JP2011153115A - Aniline derivative, and method for producing the same - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide an aniline derivative efficiently producible of an amide derivative exhibiting outstanding effects in terms of pest-controlling activity, and to provide a method for producing the aniline derivative. <P>SOLUTION: The aniline derivative represented by formula (1) is provided, which is produced by reaction of a compound represented by formula (2) with a compound represented by chemical formula (3). In these formulas, R<SP>1</SP>and R<SP>2</SP>are each independently H, 1-6C alkyl or group of C(=O)R<SP>3</SP>(wherein, R<SP>3</SP>is H, 1-6C alkyl or optionally substituted phenyl); Y<SP>1</SP>is H, a chlorine atom, bromine atom or iodine atom; Y<SP>5</SP>is trifluoromethyl, pentafluoroethyl or trifluoromethoxy; Y<SP>2</SP>, Y<SP>3</SP>and Y<SP>4</SP>are each H; and X<SP>1</SP>and X<SP>2</SP>are each independently a chlorine atom, bromine atom or iodine atom. <P>COPYRIGHT: (C)2011,JPO&INPIT

Description

  The present invention relates to an aniline derivative and a method for producing the same.

  Various compounds have been disclosed as amide derivatives having a pest control action (see, for example, Patent Documents 1 to 3). An aniline derivative that can be an intermediate of an amide derivative similar to the amide derivative has been disclosed (for example, see Patent Document 4).

International Publication No. 2005/21488 Pamphlet International Publication No. 2005/73165 Pamphlet International Publication No. 2006/137376 Pamphlet JP 2004-161768 A

  An object of the present invention is to provide an aniline derivative that is an intermediate that enables efficient production of an amide derivative that exhibits an excellent pest control action, and a method for producing the same.

The present inventors have conducted extensive research to develop a novel method for producing amide derivatives described in International Publication No. 2005/21488, International Publication No. 2005/73165, and International Publication No. 2006/137376. As a result, a useful intermediate for producing such an amide derivative was found and the present invention was completed.
That is, the present invention is as follows.
<1> The following general formula (1)

(In General Formula (1), R ¹ and R ² are each independently a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, or a group represented by C (═O) R ³ (R ³ is a hydrogen atom, Y ¹ represents a hydrogen atom, a chlorine atom, a bromine atom, or an iodine atom, and Y ⁵ represents trifluoro. A methyl group, a pentafluoroethyl group, or a trifluoromethoxy group, Y ² and Y ^{4 each} represent a hydrogen atom, and X ¹ represents a chlorine atom, a bromine atom, or an iodine atom.
<2> The aniline derivative according to <1>, wherein X ¹ in the general formula (1) is a bromine atom.
<3> The following general formula (2)

(In General Formula (2), R ¹ and R ² are each independently a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, or a group represented by C (═O) R ³ (R ³ is a hydrogen atom, Y ¹ represents a hydrogen atom, a chlorine atom, a bromine atom, or an iodine atom, and Y ⁵ represents trifluoromethyl, and represents an alkyl group having 1 to 6 carbon atoms or an optionally substituted phenyl group. A compound represented by the following formula (3): a group, a pentafluoroethyl group, or a trifluoromethoxy group, and Y ² , Y ^3, and Y ⁴ represent a hydrogen atom.

(In General Formula (3), X ¹ and X ² each independently represents a chlorine atom, a bromine atom, or an iodine atom) and a compound represented by the following general formula (1 )

(In General Formula (1), R ¹ and R ² are each independently a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, or a group represented by C (═O) R ³ (R ³ is a hydrogen atom, Y ¹ represents a hydrogen atom, a chlorine atom, a bromine atom, or an iodine atom, and Y ⁵ represents trifluoromethyl, and represents an alkyl group having 1 to 6 carbon atoms or an optionally substituted phenyl group. Group, pentafluoroethyl group, or trifluoromethoxy group, Y ² and Y ^{4 each} represent a hydrogen atom, and X ¹ represents a chlorine atom, a bromine atom, or an iodine atom. Method.
<4> The method for producing an aniline derivative according to <3>, wherein X ¹ and X ² in the general formula (1) and the general formula (3) are bromine atoms.
<5> The following general formula (2a)

(In General Formula (2a), R ¹ and R ² are each independently a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, or a group represented by C (═O) R ³ (R ³ is a hydrogen atom, Y ^1a represents a hydrogen atom, Y ⁵ represents a trifluoromethyl group, a pentafluoroethyl group, or a trifluoro group, and an alkyl group having 1 to 6 carbon atoms or an optionally substituted phenyl group. A methoxy group, and Y ² , Y ³ and Y ^{4 each} represent a hydrogen atom.) And a compound represented by the following general formula (3)

