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WO2013069481A1 - Procédé de fabrication de composé triazole et intermédiaire de composé triazole - Google Patents

Procédé de fabrication de composé triazole et intermédiaire de composé triazole Download PDF

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Publication number
WO2013069481A1
WO2013069481A1 PCT/JP2012/077762 JP2012077762W WO2013069481A1 WO 2013069481 A1 WO2013069481 A1 WO 2013069481A1 JP 2012077762 W JP2012077762 W JP 2012077762W WO 2013069481 A1 WO2013069481 A1 WO 2013069481A1
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Prior art keywords
group
compound
halogen atom
diastereomer
atom
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Japanese (ja)
Inventor
須藤　敬一
大河 正野
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Kureha Corp
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Kureha Corp
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C31/00—Saturated compounds having hydroxy or O-metal groups bound to acyclic carbon atoms
    • C07C31/18—Polyhydroxylic acyclic alcohols
    • C07C31/20—Dihydroxylic alcohols
    • 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
    • A01N43/64—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with three nitrogen atoms as the only ring hetero atoms
    • A01N43/647—Triazoles; Hydrogenated triazoles
    • A01N43/653—1,2,4-Triazoles; Hydrogenated 1,2,4-triazoles
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D249/00—Heterocyclic compounds containing five-membered rings having three nitrogen atoms as the only ring hetero atoms
    • C07D249/02—Heterocyclic compounds containing five-membered rings having three nitrogen atoms as the only ring hetero atoms not condensed with other rings
    • C07D249/08—1,2,4-Triazoles; Hydrogenated 1,2,4-triazoles
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D317/00—Heterocyclic compounds containing five-membered rings having two oxygen atoms as the only ring hetero atoms
    • C07D317/08—Heterocyclic compounds containing five-membered rings having two oxygen atoms as the only ring hetero atoms having the hetero atoms in positions 1 and 3
    • C07D317/10—Heterocyclic compounds containing five-membered rings having two oxygen atoms as the only ring hetero atoms having the hetero atoms in positions 1 and 3 not condensed with other rings
    • C07D317/14—Heterocyclic compounds containing five-membered rings having two oxygen atoms as the only ring hetero atoms having the hetero atoms in positions 1 and 3 not condensed with other rings with substituted hydrocarbon radicals attached to ring carbon atoms
    • C07D317/16—Radicals substituted by halogen atoms or nitro radicals

Definitions

  • the present invention relates to a method for producing a triazole compound.
  • Patent Document 1 discloses, as an active ingredient of a plant disease control agent, a hydroxyethylazole derivative which is a hetero 5-membered ring containing 2 or more nitrogen atoms in the ring, and further has a cycloalkyl group on the carbon atom to which the hydroxy group is bonded. Or a derivative in which an alkyl group in which some hydrogen atoms are substituted with a cycloalkyl group is bonded.
  • Patent Document 1 Since the compound described in Patent Document 1 has excellent activity as a plant disease control agent, a method for producing such a compound efficiently and at low cost is required. In addition, such a compound has a plurality of diastereomers, but there is a demand for a production method that minimizes the possibility of unnecessary diastereomers being mixed into the finally obtained compound. Yes.
  • an object of the present invention is to provide a production method for efficiently and inexpensively producing a compound that meets the above-mentioned demand.
  • a method for producing a triazole compound according to the present invention includes a diol production step of producing a diol compound represented by the following general formula (Ia) from an oxirane compound represented by the following general formula (III): ,
  • X 3 to X 5 represent a hydrogen atom or a halogen atom
  • X 5 represents a halogen atom
  • a plurality of X 4 are the same atom
  • a plurality of X 5 are the same atom.
  • X 4 and X 5 are different from each other, and n represents 0 to 3.
  • R 2 represents a C3 to C6 cycloalkyl group or a C1 to C4 substituted with the cycloalkyl group
  • the cycloalkyl group and the alkyl group are a halogen atom, a C1-C4 alkyl group, a C1-C4 haloalkyl group, a C3-C6 cycloalkyl group, an aryl group, or an arylalkyl group (alkyl
  • the aromatic ring of the aryl group and the arylalkyl group may be a halogen atom, a C1-C4 alkyl group, Haloalkyl group 1 ⁇ C4, alkoxy group of C1 ⁇ C4, or may be substituted with a haloalkoxy group having C1 ⁇ C4.
  • X 3 to X 5 represent a hydrogen atom or a halogen atom
  • X 5 represents a halogen atom
  • a plurality of X 4 are the same atom
  • a plurality of X 5 are the same atom.
  • X 4 and X 5 are different from each other, and n represents 0 to 3.
  • R 2 represents a C3 to C6 cycloalkyl group or a C1 to C4 substituted with the cycloalkyl group
  • the cycloalkyl group and the alkyl group are a halogen atom, a C1-C4 alkyl group, a C1-C4 haloalkyl group, a C3-C6 cycloalkyl group, an aryl group, or an arylalkyl group (alkyl
  • the aromatic ring of the aryl group and the arylalkyl group may be a halogen atom, a C1-C4 alkyl group, Haloalkyl group 1 ⁇ C4, alkoxy group of C1 ⁇ C4, or may be substituted with a haloalkoxy group having C1 ⁇ C4.)
  • a first oxirane diastereomer producing step for producing a first oxirane diastereomer of the oxirane compound represented by the general formula (III)
  • X 1 ⁇ X 4 represents a hydrogen atom or a halogen atom
  • X 5 represents a halogen atom
  • a plurality of X 2 are the same atom together
  • X 1 and At least one of X 2 is a halogen atom
  • a plurality of X 4 are the same atom
  • a plurality of X 5 are the same atom
  • X 4 and X 5 are different atoms
  • the intermediate compound according to the present invention is an intermediate compound of the above triazole compound, and is characterized by being represented by the following general formula (Ia).
  • X 3 to X 5 represent a hydrogen atom or a halogen atom
  • X 5 represents a halogen atom
  • a plurality of X 4 are the same atom
  • a plurality of X 5 are the same atom.
  • X 4 and X 5 are different from each other, and n represents 0 to 3.
