Method for producing halovinylimidazole compounds

Abstract

The present invention provides a method for producing a compound represented by formula (2) (in the formula, R1 and Q each represent the same as those in formula (1)), the method comprising causing a chemical reaction between sodium hyposulphite and a compound represented by formula (1) (in the formula, R1 represents a C1-6 alkyl group, Q represents a hydrogen atom or a substituted or unsubstituted pyridyl group, X represents a halogeno group, and Ra represents a C1-6 alkyl group) in the presence of a base.

Description

[Technical Field]

[0001] This invention relates to a method for producing halovinylimidazole compounds. This application claims priority based on Japanese Patent Application No. 2021-188984, filed in Japan on November 19, 2021, and the contents of that application are incorporated herein by reference. [Background technology]

[0002] Nitrogen-containing heterocycles are major substructures (building blocks) that constitute compounds that are the active ingredients of pharmaceuticals and agrochemicals. In recent years, there has been a great deal of activity in developing pest control agents for arthropods that contain imidazole rings, pyridine rings, etc. For example, Patent Document 1 shows a compound represented by formula (A).

[0003] [ka]

[0004] Vinylimidazole compounds are also useful as monomers used in polymer production. For example, Patent Document 2 discloses a method characterized by dehydrogenating a compound selected from the group consisting of 2-alkylimidazoles and 2-alkylimidazolines in the presence of a dehydrogenation catalyst to produce 2-alkenylimidazoles. Patent Document 3 discloses a method for producing a 1-vinylimidazole derivative, characterized by dehydrating a 2-hydroxyethylimidazole derivative in the liquid phase in the presence of an alkali metal hydroxide or alkoxide. Patent Document 4 discloses a method for producing a vinylimidazole compound by subjecting a hydroxyethyl group-containing imidazole compound to a dehydration reaction in a solvent whose boiling point at atmospheric pressure is 30°C or more higher than the boiling point at atmospheric pressure of the vinylimidazole compound, in the presence of a dehydrating agent. [Prior art documents] [Patent Documents]

[0005] [Patent Document 1] WO 2020 / 090585 A [Patent Document 2] Japanese Patent Application Publication No. 58-210067 [Patent Document 3] Japanese Patent Application Publication No. 4-21672 [Patent Document 4] Japanese Patent Publication No. 2011-121913 [Overview of the project] [Problems that the invention aims to solve]

[0006] The objective of this invention is to provide a method for producing halovinylimidazole compounds, which are one of the building blocks of the present invention. [Means for solving the problem]

[0007] As a result of repeated considerations to achieve the above objectives, we have completed the present invention, which encompasses the following aspects.

[0008] [1] A method for producing a compound represented by formula (2) (hereinafter sometimes referred to as compound (2)), comprising chemically reacting a compound represented by formula (1) (hereinafter sometimes referred to as compound (1)) with sodium hyposulfite in the presence of a base.

[0009] [ka] (In formula (1), R 1 represents a C1-6 alkyl group, Q represents a hydrogen atom or a substituted or unsubstituted pyridyl group, X represents a halogeno group, and R a (This indicates a C1-6 alkyl group.)

[0010] [ka] (In formula (2), R 1 A method for manufacturing the product, where Q and the other Q are the same as those in formula (1).

[0011] 〔2〕 Reacting the compound represented by formula (3) (hereinafter sometimes referred to as compound (3)) with the compound represented by formula (4) (hereinafter sometimes referred to as compound (4)) in the presence of a base or metal alkoxide, and reacting the product of the said chemical reaction with the compound represented by formula (5) (hereinafter sometimes referred to as compound (5)), the method further comprising obtaining the compound represented by the said formula (1), the production method according to 〔1〕.

[0012]

Chemical formula

[0013]

Chemical formula

[0014]

Chemical formula

[0015] 〔3〕 A compound represented by formula (2a1), formula (2a2), or formula (2a3).

[0016]

Chemical formula

Advantages of the Invention

[0017] According to the production method of the present invention, the compound represented by formula (2) can be obtained in a high yield.