(In the general formula (3), X ¹ and X ² each independently represents a chlorine atom, a bromine atom, or an iodine atom.), Which comprises reacting with a compound represented by the following general formula (1a)

(In General Formula (1a), R ¹ and R ² are each independently a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, or a group represented by C (═O) R ³ (R ³ is a hydrogen atom, Y ^1a represents a hydrogen atom, Y ⁵ represents a trifluoromethyl group, a pentafluoroethyl group, or a trifluoro group, and represents an alkyl group having 1 to 6 carbon atoms or an optionally substituted phenyl group. A methoxy group, Y ² and Y ^{4 each} represent a hydrogen atom, and X ¹ represents a chlorine atom, a bromine atom, or an iodine atom).
<6> The method for producing an aniline derivative according to <5>, wherein X ¹ and X ² in the general formula (1a) and the general formula (3) are bromine atoms.
<7> The following general formula (1a)

(In General Formula (1a), R ¹ and R ² are each independently a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, or a group represented by C (═O) R ³ (R ³ is a hydrogen atom, Y ^1a represents a hydrogen atom, Y ⁵ represents a trifluoromethyl group, a pentafluoroethyl group, or a trifluoro group, and represents an alkyl group having 1 to 6 carbon atoms or an optionally substituted phenyl group. A methoxy group, Y ² and Y ^{4 each} represent a hydrogen atom, and X ¹ represents a chlorine atom, a bromine atom, or an iodine atom), and a halogenating agent. The following general formula (1b)

(In General Formula (1b), R ¹ and R ² are each independently a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, or a group represented by C (═O) R ³ (R ³ is a hydrogen atom, Y ^1b represents a chlorine atom, a bromine atom, or an iodine atom, and Y ⁵ represents a trifluoromethyl group or a pentafluoro group, which represents a C 1-6 alkyl group or an optionally substituted phenyl group. An ethyl group or a trifluoromethoxy group, Y ² and Y ^{4 each} represent a hydrogen atom, and X ¹ represents a chlorine atom, a bromine atom, or an iodine atom.)
<8> The method for producing an aniline derivative according to <7>, wherein X ¹ in the general formula (1a) and the general formula (1b) is a bromine atom.
<9> The following general formula (2b)

(In General Formula (2b), R ¹ and R ² are each independently a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, or a group represented by C (═O) R ³ (R ³ is a hydrogen atom, Y ^1b represents a chlorine atom, a bromine atom, or an iodine atom, Y ⁵ represents a trifluoromethyl group, an alkyl group having 1 to 6 carbon atoms, or an optionally substituted phenyl group. A pentafluoroethyl group or a trifluoromethoxy group, and Y ² , Y ³ and Y ⁴ represent a hydrogen atom), and a compound represented by the following general formula (3):

(In General Formula (3), each of X ¹ and X ² independently represents a chlorine atom, a bromine atom, or an iodine atom.), Which comprises reacting with a compound represented by the following General Formula (1b)

(In General Formula (1b), R ¹ and R ² are each independently a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, or a group represented by C (═O) R ³ (R ³ is a hydrogen atom, Y ^1b represents a chlorine atom, a bromine atom, or an iodine atom, Y ⁵ represents a trifluoromethyl group, a penta group, or an alkyl group having 1 to 6 carbon atoms, or an optionally substituted phenyl group. A fluoroethyl group or a trifluoromethoxy group, Y ² and Y ^{4 each} represent a hydrogen atom, and X ¹ represents a chlorine atom, a bromine atom, or an iodine atom.)
<10> The method for producing an aniline derivative according to <9>, wherein X ¹ and X ² in the general formula (1b) and the general formula (3) are bromine atoms.

  ADVANTAGE OF THE INVENTION According to this invention, the aniline derivative which makes it possible to manufacture efficiently the amide derivative which shows the effect in pest control action, and its manufacturing method can be provided.

Hereinafter, the terms used in the general formulas of the present invention have the meanings described below in their definitions.
"Ca-Cb (a, b represents an integer of 1 or more)", for example, "C1-C3" means 1 to 3 carbon atoms, "C2-C6" Means having 2 to 6 carbon atoms.
“N-” means normal, “i-” means iso, “s-” means secondary, and “t-” means tertiary.

  “C 1-6 alkyl group” means, for example, methyl, ethyl, n-propyl, i-propyl, n-butyl, i-butyl, s-butyl, t-butyl, n-pentyl, i-pentyl, A linear or branched alkyl group having 1 to 6 carbon atoms such as neopentyl, 4-methyl-2-pentyl, n-hexyl, 3-methyl-n-pentyl and the like is represented.