  • R 2 represents a C3 to C6 cycloalkyl group or a C1 to C4 substituted with the cycloalkyl group
  • the cycloalkyl group and the alkyl group are a halogen atom, a C1-C4 alkyl group, a C1-C4 haloalkyl group, a C3-C6 cycloalkyl group, an aryl group, or an arylalkyl group (alkyl
  • the aromatic ring of the aryl group and the arylalkyl group may be a halogen atom, a C1-C4 alkyl group, Haloalkyl group 1 ⁇ C4, alkoxy group of C1 ⁇ C4, or may be substituted with a haloalkoxy group having C1 ⁇ C4.
  • the intermediate compound according to the present invention is an intermediate compound of the above-described triazole compound triazole compound, and is characterized by being represented by the following general formula (Ib).
  • X 3 to X 5 represent a hydrogen atom or a halogen atom
  • X 5 represents a halogen atom
  • a plurality of X 4 are the same atom
  • a plurality of X 5 are the same atom.
  • X 4 and X 5 are different from each other, and n represents 0 to 3.
  • R 2 represents a C3 to C6 cycloalkyl group or a C1 to C4 substituted with the cycloalkyl group
  • the cycloalkyl group and the alkyl group are a halogen atom, a C1-C4 alkyl group, a C1-C4 haloalkyl group, a C3-C6 cycloalkyl group, an aryl group, or an arylalkyl group (alkyl
  • the aromatic ring of the aryl group and the arylalkyl group may be a halogen atom, a C1-C4 alkyl group, Haloalkyl group 1 ⁇ C4, alkoxy group of C1 ⁇ C4, or may be substituted with a haloalkoxy group having C1 ⁇ C4.
  • the intermediate compound according to the present invention is the above-described triazole compound intermediate compound, and is characterized by being represented by the following general formula (Ic).
  • X 3 to X 5 represent a hydrogen atom or a halogen atom
  • X 5 represents a halogen atom
  • a plurality of X 4 are the same atom
  • a plurality of X 5 are the same atom.
  • X 4 and X 5 are mutually different atoms
  • n represents 0 to 3
  • L represents a halogen atom or a sulfonyloxy group
  • R 2 represents a C3 to C6 cycloalkyl group, Or a C1-C4 alkyl group substituted with the cycloalkyl group, wherein the cycloalkyl group and the alkyl group are a halogen atom, a C1-C4 alkyl group, a C1-C4 haloalkyl group, a C3-C6
  • the aryl group and the arylalkyl may be substituted with a cycloalkyl group, an aryl group, or an
  • a triazole compound having an excellent bactericidal action against many bacteria causing disease to plants can be produced efficiently and at low cost. Therefore, according to the present invention, a plant disease control agent comprising the triazole compound produced according to the present invention as an active ingredient and exhibiting a high control effect against a wide range of plant diseases can be produced easily and at low cost. .
  • the method for producing a triazole compound according to the present invention includes a diol production step for producing a diol compound represented by the following general formula (Ia) from an oxirane compound represented by the following general formula (III):
  • X 3 to X 5 represent a hydrogen atom or a halogen atom
  • X 5 represents a halogen atom
  • a plurality of X 4 are the same atom
  • a plurality of X 5 are the same atom.
  • X 4 and X 5 are different from each other, and n represents 0 to 3.
  • R 2 represents a C3 to C6 cycloalkyl group or a C1 to C4 substituted with the cycloalkyl group
  • the cycloalkyl group and the alkyl group are a halogen atom, a C1-C4 alkyl group, a C1-C4 haloalkyl group, a C3-C6 cycloalkyl group, an aryl group, or an arylalkyl group (alkyl
  • the aromatic ring of the aryl group and the arylalkyl group may be a halogen atom, a C1-C4 alkyl group, Haloalkyl group 1 ⁇ C4, alkoxy group of C1 ⁇ C4, or may be substituted with a haloalkoxy group having C1 ⁇ C4.
  • X 3 to X 5 represent a hydrogen atom or a halogen atom
  • X 5 represents a halogen atom
  • a plurality of X 4 are the same atom
  • a plurality of X 5 are the same atom.
  • X 4 and X 5 are different from each other, and n represents 0 to 3.
  • R 2 represents a C3 to C6 cycloalkyl group or a C1 to C4 substituted with the cycloalkyl group
  • the cycloalkyl group and the alkyl group are a halogen atom, a C1-C4 alkyl group, a C1-C4 haloalkyl group, a C3-C6 cycloalkyl group, an aryl group, or an arylalkyl group (alkyl
  • the aromatic ring of the aryl group and the arylalkyl group may be a halogen atom, a C1-C4 alkyl group, Haloalkyl group 1 ⁇ C4, alkoxy group of C1 ⁇ C4, or may be substituted with a haloalkoxy group having C1 ⁇ C4.)
  • a first oxirane diastereomer producing step for producing a first oxirane diastereomer of the oxirane compound represented by the general formula (III)
  • X 1 ⁇ X 4 represents a hydrogen atom or a halogen atom
  • X 5 represents a halogen atom
  • a plurality of X 2 are the same atom together
  • X 1 and At least one of X 2 is a halogen atom
  • a plurality of X 4 are the same atom
  • a plurality of X 5 are the same atom
  • X 4 and X 5 are different atoms
  • Triazole compound The triazole compound produced by the method for producing a triazole compound in the present embodiment is represented by the following general formula (I):
  • X 1 ⁇ X 4 represents a hydrogen atom or a halogen atom
  • X 5 represents a halogen atom
  • a plurality of X 2 are the same atom together
  • X 1 and At least one of X 2 is a halogen atom
  • a plurality of X 4 are the same atom
  • a plurality of X 5 are the same atom
  • X 4 and X 5 are different atoms
  • X 1 to X 4 each independently represents a hydrogen atom or a halogen atom
  • X 5 represents a halogen atom
  • Examples of the halogen atom in X 1 to X 4 and X 5 include a fluorine atom, a chlorine atom, a bromine atom and an iodine atom, and among them, a chlorine atom and a bromine atom are preferable.
  • a plurality (four) of X 2 are the same atom, and at least one of X 1 and X 2 is a halogen atom. Of these, X 1 is a halogen atom, it is preferred that X 2 is a hydrogen atom.
  • X 3 is a hydrogen atom or a halogen atom, and preferably a hydrogen atom.
  • Plural (two) X 4 are the same atom, and similarly plural (two) X 5 are the same atom.
  • X 4 and X 5 are atoms different from each other. For example, when two X 4 are both hydrogen atoms and two X 5 are both chlorine atoms, or two X 4 are both hydrogen atoms and two X 5 are Examples of these include, but are not limited to, a bromine atom.