Modes for Carrying Out the Invention

[0018] In this invention, the term "unsubstituted" means that only the core group is present. When the term "substituted" is not used and only the name of the core group is given, it means "unsubstituted" unless otherwise specified. On the other hand, the term "substitution" means that one of the hydrogen atoms of the core group is substituted by a group (substituent) that has the same or a different structure as the core group. Therefore, a "substituent" is another group bonded to the core group. There may be one substituent or two or more substituents. The two or more substituents may be the same or different. Terms such as "C1-6" indicate that the parent group has 1 to 6 carbon atoms. This number of carbon atoms does not include the number of carbon atoms in substituents. For example, a butyl group with an ethoxy group as a substituent is classified as a C2 alkoxy C4 alkyl group. The "substituents" are chemically acceptable and not particularly limited insofar as they have the effects of the present invention.

[0019] The following are examples of groups that can act as "substituents". C1-6 alkyl groups such as methyl group, ethyl group, n-propyl group, i-propyl group, n-butyl group, s-butyl group, i-butyl group, t-butyl group, n-pentyl group, and n-hexyl group; C2-6 alkenyl groups such as vinyl group, 1-propenyl group, 2-propenyl group (allyl group), 1-butenyl group, 2-butenyl group, 3-butenyl group, 1-methyl-2-propenyl group, and 2-methyl-2-propenyl group; C2-6 alkynyl groups such as ethynyl group, 1-propynyl group, 2-propynyl group, 1-butynyl group, 2-butynyl group, 3-butynyl group, and 1-methyl-2-propynyl group;

[0020] C3-6 cycloalkyl groups such as cyclopropyl, cyclobutyl, cyclopentyl, and cyclohexyl groups; Phenyl group; A heterocyclyl group with 3 to 6 members;

[0021] C1-6 alkoxy groups such as methoxy, ethoxy, n-propoxy, i-propoxy, n-butoxy, s-butoxy, i-butoxy, and t-butoxy groups; C6-10 aryloxy groups such as phenoxy and naphthoxy groups; Five- to six-membered heteroaryloxy groups such as thiazolyloxy and pyridyloxy groups;

[0022] C1-6 alkoxycarbonyl groups such as methoxycarbonyl groups, ethoxycarbonyl groups, n-propoxycarbonyl groups, i-propoxycarbonyl groups, n-butoxycarbonyl groups, and t-butoxycarbonyl groups;

[0023] Halogeno groups such as fluoro groups, chloro groups, bromo groups, and iod groups; C1-6 haloalkyl groups such as chloromethyl, chloroethyl, trifluoromethyl, 1,2-dichloro-n-propyl, 1-fluoro-n-butyl, and perfluoro-n-pentyl groups; C1-6 haloalkoxy groups such as trifluoromethoxy, 2-chloro-n-propoxy, and 2,3-dichlorobutoxy;

[0024] Formylamino group; C1-6 alkylcarbonylamino groups such as acetylamino groups, propanoylamino groups, butyrylamino groups, and i-propylcarbonylamino groups; C1-6 alkoxycarbonylamino groups such as methoxycarbonylamino groups, ethoxycarbonylamino groups, n-propoxycarbonylamino groups, and i-propoxycarbonylamino groups; Unsubstituted or substituted aminocarbonyl groups such as aminocarbonyl groups, dimethylaminocarbonyl groups, phenylaminocarbonyl groups, and N-phenyl-N-methylaminocarbonyl groups;

[0025] C1-6 alkylthio groups such as methylthio group, ethylthio group, n-propylthio group, i-propylthio group, n-butylthio group, i-butylthio group, s-butylthio group, and t-butylthio group; C1-6 haloalkylthio groups such as trifluoromethylthio group and 2,2,2-trifluoroethylthio group; C1-6 alkylsulfonyl groups such as methylsulfonyl groups, ethylsulfonyl groups, and t-butylsulfonyl groups; C1-6 haloalkylsulfonyl groups such as trifluoromethylsulfonyl group and 2,2,2-trifluoroethylsulfonyl group;

[0026] Cyano group; nitro group.