Examples of the substituent in the optionally substituted phenyl group include a halogen atom, a C1-C6 alkyl group, a C1-C6 haloalkyl group, a C3-C9 cycloalkyl group, a C3-C9 halocycloalkyl group, and a C2-C6 alkenyl group. C2-C6 haloalkenyl group, C2-C6 alkynyl group, C2-C6 haloalkynyl group, C1-C6 alkoxy group, C1-C6 haloalkoxy group, C1-C6 alkylthio group, C1-C6 haloalkylthio group, C1-C6 Alkylsulfinyl group, C1-C6 haloalkylsulfinyl group, C1-C6 alkylsulfonyl group, C1-C6 haloalkylsulfonyl group, C2-C7 alkylcarbonyl group, C2-C7 haloalkylcarbonyl group, C2-C7 alkylcarbonyloxy group, C2-C7 Haloalkylcal Nyloxy group, C1-C6 alkylsulfonyloxy group, C1-C6 haloalkylsulfonyloxy group, C2-C7 alkoxycarbonyl group, C2-C7 haloalkoxycarbonyl group, C2-C7 alkylcarbonylamino group, C2-C7 haloalkylcarbonylamino group, C2-C7 alkoxycarbonylamino group, C2-C7 haloalkoxycarbonylamino group, C2-C7 alkylaminocarbonyl group, C2-C7 haloalkylaminocarbonyl group, C1-C6 alkylamino group, C1-C6 haloalkylamino group, C2-C6 Alkenylamino group, C2-C6 haloalkenylamino group, C2-C6 alkynylamino group, C2-C6 haloalkynylamino group, C3-C9 cycloalkylamino group, C3-C9 halocycloalkylamino group Group, C3-C7 alkenylaminocarbonyl group, C3-C7 haloalkenylaminocarbonyl group, C3-C7 alkynylaminocarbonyl group, C3-C7 haloalkynylaminocarbonyl group, C4-C10 cycloalkylaminocarbonyl group, C4-C10 halocyclo group Alkylaminocarbonyl group, amino group, carbamoyl group, sulfamoyl group, cyano group, nitro group, hydroxyl group, carboxyl group, pentafluorosulfanyl group, optionally substituted phenyl group, having a substituent A heterocyclic group which may have a substituent, a benzyl group which may have a substituent, a phenylcarbonyl group which may have a substituent, a phenylamino group which may have a substituent, and a substituent. Substituents selected from optionally substituted phenylcarbonylamino groups And when there are two or more substituents, each substituent may be the same or different.
In the present invention, each of the substituents may further have a substituent if possible, and examples of the substituent are the same as those of the optionally substituted phenyl group. is there.

  The aniline derivative of the present invention is represented by the following general formula (1).

In General Formula (1), R ¹ and R ² are each independently a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, or a group represented by C (═O) R ³ (R ³ is a hydrogen atom, carbon An alkyl group of 1 to 6 or a phenyl group which may be substituted).
Y ¹ represents a hydrogen atom, a chlorine atom, a bromine atom, or an iodine atom, Y ⁵ represents a trifluoromethyl group, a pentafluoroethyl group, or a trifluoromethoxy group, and Y ² and Y ⁴ represent a hydrogen atom. Show. X ¹ represents a chlorine atom, a bromine atom, or an iodine atom.

The compound represented by the general formula (1) in the present invention may contain one or more asymmetric carbon atoms or asymmetric centers in the structural formula, and two or more optical isomers exist. However, the present invention includes all of the optical isomers and a mixture containing them in an arbitrary ratio.
In addition, the compound represented by the general formula (1) and the like in the present invention may include two or more geometric isomers derived from a carbon-carbon double bond in the structural formula. Also included are all mixtures containing geometric isomers in any proportion.

Preferred substituents such as substituents in the aniline derivative represented by the general formula (1) of the present invention or combinations of atoms are as follows.
R ¹ and R ² are preferably hydrogen atoms, Y ¹ is preferably a hydrogen atom, bromine atom, or iodine atom, and Y ⁵ is preferably a trifluoromethyl group. X ¹ is preferably a bromine atom or an iodine atom, and more preferably a bromine atom.
R ¹ and R ² are hydrogen atoms, Y ¹ is a hydrogen atom, bromine atom, or iodine atom, Y ⁵ is a trifluoromethyl group, and X ¹ is a bromine atom or iodine atom. R ¹ and R ² are preferably hydrogen atoms, Y ¹ is a hydrogen atom, bromine atom, or iodine atom, Y ⁵ is a trifluoromethyl group, and X ¹ is bromine. More preferably it is an atom.
When the aniline derivative represented by the general formula (1) is in this mode, an amide derivative that is further excellent in pest control action can be produced more efficiently.