  • X 4 and X 5 may be different halogen atoms.
  • M and n each independently represents an integer of 0 to 3.
  • m is preferably 0 or 1, and 0 is particularly preferable.
  • n is preferably from 0 to 2, particularly preferably 1 or 2.
  • compound (I) examples include, for example, a compound represented by the following formula (I-1).
  • Compound (I) has two asymmetric carbon atoms. Accordingly, compound (I) has a plurality of diastereomers.
  • the “diastereomer” refers to a stereoisomer generated by the presence of a plurality of asymmetric carbon atoms in a molecule and not having a mirror image relationship.
  • the triazole compound is a more active diastereomer among a plurality of diastereomers.
  • all diastereomers other than the higher activity diastereomers among the plurality of diastereomers are referred to as lower activity diastereomers.
  • the term “higher activity diastereomer” intends a diastereomer having an excellent control effect against plant diseases than other diastereomers. Further, the “lower activity diastereomer” intends a diastereomer having a control effect which is inferior to the above-mentioned “higher activity diastereomer” against plant diseases.
  • X 1 to X 4 represent a hydrogen atom or a halogen atom
  • X 5 represents a halogen atom
  • a plurality of X 2 are the same atom
  • At least one of 1 and X 2 is a halogen atom
  • a plurality of X 4 are the same atom
  • a plurality of X 5 are the same atom
  • X 4 and X 5 are atoms different from each other
  • m And n represents 0 to 3.
  • * represents an asymmetric carbon atom.
  • compound (IA) Of the two diastereomers in the compound represented by the formula (I-2), the more active diastereomer is referred to as “compound (IA)”. Of the two diastereomers in the compound represented by the formula (I-2), the less active diastereomer is referred to as “compound (IB)”.
  • compound (I) is a compound represented by the following formula (VII) obtained by a known technique (hereinafter referred to as “compound (VII)”), and a compound represented by the following known technique. It can be produced from a compound represented by the formula (VI) (hereinafter referred to as “compound (VI)”).
  • X 3 , X 4 and n are synonymous with the above-mentioned X 3 , X 4 and n.
  • X 6 represents a halogen atom.
  • L 1 represents alkali metal, alkaline earth metal-Q1 (Q1 is a halogen atom), 1/2 (Cu alkali metal), or zinc-Q2 (Q2 is a halogen atom).
  • the alkali metal include lithium, sodium, and potassium, and lithium is particularly preferable.
  • magnesium etc. are mentioned as an alkaline-earth metal.
  • R 2 represents a functional group represented by the following formula (XIV).
  • X 1 , X 2 and m have the same meanings as X 1 , X 2 and m described above.
  • the solvent used is not particularly limited as long as it is an inert solvent, and examples thereof include ethers such as diethyl ether, tetrahydrofuran and dioxane, and aromatic hydrocarbons such as benzene, toluene and xylene. These solvents can also be used as a mixture.
  • water when used for the reaction, it can be used by mixing with an organic solvent.
  • a tetrabutylammonium salt, trimethylbenzylammonium salt is added to the reaction mixture as necessary. It is also possible to carry out the reaction by adding a phase transfer catalyst such as a salt and a quaternary ammonium salt such as triethylbenzylammonium salt, and crown ether and the like.
  • the amount of compound (VI) to be used relative to compound (VII) is, for example, 0.5 to 10 times mol, preferably 0.8 to 5 times mol.
  • Compound (VI) is preferably prepared just before the reaction. Moreover, it may be possible to carry out the reaction while generating the compound (VI) in the reaction system. In particular, when L 1 is zinc-Q2 (Q2 is a halogen atom), it is preferable to carry out the reaction while generating compound (IX) in the reaction system.
  • a Lewis acid may be added if desired.
  • the amount of the Lewis acid used relative to compound (VI) is, for example, 0 to 5 times mol (excluding 0), preferably 0.1 to 2 times mol.
  • the Lewis acid include aluminum chloride, zinc chloride, cerium chloride and the like.
  • the reaction temperature and reaction time can be appropriately set depending on the type of the solvent, compound (VI), compound (VI) and the like.
  • the reaction temperature is preferably ⁇ 100 ° C. to 200 ° C., more preferably ⁇ 70 ° C. to 100 ° C.
  • the reaction time is preferably 0.1 to 12 hours, and more preferably 0.5 to 6 hours.
  • compound (VI) a commercially available compound or a compound that can be produced by an existing synthesis technique such as conversion of a halogenated alkenyl compound into an organometallic reagent can be used.
  • compound (VII) a commercially available compound or a compound that can be produced by existing techniques can be used.
  • the amount of the base used for compound (V) is, for example, 0.5 to 20 times mol, preferably 0.8 to 5 times mol.
  • Bases used include alkali metal or alkaline earth metal hydroxide salts such as sodium hydroxide, potassium hydroxide and calcium hydroxide, and alkali metal carbonates or hydrogen carbonates such as sodium carbonate and potassium carbonate. However, it is not limited to these.
  • the solvent to be used is not particularly limited.
  • alcohols such as methanol, ethanol and isopropanol
  • ethers such as diethyl ether, tetrahydrofuran and dioxane
  • N, N-dimethylformamide, N, N-dimethylacetamide and N -Amides such as methyl-2-pyrrolidinone
  • Hydrocarbons such as n-hexane, methylcyclohexane, benzene, toluene and xylene
  • Halogenated hydrocarbons such as dichloroethane and chloroform
  • mixed solvents thereof are examples of mixed solvents thereof.
  • the reaction mixture contains quaternary ammonium salts such as tetrabutylammonium salt, trimethylbenzylammonium salt and triethylbenzylammonium salt, and interphases such as crown ether and the like. It is also possible to carry out the reaction by adding a transfer catalyst.
  • the reaction temperature and reaction time can be appropriately set depending on the solvent, the type of compound (V), and the like.
  • the reaction temperature is preferably ⁇ 20 ° C. to 150 ° C., and more preferably 0 ° C. to 100 ° C.
  • the reaction time is preferably 0.1 to 24 hours, and more preferably 0.5 to 12 hours.
  • X 5 has the same meaning as X 5 above.
  • trihalomethane used examples include chloroform, bromoform, chlorodifluoromethane, dichlorofluoromethane, and dibromofluoromethane.