[0027] Furthermore, in these "substituents," any hydrogen atom in the substituent may be substituted with a group of a different structure. Examples of substituents in this case include C1-6 alkyl groups, C1-6 haloalkyl groups, C1-6 alkoxy groups, C1-6 haloalkoxy groups, halogeno groups, cyano groups, and nitro groups.

[0028] Furthermore, the above-mentioned "3-6 membered heterocyclyl group" refers to a group that contains 1 to 4 heteroatoms selected from the group consisting of nitrogen, oxygen, and sulfur atoms as constituent atoms of the ring. The heterocyclyl group may be monocyclic or polycyclic. In a polycyclic heterocyclyl group, at least one ring may be heterocyclic, and the remaining rings may be saturated alicyclic, unsaturated alicyclic, or aromatic rings. Examples of "3-6 membered heterocyclyl groups" include 3-6 membered saturated heterocyclyl groups, 5-6 membered heteroaryl groups, and 5-6 membered partially unsaturated heterocyclyl groups. Examples of 3-6 member saturated heterocyclyl groups include azilidinyl group, epoxy group, pyrrolidinyl group, tetrahydrofuranyl group, thiazolidinyl group, piperidyl group, piperazinyl group, morpholinyl group, dioxolanyl group, and dioxanyl group. Examples of the 5-membered heteroaryl group include a pyrrolyl group, a furyl group, a thienyl group, an imidazolyl group, a pyrazolyl group, an oxazolyl group, an isoxazolyl group, a thiazolyl group, an isothiazolyl group, a triazolyl group, an oxadiazolyl group, a thiadiazolyl group, a tetrazolyl group, and the like. Examples of the 6-membered heteroaryl group include a pyridyl group, a pyrazinyl group, a pyrimidinyl group, a pyridazinyl group, a triazinyl group, and the like. Examples of the 5-membered partially unsaturated heterocyclic group include a pyrrolinyl group, a dihydrofuranyl group, an imidazolinyl group, a pyrazolinyl group, an oxazolinyl group, an isoxazolinyl group, and the like. Examples of the 6-membered partially unsaturated heterocyclic group include a dihydropyranyl group, and the like.

[0029] The method for producing the compound (2) of the present invention includes subjecting the compound (1) and sodium bisulfite to a chemical reaction (hereinafter sometimes referred to as the third reaction) in the presence of a base.

[0030] The compound (1) is represented by the following formula (1).

[0031] [Chemical formula]

[0032] In the formula (1), R 1 represents a C1-6 alkyl group. R 1 The C1-6 alkyl group in may be linear or branched. Examples of the C1-6 alkyl group in R 1 include a methyl group, an ethyl group, an n-propyl group, an n-butyl group, an n-pentyl group, an n-hexyl group, an i-propyl group, an i-butyl group, an s-butyl group, a t-butyl group, an i-pentyl group, a neopentyl group, a 2-methylbutyl group, a 2,2-dimethylpropyl group, an i-hexyl group, and the like.

[0033] In formula (1) above, Q represents a hydrogen atom or a substituted or unsubstituted pyridyl group. Q is preferably a hydrogen atom.

[0034] Substituents on the "pyridyl group" in Q include: halogen groups such as fluoro, chloro, bromo, and iod groups; C1-6 alkyl groups such as methyl, ethyl, n-propyl, i-propyl, n-butyl, s-butyl, i-butyl, t-butyl, n-pentyl, and n-hexyl groups; C1-6 haloalkyl groups such as difluoromethyl, trifluoromethyl, perfluoroethyl, 1,2,2,3,3,3-hexafluoropropyl, perfluoropropyl, and 1,2,3,3,3-pentafluoro-2-(trifluoromethyl)propyl groups; C3-6 cycloalkyl groups such as cyclopropyl and cyclobutyl groups; and C1-6 alkoxy groups such as methoxy, ethoxy, n-propoxy, i-propoxy, n-butoxy, s-butoxy, i-butoxy, and t-butoxy groups. Examples include C1-6 haloalkoxy groups such as difluoromethoxy, trifluoromethoxy, 2,2-difluoroethyl, and 2,2,2-trifluoroethyl; C1-6 alkylthio groups such as methylthio and ethylthio; C1-6 alkylsulfinyl groups such as methylsulfinyl and ethylsulfinyl; C1-6 alkylsulfonyl groups such as methylsulfonyl and ethylsulfonyl; phenyl groups; phenyl groups substituted with halogeno, C1-6 alkyl, C1-6 haloalkyl, or C1-6 haloalkoxy groups; 5-6 membered heteroaryl groups such as triazolyl and pyrimidinyl groups; 5-6 membered heteroaryl groups substituted with halogeno, C1-6 alkyl, C1-6 haloalkyl, or C1-6 haloalkoxy groups; or cyano groups.