Although the manufacturing method of the aniline derivative of this invention and the compound used as the manufacturing intermediate which can be used suitably for this manufacturing method and its manufacturing method are shown below, this invention is not limited to these.
In the general formulas shown in the following production methods 1 to 3, R ¹ , R ² , Y ¹ , Y ² , Y ⁴ , Y ⁵ , and X ¹ are R ¹ in the general formula (1), R ² , Y ¹ , Y ² , Y ⁴ , Y ⁵ , and X ¹ are the same. Y ³ represents a hydrogen atom, and X ² represents a chlorine atom, a bromine atom or an iodine atom independently of X ¹ .

R ⁴ is an optionally substituted alkyloxycarbonyl group, an optionally substituted phenyloxycarbonyl group, an optionally substituted alkyl group, an optionally substituted alkylsulfonyl group, a substituted And an optionally substituted phenylsulfonyl group, an optionally substituted alkylcarbonyl group, or an optionally substituted benzoyl group.

  The alkyloxycarbonyl group which may be substituted, the phenyloxycarbonyl group which may be substituted, the alkyl group which may be substituted, the alkylsulfonyl group which may be substituted, the phenylsulfonyl which may be substituted The substituent in the group, the optionally substituted alkylcarbonyl group, and the optionally substituted benzoyl group is the same as the substituent in the optionally substituted phenyl group.

  The alkyl group in the alkyloxycarbonyl group which may be substituted, the alkyl group which may be substituted, the alkylsulfonyl group which may be substituted, and the alkylcarbonyl group which may be substituted is the carbon number described above. It is preferable that it is the same as that of the alkyl group of 1-6.

LG represents a functional group having a leaving ability such as a halogen atom, a hydroxyl group, and an acyloxy group.
Furthermore, the “halogen atom” represents a fluorine atom, a chlorine atom, a bromine atom or an iodine atom.

<Manufacturing method 1>
The production method of the aniline derivative represented by the general formula (1) of the present invention is represented by the following reaction formula (1). With such a configuration, the aniline derivative represented by the general formula (1) can be efficiently produced.

1- (i): General formula (2) + General formula (3) → General formula (1)
The aniline derivative represented by the general formula (1) can be produced by reacting the compound represented by the general formula (2) with the compound represented by the general formula (3).
This reaction is carried out in a solvent. Examples of the solvent include water, benzene, toluene, xylene, chlorobenzene, dichlorobenzene, and other halogenated aromatic hydrocarbons, hexane, cyclohexane, dichloromethane, chloroform, Optional halogenated aliphatic hydrocarbons such as carbon chloride, chain ethers or cyclic ethers such as diethyl ether, dioxane, tetrahydrofuran, 1,2-dimethoxyethane, t-butyl methyl ether, ethyl acetate, butyl acetate, etc. Esters, alcohols such as methanol and ethanol, ketones such as acetone, methyl isobutyl ketone and cyclohexanone, amides such as dimethylformamide and dimethylacetamide, sulfoxides such as dimethyl sulfoxide, tetra Sulfones such as Chirensuruhon, nitriles such as acetonitrile, can exhibit an inert solvent such as 1,3-dimethyl-2-imidazolidinone. These solvents can be used alone or in combination of two or more.

  It can also be carried out in a multiphase reaction medium of water and an organic solvent, and the organic solvent for the multiphase reaction medium is, for example, a halogenated aromatic such as benzene, toluene, xylene, chlorobenzene, dichlorobenzene. Hydrocarbons, hexane, cyclohexane, dichloromethane, chloroform, carbon tetrachloride and the like, optionally halogenated aliphatic hydrocarbons, diethyl ether, dioxane, tetrahydrofuran, 1,2-dimethoxyethane, t-butyl methyl ether, etc. Examples thereof include linear or cyclic ethers, esters such as ethyl acetate and butyl acetate, and ketones such as cyclohexanone, butanone and methyl isobutyl ketone.