  • the amount of trihalomethane used with respect to compound (IV) is not particularly limited, and is, for example, 0.5 to 1000 times mol, preferably 0.8 to 100 times mol.
  • trihalomethane itself or other solvents such as dichloromethane and toluene inert to the reaction can be used.
  • phase transfer catalyst When adding a base, when using an aqueous solution such as an aqueous sodium hydroxide solution, it is preferable to use a phase transfer catalyst.
  • the phase transfer catalyst is not particularly limited, and includes quaternary ammonium salts such as tetramethylammonium chloride, tetrabutylammonium bromide, cetyltrimethylammonium bromide, benzyltriethylammonium chloride and benzyltrimethylammonium chloride, and three such as triethylamine and tripropylamine. Secondary amines can be used.
  • the amount of the phase transfer catalyst used relative to the compound (IV) is, for example, 0.001 to 5 times mol, preferably 0.01 to 2 times mol.
  • the base to be used is not particularly limited, and examples thereof include alkali metal hydroxides such as sodium hydroxide and potassium hydroxide, and are often used as an aqueous solution.
  • the amount of the base used relative to compound (IV) is, for example, 0.1 to 100 times mol, preferably 0.8 to 50 times mol.
  • the concentration of the aqueous solution of alkali metal hydroxide at this time is, for example, 10% to a saturated aqueous solution, and preferably 30% to a saturated aqueous solution.
  • the reaction temperature is, for example, 0 ° C. to 200 ° C., preferably 10 ° C. to 150 ° C.
  • the reaction time is, for example, 0.1 hour to several days, preferably 0.2 hour to 2 days.
  • M represents a hydrogen atom or an alkali metal.
  • the solvent to be used is not particularly limited, and examples thereof include amides such as N-methylpyrrolidone and N, N-dimethylformamide.
  • the amount of the compound (II) used relative to the compound (III) is, for example, 0.5 to 10 times mol, preferably 0.8 to 5 times mol. Moreover, you may add a base if desired. In this case, the amount of the base used relative to the compound (II) is, for example, 0 to 10 times mol (excluding 0), preferably 0.5 to 5 times mol.
  • the reaction temperature and reaction time can be appropriately set depending on the solvent, base and the like.
  • the reaction temperature is preferably 0 ° C. to 250 ° C., more preferably 10 ° C. to 150 ° C.
  • the reaction time is preferably 0.1 hour to several days, more preferably 0.5 hour to 2 days.
  • the compound (IA) can be efficiently produced without requiring a separation step of the compound (I) from the diastereomer mixture.
  • an intermediate which is separated and no longer necessary in the production process of compound (IA) can be reused and used for the production of compound (IA).
  • compound (IA) can be produced efficiently and at low cost.
  • the following compounds (Ia), (Ib) and (Ic), which are intermediate compounds of the triazole compound used in the method for producing a triazole compound according to the present invention, are also included in the category of the present invention. .
  • compound (IA) can be produced from compound (III) obtained by a known technique as shown in Scheme 2 below.
  • the amount of the acid catalyst used relative to compound (III) is, for example, 0.001 to 2 times mol, preferably 0.01 to 1 times mol.
  • the acid catalyst used include sulfuric acid, hydrochloric acid, hydrobromic acid and perchloric acid.
  • the reaction temperature and reaction time can be appropriately set depending on the type of solvent and acid catalyst.
  • the reaction temperature is preferably 0 to 200 ° C, more preferably 80 to 150 ° C.
  • the reaction time is preferably 0.1 to 12 hours, more preferably 0.5 to 2 hours.
  • compound (Ia) acetonides compound (III) in a solvent containing a Lewis acid catalyst to obtain a dioxolane compound represented by the following formula (Ib) (hereinafter referred to as “compound (Ib)”). It can also be obtained by deprotecting compound (Ib) in a solvent containing a catalyst (the following reaction formula (6)).
  • the amount of the Lewis acid catalyst used relative to compound (III) is, for example, 0.001 to 2 times mol, preferably 0.01 to 0.1 times mol.
  • the Lewis acid catalyst used include tin (II) chloride, tin (IV) chloride, boron trifluoride, copper sulfate, copper (II) trifluoromethanesulfonate, and titanium (IV) chloride.
  • the reaction temperature and each reaction time can be appropriately set depending on the type of solvent and acid catalyst.
  • the reaction temperature is preferably ⁇ 20 to 50 ° C., more preferably ⁇ 10 to 30 ° C.
  • the reaction time is preferably 0.1 to 12 hours, more preferably 0.5 to 3 hours.
  • the amount of the acid catalyst used relative to compound (Ib) is, for example, 0.01 to 20 times mol, preferably 0.1 to 2 times mol.
  • the acid catalyst used include hydrochloric acid, sulfuric acid, acetic acid, methanesulfonic acid, and p-toluenesulfonic acid.
  • the reaction temperature and each reaction time can be appropriately set depending on the type of solvent and acid catalyst.
  • the reaction temperature is preferably ⁇ 20 to 150 ° C., more preferably 20 to 100 ° C.
  • the reaction time is preferably 0.5 to 24 hours, and more preferably 1 to 12 hours.
  • Compound (Ia) is produced from a compound represented by the following formula (Ia-1) obtained by a known technique (hereinafter referred to as “compound (Ia-1)”) as shown in Scheme 3 below. You can also
  • compound (Ia-1) is hydrolyzed in a solvent containing an acid catalyst to obtain a diol compound represented by the above formula (Ia-2) (hereinafter referred to as “compound (Ia-2)”).
  • compound (Ia-2) is acetonated in acetone containing an acid catalyst to obtain a dioxolane compound represented by the above formula (Ia-3) (hereinafter referred to as “compound (Ia-3)”).
  • compound (Ia-3) 2,2-dimethoxypropane may be allowed to coexist in acetone.
  • compound (Ib) is synthesized from compound (Ia-3) by reaction of trihalomethane with a base.
  • Compound (Ia) is obtained by deprotecting the obtained compound (Ib) in a solvent containing an acid catalyst.
  • compound (IbA) A diastereomer (hereinafter referred to as “compound (IbA)”) finally derived from compound (IA) is separated from the obtained diastereomeric mixture of compound (Ib), and compound (IbA) is used. To obtain compound (Ia). Thus obtained compound (Ia) is a diastereomer finally derived from compound (IA).
  • compound (IaA) the diastereomer derived from compound (IA) is referred to as “compound (IaA)” or “first diol diastereomer”.