[0035] In formula (1) above, X represents a halogen group.

[0036] Examples of "halogeno groups" in X include fluoro groups, chloro groups, bromo groups, and iod groups. Preferred X groups include chloro groups and bromo groups.

[0037] In equation (1) above, R a This represents a C1-6 alkyl group.

[0038] R a In this context, "C1-6 alkyl groups" are R 1 We can cite the same thing as in [the previous example].

[0039] The compound (1) used in the present invention may be synthesized by the present inventors using known methods, or it may be synthesized by others using some method and commercially available.

[0040] Compound (1) used in the present invention can be obtained, for example, by a method comprising a chemical reaction (hereinafter sometimes referred to as the first reaction) between compound (3) and compound (4) in the presence of a base or a metal alkoxide, and a chemical reaction (hereinafter sometimes referred to as the second reaction) between the product of the first reaction and compound (5).

[0041] [ka]

[0042] In the above equation (3), R 1 represents a C1-6 alkyl group, and Q represents a hydrogen atom or a substituted or unsubstituted pyridyl group. Examples of the compound (3) include 1-methyl-1H-imidazole-5-carbaldehyde.

[0043] [ka]

[0044] In formula (4) above, X represents a halogeno group. Examples of the compound (4) include 2,2-dichloro-1,1,1-trifluoroethane (HCFC-123) and 2-bromo-2-chloro-1,1,1-trifluoroethane (halothane), with 2-bromo-2-chloro-1,1,1-trifluoroethane being preferred.

[0045] [ka]

[0046] In equation (5) above, R a This represents a C1-6 alkyl group. Examples of the compound (5) include acetic anhydride and propionic anhydride.

[0047] Compounds (3), (4), and (5) used in the first or second reaction may be synthesized by the user using known methods, or they may be synthesized by others and commercially available. In the first reaction described above, the amount of compound (4) is, for example, 1.0 to 5.0 moles, preferably 1.2 to 2.0 moles, per mole of compound (3).

[0048] Examples of bases to be present in the first reaction include inorganic bases such as sodium carbonate, sodium bicarbonate, potassium carbonate, potassium bicarbonate, sodium hydroxide, potassium hydroxide, sodium hydride, and potassium hydride; and organic bases such as triethylamine, tetramethylethylenediamine, N,N-diisopropylamine, N,N-dimethylaniline, N,N-diethylaniline, 4-methylmorpholine, 1-azabicyclo[2.2.2]octane, 1,4-diazabicyclo[2.2.2]octane (abbreviation: DABCO), 1,8-diazabicyclo[5.4.0]undeca-7-ene, 1,5-diazabicyclo[4.3.0]nona-5-ene, pyridine, 4-(dimethylamino)pyridine, and 2,6-dimethylpyridine.

[0049] The amount of base used is, for example, 1.0 to 5.0 moles, preferably 1.5 to 2.0 moles, per mole of compound (3).

[0050] Examples of metal alkoxides to be present in the first reaction include sodium methoxide, sodium ethoxide, and potassium t-butoxide, with potassium t-butoxide being preferred.

[0051] The amount of the metal alkoxide used is, for example, 1.0 to 5.0 moles, preferably 1.2 to 2.0 moles, per mole of compound (3).

