (fr) * 2005-03-17 2006-11-02 Pfizer Products Inc. Derives d'aryl-1,4-pyrazine
WO2017065228A1 (fr) * 2015-10-16 2017-04-20 住友化学株式会社 Composé pyrazine et agent de lutte contre les arthropodes nuisibles contenant celui-ci
WO2017150209A1 (fr) * 2016-02-29 2017-09-08 住友化学株式会社 Composé hétérocyclique
WO2019111869A1 (fr) * 2017-12-05 2019-06-13 住友化学株式会社 Procédé de production d'un composé pyridine 3-éthylsulfonyle à substitution en position 2 et analogues

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
KOMREDDY, V ET AL.: "Synthesis and Characterization of 2-(2- Pyridinyl)pyrazine and 2,2'-Bipyrazine Derivatives", JOURNAL OF HETEROCYCLIC CHEMISTRY, vol. 56, 29 January 2019 (2019-01-29), pages 972 - 979, XP055734640 *

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