  • the compound (IaA) thus obtained may contain other diastereomers, it is possible to further purify the compound by further separating other diastereomers from the obtained compound (IaA). High compound (IaA) is obtained.
  • the amount of the acid catalyst used relative to compound (Ia-1) is, for example, 0.001 to 2 times mol, preferably 0.01 to 1 times mol.
  • the acid catalyst used include sulfuric acid, hydrochloric acid, hydrobromic acid and perchloric acid.
  • the reaction temperature and reaction time can be appropriately set depending on the type of solvent and acid catalyst.
  • the reaction temperature is preferably 0 to 200 ° C, more preferably 80 to 150 ° C.
  • the reaction time is preferably 0.1 to 12 hours, more preferably 0.5 to 2 hours.
  • the amount of the acid catalyst used relative to compound (Ia-2) is, for example, 0.001 to 2 moles, preferably 0.01 to 1 moles.
  • the acid catalyst used include hydrochloric acid, sulfuric acid, p-toluenesulfonic acid and the like.
  • 2,2-dimethoxypropane can be added to the solvent, and the amount used is, for example, 0.1 to 10 times mol, preferably 1 to 5 times mol.
  • the reaction temperature and reaction time can be appropriately set depending on the type of solvent and acid catalyst.
  • the reaction temperature is preferably 0 to 150 ° C., more preferably 20 to 80 ° C.
  • the reaction time is preferably 1 to 24 hours, and more preferably 2 to 10 hours.
  • the amount of trihalomethane used in the synthesis using compound (Ia-3) is, for example, 0.5 to 1000 times mol, preferably 0.8 to 100 times mol.
  • examples of the trihalomethane used include chloroform, bromoform, chlorodifluoromethane, dichlorofluoromethane, and dibromofluoromethane.
  • the amount of base used in the synthesis using compound (Ia-3) is, for example, 0.1 to 100 times mol, preferably 0.8 to 50 times mol.
  • the phase transfer catalyst is not particularly limited, and includes quaternary ammonium salts such as tetramethylammonium chloride, tetrabutylammonium bromide, cetyltrimethylammonium bromide, benzyltriethylammonium chloride and benzyltrimethylammonium chloride, and three such as triethylamine and tripropylamine. Secondary amines can be used.
  • the amount of the phase transfer catalyst used is, for example, 0.001 to 5 times mol, preferably 0.01 to 2 times mol, of the compound (IV).
  • alkali metal hydroxides such as sodium hydroxide and potassium hydroxide are preferably used, and in many cases, used as an aqueous solution.
  • the amount of the base to be used is, for example, 0.1 to 100 times mol, preferably 0.8 to 50 times mol with respect to compound (IV). Further, the concentration of the aqueous solution of alkali metal hydroxide at this time is, for example, 10% to a saturated aqueous solution, and preferably 30% to a saturated aqueous solution.
  • the reaction temperature is, for example, 0 ° C. to 200 ° C., preferably 10 ° C. to 150 ° C.
  • the reaction time is, for example, 0.1 hour to several days, preferably 0.2 hour to 2 days.
  • the amount of the acid catalyst used relative to compound (Ib) is, for example, 0.01 to 20 times mol, preferably 0.1 to 2 times mol.
  • the acid catalyst used include hydrochloric acid, sulfuric acid, acetic acid, methanesulfonic acid and p-toluenesulfonic acid.
  • the reaction temperature and each reaction time can be appropriately set depending on the type of solvent and acid catalyst.
  • the reaction temperature is preferably ⁇ 20 to 150 ° C., more preferably 20 to 100 ° C.
  • the reaction time is preferably 0.5 to 24 hours, and more preferably 1 to 12 hours.
  • a halohydrin compound represented by the following formula (Ic) (L represents a halogen atom) from the compound (Ia) obtained in Step B1, Step B1-1, or Step C1 by reaction with a halogenating agent Alternatively, a sulfonyl compound represented by the following formula (Ic) (L represents a sulfonyloxy group) is obtained by reaction with a sulfonyl halide (see the following reaction formula (7)).
  • these compounds are referred to as “compound (Ic)”.
  • the amount of the halogenating agent used relative to compound (Ia) is, for example, 0.5 to 10 times mol, preferably 0.8 to 2 times mol.
  • the halogenating agent used include phosphorus pentachloride, phosphorus pentabromide, sulfuryl chloride, thionyl chloride and the like.
  • the reaction temperature and reaction time for obtaining the halohydrin compound can be appropriately set depending on the type of the solvent and the halogenating agent.
  • the reaction temperature is preferably ⁇ 20 to 100 ° C., more preferably 0 to 50 ° C.
  • the reaction time is preferably 0.5 to 24 hours, and more preferably 1 to 12 hours.
  • the amount of the sulfonyl halide used relative to the compound (Ia) is, for example, 0.5 to 10 times mol, preferably 0.8 to 2 times mol. .
  • the sulfonyl halide used include mesyl chloride and tosyl chloride.
  • the reaction temperature and reaction time for obtaining the sulfonyl compound can be appropriately set depending on the solvent, the type of sulfonyl halide, and the like.
  • the reaction temperature is preferably ⁇ 20 to 100 ° C., more preferably 0 to 50 ° C.
  • the reaction time is preferably 0.5 to 24 hours, and more preferably 1 to 12 hours.
  • compound (Ia) a diastereomer mixture of compound (Ia) may be used, compound (IaA) separated from diastereomer mixture of compound (Ia), or compound obtained from compound (IbA) (IaA) may be used.
  • Compound (Ic) obtained using compound (IaA) is a diastereomer finally derived from compound (IA).
  • the diastereomer derived from compound (IA) is referred to as “compound (IcA)” or “first halohydrin or sulfonyl diastereomer”.
  • the compound (IcA) having higher purity can be obtained by further separating other diastereomers from the obtained compound (IcA). ) Is obtained.
  • the amount of the base used relative to compound (Ic) is, for example, 0.5 to 20 times mol, preferably 0.8 to 5 times mol.
  • Examples of the base used include sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate and the like.
  • the reaction temperature and reaction time can be appropriately set depending on the type of solvent and base.
  • the reaction temperature is preferably ⁇ 20 to 150 ° C., more preferably 20 to 100 ° C.
  • the reaction time is preferably 0.1 to 24 hours, and more preferably 0.5 to 12 hours.