[0052] The first reaction can be carried out without a solvent or in a solvent. Considering ease of operation, it is preferable to carry out the first reaction in an organic solvent. Examples of organic solvents include ethers such as diethyl ether, diisopropyl ether, diethylene glycol dimethyl ether (product name: Digrime), and tetrahydrofuran (abbreviation: THF); halogenated hydrocarbons such as dichloromethane, chloroform, and 1,2-dichloroethane (abbreviation: DCE); aliphatic hydrocarbons such as pentane, hexane, cyclohexane, heptane, and octane; aromatic hydrocarbons such as toluene and xylene; aproton polar solvents such as N,N-dimethylformamide (abbreviation: DMF), N,N'-dimethylpropylene urea (abbreviation: DMPU), hexamethylphosphate triamide (abbreviation: HMPA); and acetonitrile, with ethers such as tetrahydrofuran being preferred. The amount of the organic solvent used is preferably 10 to 2000 parts by weight per 1 part by weight of compound (3).

[0053] The order in which the compounds (3), (4), metal alkoxide or base, and organic solvent used as needed in the first reaction are added to the reaction site is not particularly limited. For example, it is preferable to add the solvent to the reaction vessel, then add compounds (3) and (4), and then add the metal alkoxide or base. The mixing temperature is preferably between -70°C and 0°C, and more preferably between -70°C and -50°C. When mixing, it is preferable to mix under stirring. It is preferable to add the metal alkoxide or base gradually in small amounts, such as by dropwise addition.

[0054] The temperature in the first reaction is preferably -70°C to 0°C, and more preferably -70°C to -50°C. The pressure in the first reaction is not particularly limited and is, for example, atmospheric pressure. The reaction time in the first reaction is, for example, 5 minutes to 24 hours, and more preferably 5 minutes to 1 hour. The first reaction is preferably carried out under an inert gas atmosphere. After the completion of the first reaction, the liquid containing the first reaction product can be used directly in the second reaction. Alternatively, after the completion of the first reaction, the liquid containing the first reaction product may be subjected to post-treatment and, if necessary, purification. Post-treatment may include, for example, extraction with an organic solvent, followed by drying and concentration of the resulting organic layer. Purification may include, for example, recrystallization and chromatography.

[0055] In the second reaction described above, the amount of compound (5) is, for example, 1.0 to 5.0 moles, preferably 1.2 to 3.0 moles, per mole of compound (3).

[0056] The temperature in the second reaction is preferably -70°C to 0°C, and more preferably -70°C to -50°C. The pressure in the second reaction is not particularly limited and is, for example, atmospheric pressure. The reaction time in the second reaction is, for example, 0.5 hours to 24 hours, preferably 0.5 hours to 2 hours. The second reaction is preferably carried out under an inert gas atmosphere.

[0057] After the completion of the second reaction, the solution containing compound (1) can be used directly in the third reaction. Alternatively, after the completion of the second reaction, the solution containing compound (1) may be subjected to post-treatment and, if necessary, purification. Post-treatment may include, for example, extraction with an organic solvent, followed by drying and concentration of the resulting organic layer. Purification may include, for example, recrystallization and chromatography.

[0058] The aforementioned sodium hyposulfite can be obtained by electrolytic reduction of sodium bisulfite. Alternatively, it can be obtained by the reaction of sulfur dioxide and its sodium salt mediated by metallic zinc, and then by purification. Sodium hyposulfite has strong reducing power. The amount of sodium hyposulfite used is, for example, 1.0 to 5.0 moles, preferably 1.1 to 3.0 moles, per mole of compound (1).