  • compound (Ic) it is preferable to use (IcA) separated from the diastereomeric mixture of compound (Ic) or compound (IcA) obtained from compound (IaA).
  • Compound (III) obtained using compound (IcA) is a diastereomer finally derived from compound (IA).
  • the diastereomer derived from compound (IA) is referred to as “compound (IIIA)” or “first oxirane diastereomer”.
  • Compound (IA) can be produced by reacting compound (IIIA) obtained in this step according to the above step A4.
  • the diastereomer derived from the diastereomer of the target compound (I) (compound (IA)) is separated from the intermediate diastereomer mixture obtained in the production process of the compound (I). Used for the production of compound (IA).
  • separating the target diastereomer from the diastereomeric mixture of the compound (I) which is a final product is unnecessary, and a compound (IA) can be manufactured efficiently.
  • Compound (IaA) is obtained from the diastereomeric mixture of compound (Ia) obtained in the above-described step, Compound (IbA) is obtained from the diastereomeric mixture of compound (Ib), and Compound is obtained from the diastereomeric mixture of compound (Ic). Compound (Ia) is obtained from diastereomer remaining after separation of (IcA), and is reused in the production of compound (IA) (see the following reaction formula (9)).
  • the diastereomer remaining after separating the compound (IaA) from the diastereomeric mixture of the compound (Ia) is referred to as “compound (IaB)” or “second diol diastereomer”.
  • the diastereomer remaining after separation of compound (IbA) from the diastereomeric mixture of compound (Ib) is referred to as “compound IbB”.
  • the diastereomer remaining after separation of the compound (IcA) from the diastereomeric mixture of the compound (Ic) is referred to as “compound (IcB)” or “second halohydrin or sulfonyl diastereomer”.
  • diastereomers other than compound (IIIA) are referred to as “compound (IIIB)” or “second oxirane diastereomer”.
  • reaction formula (9) compound (IbB) to compound (IaB), compound (IaB) to compound (IcB), compound (IcB) to compound (IIIB), compound (IIIB) to compound (Ia)
  • the above-described method can be employed.
  • the method mentioned above is employable also about the method of obtaining compound (IA) from compound (Ia).
  • the catalyst and solvent to be used, the amount used, the reaction temperature, the reaction time, etc. are appropriately selected.
  • Compound (IaB), Compound (IbB), Compound (IcB) and Compound (IIIB) are each derived from Compound (IB).
  • compound (IA) and each intermediate derived from compound (IA) are sometimes referred to as “diastereomers (A)” in comparison with other diastereomers, respectively.
  • compound (IB) and each intermediate derived from compound (IB) may be referred to as “diastereomer (B)” in comparison with other diastereomers, respectively.
  • Compound (IaB), Compound (IbB), Compound (IcB) and Compound (IIIB) are not required in the production of Compound (IA).
  • compound (Ia) is obtained from compound (IaB), compound (IbB), compound (IcB) and compound (IIIB), and is reused in the production of compound (IA).
  • compound (IA) can be produced at low cost without wasting diastereomers.
  • silica gel As the stationary phase in column chromatography, silica gel, a highly polar stationary phase such as alumina, and a low polarity stationary phase such as alkyl group-bonded silica gel such as octadecylsilyl silica gel can be used.
  • organic solvents such as hexane, ethyl acetate, chloroform, alcohols and acetonitrile, water, and a mixture thereof can be used, and can be appropriately determined according to the type of stationary phase.
  • a plurality of separation methods may be combined, for example, after separation by column chromatography, separation and purification by recrystallization may be further performed.
  • optical center carbon of each diastereomer separated may be determined according to a conventionally known method.
  • the solvent, base, acid, and the like used can be as follows unless otherwise specified.
  • the solvent used is not particularly limited as long as it does not participate in the reaction, but usually ethers such as diethyl ether, tetrahydrofuran and dioxane; alcohols such as methanol, ethanol and isopropanol; aromatics such as benzene, toluene and xylene Hydrocarbons; aliphatic ethers such as petroleum ether, hexane and methylcyclohexane; and amides such as N, N-dimethylformamide, N, N-dimethylacetamide and N-methyl-2-pyrrolidinone it can.
  • ethers such as diethyl ether, tetrahydrofuran and dioxane
  • alcohols such as methanol, ethanol and isopropanol
  • aromatics such as benzene, toluene and xylene Hydrocarbons
  • aliphatic ethers such as petroleum ether, hexane and methylcyclohex
  • solvent water, acetonitrile, ethyl acetate, acetic anhydride, acetic acid, pyridine, dimethyl sulfoxide, and the like can be used as the solvent. These solvents may be used as a mixture of two or more.
  • examples of the solvent include a solvent composition composed of solvents that do not form a uniform layer with each other.
  • a phase transfer catalyst such as a conventional quaternary ammonium salt or crown ether may be added to the reaction system.
  • the base used is not particularly limited.
  • examples of the base include alkali metal carbonates such as sodium carbonate, sodium hydrogen carbonate, potassium carbonate and potassium hydrogen carbonate; alkaline earth metal carbonates such as calcium carbonate and barium carbonate; sodium hydroxide and potassium hydroxide Alkali metal hydroxides; alkali metals such as lithium, sodium and potassium; alkali metal alkoxides such as sodium methoxide, sodium ethoxide and potassium t-butoxide; sodium hydride, potassium hydride and lithium hydride, etc.
  • Alkali metal hydrogen compounds such as n-butyllithium; alkali metal amides such as lithium diisopropylamide; and triethylamine, pyridine, 4-dimethylaminopyridine, N, N-dimethyla Phosphorus and 1,8-diazabicyclo-7- [5.4.0] Organic amines such as undecene, and the like.
  • the acid used is not particularly limited.
  • the acid include inorganic acids such as hydrochloric acid, hydrobromic acid, hydroiodic acid and sulfuric acid; organic acids such as formic acid, acetic acid, butyric acid, trifluoroacetic acid and p-toluenesulfonic acid; and lithium chloride, bromide Mention may be made of Lewis acids such as lithium, rhodium chloride, aluminum chloride and boron trifluoride.
  • the triazole compound according to the present embodiment can be used in a plant disease control agent and a plant disease control method using the same.
  • Triazole compounds have a controlling effect against a wide range of plant diseases including foliage diseases, seed infectious diseases and soil infectious diseases.
  • triazole compounds exhibit an effect of increasing the yield by controlling the growth and an effect of improving the quality of a wide variety of crops and horticultural plants.
  • the plant disease control agent containing a triazole compound can be applied by non-foliage treatment such as seed treatment, irrigation treatment, water surface treatment, etc. in addition to foliage treatment such as foliage spraying.
  • non-foliage treatment such as seed treatment, irrigation treatment, water surface treatment, etc.
  • foliage treatment such as foliage spraying.
  • a labor can be reduced compared with the case where a foliage process is performed.
  • the plant disease control agent containing a triazole compound can control not only non-foliage diseases but also foliage diseases by non-foliage treatment.
  • reaction solution was poured into ice water and extracted with dichloromethane.
  • the organic layer was washed with water and saturated brine, and then dried over anhydrous sodium sulfate.
  • the solvent was distilled off under reduced pressure, and excess bromoform was distilled off from the resulting crude extract by distillation under reduced pressure.
  • the distillation residue partially solidified and separated into two diastereomers when the solid and oil were separated.
  • the solvent was distilled off under reduced pressure to obtain 0.45 g of a crude product of the diastereomer (A) of the target compound (Ia-a) as a pale yellow oil which was later solidified at room temperature as a pale yellow solid. .
  • the yield was 93%.
  • the diastereomer (B) of the compound (Ib-a) reacted in the same manner to obtain 0.49 g of a crude product containing the diastereomer (B) of the target compound (Ia-a).
  • the olefin compound derived from the compound (Ia-3a) and other impurities, which are impurities contained in the diastereomer (B) of the compound (Ia-a) are distilled away by washing with hexane, and the target compound (Ia-a) 0.31 g of diastereomer (B) was obtained as a white solid. The yield was 64%.
  • the organic layer was washed with saturated aqueous sodium hydrogen carbonate, water and saturated brine, and dried over anhydrous sodium sulfate.
  • the solvent was distilled off under reduced pressure to obtain 0.51 g of the diastereomer (A) of the target compound (Ic-a) as a yellow oil. The yield was 96%.
  • the diastereomer (B) of the compound (Ic-a) reacted in the same manner to obtain 0.36 g of the diastereomer (B) of the target compound (Ic-a) as a white solid.
  • the yield was 99%.
  • ethyl acetate was used instead of toluene as an extraction solvent after the reaction.
  • the diastereomer (B) of the compound (Ic-a) reacted in the same manner to obtain 0.25 g of the diastereomer (B) of the target compound (III-a) as a colorless oil.
  • the yield was 92%.
  • the respective diastereomeric ratios are as follows.
  • the organic layer was washed with saturated aqueous sodium hydrogen carbonate, water and saturated brine, and dried over anhydrous sodium sulfate.
  • the solvent was distilled off under reduced pressure, and 0.37 g of the target compound (Ic-b) was quantitatively obtained as a diastereomeric mixture of yellow oil.
  • the diastereomer (B) of the compound (Ia-b) was subjected to the same reaction as described above to obtain 0.32 g of the target compound (Ic-b) as a white crystal diastereomer mixture.
  • the yield was 94%.
  • the diastereomer ratio in the obtained diastereomer mixture is almost different from the ratio in the diastereomer (B) of the starting compound (Ia-b). Not estimated.
  • the solvent was distilled off under reduced pressure to obtain 0.21 g of the objective compound (III-b) as a diastereomeric mixture of pale yellow oil.
  • the yield was 91%.
  • This crude extract was dissolved in 2.0 ml of methanol, and a solution in which 0.40 g of sodium hydroxide was dissolved in 1.0 ml of water was added. After stirring at room temperature for 1 hour, the reaction solution was poured into ice water and extracted with hexane. The organic layer was washed with water and saturated brine, and then dried over anhydrous sodium sulfate. The solvent was distilled off under reduced pressure, and the resulting oil was purified by silica gel column chromatography. 0.13 g of the target compound (III-b) was obtained as a diastereomeric mixture of pale yellow oil. The yield was 53%.
  • the present invention can also be expressed as follows.
  • the method for producing a triazole compound according to the present invention includes a second oxirane diastereomer that produces a second oxirane diastereomer of the oxirane compound represented by the general formula (III) from the diol compound produced in the diol production step.
  • the method further includes a stereomer production step and a diol regeneration step of producing the diol compound using the second oxirane diastereomer produced in the second oxirane diastereomer production step.
  • the oxirane compound is hydrolyzed to produce a diol compound.
  • the oxirane compound in the diol production step, is acetonated to produce a dioxolane compound represented by the following general formula (Ib):
  • X 3 to X 5 represent a hydrogen atom or a halogen atom
  • X 5 represents a halogen atom
  • a plurality of X 4 are the same atom
  • a plurality of X 5 are the same atom.
  • X 4 and X 5 are different from each other, and n represents 0 to 3.
  • R 2 represents a C3 to C6 cycloalkyl group or a C1 to C4 substituted with the cycloalkyl group
  • the cycloalkyl group and the alkyl group are a halogen atom, a C1-C4 alkyl group, a C1-C4 haloalkyl group, a C3-C6 cycloalkyl group, an aryl group, or an arylalkyl group (alkyl
  • the aromatic ring of the aryl group and the arylalkyl group may be a halogen atom, a C1-C4 alkyl group, Haloalkyl group 1 ⁇ C4, alkoxy group of C1 ⁇ C4, or may be substituted with a haloalkoxy group having C1 ⁇ C4.) It is preferable to hydrolyze the dioxolane compound to produce a diol compound.
  • a first dioxolane diastereomer is separated from the dioxolane compound, and the first dioxolane diastereomer is hydrolyzed to obtain a diol compound. It is preferable to produce.
  • a halohydrin or sulfonyl compound represented by the following general formula (Ic) is obtained from the diol compound produced in the diol production step in the first oxirane diastereomer production step.
  • X 3 to X 5 represent a hydrogen atom or a halogen atom
  • X 5 represents a halogen atom
  • a plurality of X 4 are the same atom
  • a plurality of X 5 are the same atom.