[0059] Examples of bases to be present in the third reaction include inorganic bases such as sodium carbonate, sodium bicarbonate, potassium carbonate, potassium bicarbonate, sodium hydroxide, potassium hydroxide, sodium hydride, and potassium hydride; and organic bases such as triethylamine, tetramethylethylenediamine, N,N-diisopropylamine, N,N-dimethylaniline, N,N-diethylaniline, 4-methylmorpholine, 1-azabicyclo[2.2.2]octane, 1,4-diazabicyclo[2.2.2]octane (abbreviation: DABCO), 1,8-diazabicyclo[5.4.0]undeca-7-ene, 1,5-diazabicyclo[4.3.0]nona-5-ene, pyridine, 4-(dimethylamino)pyridine, and 2,6-dimethylpyridine, with inorganic bases such as sodium bicarbonate being preferred. The amount of base used is, for example, 1.0 to 5.0 moles, preferably 1.1 to 3.0 moles, per mole of compound (1).

[0060] The third reaction can be carried out without a solvent or in a solvent. Considering ease of operation, it is preferable to carry out the reaction in a solvent. Since sodium hyposulfite is used, it is preferable to use a mixed solvent of water and an organic solvent. Examples of organic solvents include alcohols such as methanol and ethanol; ketones such as acetone and methyl ethyl ketone; ethers such as diethyl ether, diisopropyl ether, diethylene glycol dimethyl ether (product name: Digrime), and tetrahydrofuran (abbreviation: THF); aromatic hydrocarbons such as toluene and xylene; aproton polar solvents such as N,N-dimethylformamide (abbreviation: DMF), N,N'-dimethylpropylene urea (abbreviation: DMPU), and hexamethyl phosphate triamide (abbreviation: HMPA); and acetonitrile, with ketones such as acetone being preferred. The amount of solvent used is preferably 2 to 100 parts by weight per 1 part by weight of compound (1).

[0061] The order in which compound (1), sodium hyposulfite, the base, and any solvent used as needed are added to the reaction site in the third reaction is not particularly limited.

[0062] One embodiment involves adding compound (1) to a solvent or solvent-free solution in a container, adding sodium hyposulfite and a base to obtain a mixture, and completing the chemical reaction while stirring this mixture. Mixing is preferably carried out under stirring. Each substance may be added either all at once or gradually in small amounts.

[0063] The temperature in the third reaction is not particularly limited, and is, for example, between 0°C and the solvent boiling point, for example, around 20°C to 30°C. The pressure in the third reaction is, for example, 0.1 to 1 MPa, preferably 0.1 to 0.5 MPa. The reaction time in the third reaction is not particularly limited, and is, for example, 0.5 hours to 24 hours. The third reaction is preferably carried out under an inert gas atmosphere. The third reaction is preferably quenched by adding a saturated aqueous solution of sodium bicarbonate or the like. After the completion of the third reaction, the resulting organic layer can be extracted with an organic solvent and then dried and concentrated for post-treatment. Furthermore, if necessary, the product of the third reaction may be purified by operations such as recrystallization and chromatography.

[0064] Compound (2) obtained by the production method of the present invention is represented by formula (2).

[0065] [ka]

[0066] In equation (2) above, R 1 , and Q represent the same things as those in equation (1) above.

[0067] The following notations in chemical formulas represent undefined double stereo bonds.

[0068] [ka]

[0069] Stereoisomers can be separated and purified using techniques such as chromatography.

[0070] Among the compounds (2) obtained by the production method of the present invention, the compounds represented by the following formulas (2a1), (2a2), or (2a3) are novel compounds and are particularly useful as intermediates in the production of pharmaceuticals and agrochemicals, or as monomers for polymer production.

[0071] [ka]

[0072] In the above formulas (2a1), (2a2), or (2a3), R 1This represents a C1-6 alkyl group, preferably a methyl group. Specifically, the following compounds are preferred as compounds represented by formula (2a1), formula (2a2), or formula (2a3).

[0073] [ka]

[0074] The present invention will be described in more detail below with reference to examples. However, the present invention is not limited to the following examples.

[0075] [Example 1] (EZ)-5-(2-chloro-3,3,3-trifluoropropane-1-en-1-yl)-1-methyl-1H-imidazole was prepared using the following procedure.