  • X 4 and X 5 are mutually different atoms
  • n represents 0 to 3
  • L represents a halogen atom or a sulfonyloxy group
  • R 2 represents a C3 to C6 cycloalkyl group, Or a C1-C4 alkyl group substituted with the cycloalkyl group, wherein the cycloalkyl group and the alkyl group are a halogen atom, a C1-C4 alkyl group, a C1-C4 haloalkyl group, a C3-C6
  • the aryl group and the arylalkyl may be substituted with a cycloalkyl group, an aryl group, or an
  • the method for producing a triazole compound according to the present invention includes separating the first diol diastereomer from the diol compound produced in the diol production step in the first oxirane diastereomer production step. From the diol diastereomer, a first halohydrin or sulfonyl diastereomer of a halohydrin or sulfonyl compound represented by the following general formula (Ic) is produced:
  • X 3 to X 5 represent a hydrogen atom or a halogen atom
  • X 5 represents a halogen atom
  • a plurality of X 4 are the same atom
  • a plurality of X 5 are the same atom.
  • X 4 and X 5 are mutually different atoms
  • n represents 0 to 3
  • L represents a halogen atom or a sulfonyloxy group
  • R 2 represents a C3 to C6 cycloalkyl group, Or a C1-C4 alkyl group substituted with the cycloalkyl group, wherein the cycloalkyl group and the alkyl group are a halogen atom, a C1-C4 alkyl group, a C1-C4 haloalkyl group, a C3-C6
  • the aryl group and the arylalkyl may be substituted with a cycloalkyl group, an aryl group, or an
  • the first oxirane diastereomer is generated from the first halohydrin or sulfonyl diastereomer.
  • a halohydrin or sulfonyl compound represented by the following general formula (Ic) is obtained from the diol compound produced in the diol production step in the second oxirane diastereomer production step.
  • X 3 to X 5 represent a hydrogen atom or a halogen atom
  • X 5 represents a halogen atom
  • a plurality of X 4 are the same atom
  • a plurality of X 5 are the same atom.
  • X 4 and X 5 are mutually different atoms
  • n represents 0 to 3
  • L represents a halogen atom or a sulfonyloxy group
  • R 2 represents a C3 to C6 cycloalkyl group, Or a C1-C4 alkyl group substituted with the cycloalkyl group, wherein the cycloalkyl group and the alkyl group are a halogen atom, a C1-C4 alkyl group, a C1-C4 haloalkyl group, a C3-C6
  • the aryl group and the arylalkyl may be substituted with a cycloalkyl group, an aryl group, or an
  • the second halohydrin or sulfonyl diastereomer is separated from the halohydrin or sulfonyl compound to produce the second oxirane diastereomer from the second halohydrin or sulfonyl diastereomer.
  • the second diol diastereomer is separated from the diol compound produced in the diol production step.
  • a second halohydrin or sulfonyl diastereomer of the halohydrin or sulfonyl compound represented by the following general formula (Ic) is produced:
  • X 3 to X 5 represent a hydrogen atom or a halogen atom
  • X 5 represents a halogen atom
  • a plurality of X 4 are the same atom
  • a plurality of X 5 are the same atom.
  • X 4 and X 5 are mutually different atoms
  • n represents 0 to 3
  • L represents a halogen atom or a sulfonyloxy group
  • R 2 represents a C3 to C6 cycloalkyl group, Or a C1-C4 alkyl group substituted with the cycloalkyl group, wherein the cycloalkyl group and the alkyl group are a halogen atom, a C1-C4 alkyl group, a C1-C4 haloalkyl group, a C3-C6
  • the aryl group and the arylalkyl may be substituted with a cycloalkyl group, an aryl group, or an
  • the second oxirane diastereomer is produced from the second halohydrin or sulfonyl diastereomer.
  • the present invention can be suitably used as a method for producing an active ingredient of a control material capable of controlling plant diseases by foliage treatment and non-foliage treatment.

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  • Organic Chemistry (AREA)
  • Chemical & Material Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
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  • Health & Medical Sciences (AREA)
  • Engineering & Computer Science (AREA)
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  • Wood Science & Technology (AREA)
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  • Epoxy Compounds (AREA)

Abstract

L'invention concerne un procédé de fabrication d'un composé triazole, selon lequel un composé diol est obtenu d'un composé oxirane, un premier diastéréomère d'oxirane est obtenu du composé diol et un composé triazole est obtenu à l'aide du premier diastéréomère d'oxirane. Le premier diastéréomère d'oxirane est un diastéréomère à partir duquel un diastéréomère du composé triazole visé est issu. Par conséquent, un composé triazole est obtenu de façon efficace à un faible coût.
PCT/JP2012/077762 2011-11-09 2012-10-26 Procédé de fabrication de composé triazole et intermédiaire de composé triazole Ceased WO2013069481A1 (fr)

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Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2008146826A1 (fr) * 2007-05-29 2008-12-04 Nihon Nohyaku Co., Ltd. Procédé de production d'un composé d'oxyde de styrène actif sur le plan optique
WO2010023862A1 (fr) * 2008-08-26 2010-03-04 Kureha Corporation Dérivés de 5-benzyl-4-azolylméthyl-4-spiro[2.4]heptanol, leurs procédés de fabrication et agents pour l’agriculture et l’horticulture et agents de protection de matériel industriel correspondants
WO2010142779A1 (fr) * 2009-06-12 2010-12-16 Basf Se Dérivés antifongiques de 1,2,4-triazolyle ayant un substituant soufré en 5
WO2011070742A1 (fr) * 2009-12-08 2011-06-16 Kureha Corporation Dérivés azole et leurs procédés de production, composés intermédiaires pour synthétiser les dérivés et leurs procédés de production, et agents agro-horticoles et agents de protection de produits industriels contenant les dérivés

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2008146826A1 (fr) * 2007-05-29 2008-12-04 Nihon Nohyaku Co., Ltd. Procédé de production d'un composé d'oxyde de styrène actif sur le plan optique
WO2010023862A1 (fr) * 2008-08-26 2010-03-04 Kureha Corporation Dérivés de 5-benzyl-4-azolylméthyl-4-spiro[2.4]heptanol, leurs procédés de fabrication et agents pour l’agriculture et l’horticulture et agents de protection de matériel industriel correspondants
WO2010142779A1 (fr) * 2009-06-12 2010-12-16 Basf Se Dérivés antifongiques de 1,2,4-triazolyle ayant un substituant soufré en 5
WO2011070742A1 (fr) * 2009-12-08 2011-06-16 Kureha Corporation Dérivés azole et leurs procédés de production, composés intermédiaires pour synthétiser les dérivés et leurs procédés de production, et agents agro-horticoles et agents de protection de produits industriels contenant les dérivés

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