[0076] (Process 1) Synthesis of 2-bromo-2-chloro-3,3,3-trifluoro-1-(1-methyl-1H-imidazole-5-yl)propyl acetate

[0077] [ka]

[0078] 1-Methyl-1H-imidazole-5-carbaldehyde (37 g) and halothane (92.8 g, 1.4 eq.) were dissolved in tetrahydrofuran (1100 mL) and cooled to -70°C. Potassium t-butoxide (49.0 g, 1.3 eq.), diluted in tetrahydrofuran (700 mL), was slowly added dropwise while stirring, and stirring was continued for 5 minutes. Subsequently, acetic anhydride (54.8 g, 1.6 eq.) was added, and the mixture was stirred at -70°C for 1 hour. After that, it was allowed to return to room temperature. The resulting solution was quenched with saturated sodium bicarbonate solution. Then, it was extracted with ethyl acetate. The resulting organic layer was concentrated under reduced pressure to obtain 107.9 g of crude product (crude yield 92%).

[0079] (Process 2) Synthesis of (EZ)-5-(2-chloro-3,3,3-trifluoropropane-1-en-1-yl)-1-methyl-1H-imidazole

[0080] [ka]

[0081] The crude product (2-bromo-2-chloro-3,3,3-trifluoro-1-(1-methyl-1H-imidazole-5-yl)propyl acetate) obtained in step 1 (24.3 g), sodium hyposulfite (24.2 g, 2 eq.), and sodium bicarbonate (11.7 g, 2 eq.) were mixed in acetone (140 mL) and stirred at room temperature. Water (27 mL) was then added dropwise while stirring. The temperature was then raised to 40 °C and stirred for 2 hours. After returning to room temperature, saturated sodium bicarbonate solution was added and the mixture was extracted with ethyl acetate. The resulting organic layer was concentrated under reduced pressure, and the concentrate was purified by silica gel chromatography to obtain 12.8 g of the target product (yield 88%, E / Z = 20 / 80). The NMR signal of (EZ)-5-(2-chloro-3,3,3-trifluoropropane-1-en-1-yl)-1-methyl-1H-imidazole is shown below. 1H-NMR (400 MHz, CDCl3): Z-body δ 7.97 (s, 1H), 7.58 (s, 1H), 7.10 (s, 1H), 3.70 (s, 3H). E-body δ 7.52 (s, 1H), 7.37 (s, 1H), 6.86 (s, 1H), 3.65 (s, 3H). 19F-NMR (376 MHz, CDCl3): Z-isomer δ -67.9 (s). E-isomer δ -63.2 (s). [Industrial applicability]

[0082] The manufacturing method of the present invention can efficiently obtain halovinylimidazole compounds, which are major substructures that make up compounds that serve as active ingredients for pharmaceuticals and agrochemicals.

Claims

1. Compound represented by formula (1): 【Chemistry 1】 (In formula (1), R １ represents a C1-6 alkyl group, Q represents a hydrogen atom or a substituted or unsubstituted pyridyl group, X represents a halogeno group, and R represents a C1-6 alkyl group. ａ (represents a C1-6 alkyl group) and Sodium hypochlorite and This includes carrying out chemical reactions in the presence of a base. Compound represented by formula (2): 【Chemistry 2】 (In formula (2), R １ , and Q represent the same things as those in equation (1). A method for manufacturing this product.

2. Compound represented by formula (3): 【Transformation 3】 (In formula (3), R １ (wherein Q represents a C1-6 alkyl group, and Q represents a hydrogen atom or a substituted or unsubstituted pyridyl group), Compound represented by formula (4): 【Chemistry 4】 (In formula (4), X represents a halogeno group) and The chemical reaction in the presence of a base or metal alkoxide, and The products of the aforementioned chemical reaction, Compound represented by formula (5): 【Transformation 5】 (In formula (5), R ａ (representing C1-6 alkyl groups) and The manufacturing method according to claim 1, further comprising obtaining a compound represented by formula (1) by a method including a chemical reaction.

3. Compounds represented by formula (2a1), formula (2a2), or formula (2a3): 【Transformation 6】 (In equations (2a1), (2a2), or (2a3), R １ (This represents a C1-6 alkyl group).

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