When reacting in a multiphase reaction medium, it is advantageous to carry out the reaction in the presence of a phase transfer catalyst. Examples of the phase transfer catalyst include 18-crown-6, 12-crown-4, and dibenzo-18-crown. -6-, crown ethers such as dibenzo-12-crown-4-, cryptands such as cryptand [2.2.2], podands, polyglycol ether, tetra-n-butylammonium iodide, tetra-n - butylammonium bromide, tetra -n- butylammonium chloride, tri -n- butyl methyl bromide, tetra -n- butylammonium hydrogensulfate sulfate, trimethyl _-C 13 _{/ C 15} - alkyl ammonium chloride, trimethyl _-C 13 / C ₁₅ - alkyl ammonium bromide, Jibe Jill dimethyl ammonium methyl sulfate, dimethyl -C 12 _{/ C} 14 _- alkyl benzyl ammonium chloride, dimethyl -C 12 _{/ C} 14 _- alkyl benzyl ammonium bromide, triethylbenzylammonium chloride, methyl trioctyl ammonium chloride, trimethylbenzylammonium chloride, tetrakis Examples thereof include diethylaminophosphonium chloride, tetrakisdiethylaminophosphonium bromide, tetrakisdiethylaminophosphonium iodide, tris- [2- (2-methoxyethoxy) ethyl] amine, and compounds represented by the following formula (I).

(Cation ⁺ ) (anion ⁻ ) Formula (I)

In the formula (I), (cation ⁺ ) is a substituted quaternary ammonium or phosphonium cation, and (anion ⁻ ) is an anion of an organic acid or an inorganic salt.

This reaction is preferably carried out in the presence of a reducing agent and / or in the presence of light having a wavelength of 400 nm or less.
Suitable reducing agents are sulfur compounds with an average formal oxidation state of + III, + IV, and + V, and sulfur compounds in mixtures with metals having a standard reduction potential of 0 V or less. Specifically, for example, alkali metal dithionite such as sodium dithionite and potassium dithionite, or sulfur dioxide can be used.
Suitable metals are, for example, manganese, zinc and aluminum.
As a light source that generates light having a wavelength of 400 nm or less, a commonly used UV lamp can be used without particular limitation, and a high-pressure mercury lamp can be mentioned in particular.

  This reaction is preferably carried out in the presence of a base. Suitable bases include, for example, alkaline earth metals or alkali metal hydroxides such as sodium hydroxide, potassium hydroxide, sodium acetate, potassium acetate, calcium acetate, sodium carbonate, potassium carbonate, potassium bicarbonate, and sodium bicarbonate. , Acetate, phosphate, hydrogen phosphate, carbonate, bicarbonate, ammonium acetate such as ammonium acetate, ammonium carbonate, trimethylamine, triethylamine, tributylamine, diisopropylethylamine, tetramethylguanidine, N, N-dimethylaniline , Amines such as diazabicyclooctane (DABCO), diazabicyclononene (DBN), diazabicycloundecene (DBU), N-methylpiperidine, piperidine, pyridine, 2-, 3-, and 4-N, N-dimethyl It may indicate an aromatic nitrogen compound such as aminopyridine.

The molar ratio of the compound represented by the general formula (2) and the compound represented by the general formula (3) is 0.7 to 1.8.
The reaction temperature may be appropriately selected within the range of −10 ° C. to the reflux temperature of the solvent used under the reaction pressure. The reaction pressure may be appropriately selected within the range of 0.5 to 100 bar.
Furthermore, the reaction time may be appropriately selected within the range of several minutes to 96 hours.

  The method for producing an aniline derivative represented by the general formula (1b) in the present invention is preferably represented by the following reaction formula (2). The details of the following reaction formula (2) are the same as the above-described reaction formula (1), and the preferred embodiments are also the same.

Y ^1b represents a chlorine atom, a bromine atom or an iodine atom.

  Moreover, it is also preferable that the manufacturing method of the aniline derivative represented by General formula (1a) in this invention is represented by following Reaction formula (3). The details of the following reaction formula (3) are the same as the above-described reaction formula (1), and the preferred embodiments are also the same.

Y ^1a represents a hydrogen atom.

1- (ii): General formula (1a) → General formula (1b)
Moreover, the aniline derivative represented by the said General formula (1b) can be efficiently manufactured by making the aniline derivative represented by the said General formula (1a) react, and a halogenating agent.
Examples of the method of reacting the aniline derivative represented by the general formula (1a) with the halogenating agent include the methods described in Experimental Chemistry Course 19, pages 424 to 427 and 466 to 467. Specific examples of the halogenating agent include chlorine, bromine, iodine, sulfuryl chloride, N-chlorosuccinimide, N-bromosuccinimide, N-iodosuccinimide, iodine monochloride, 1,3-diiodo-5,5,- Dimethylhydantoin and the like can be shown.

<Manufacturing method 2>
From the aniline derivative represented by the general formula (1b) in the present invention, the aniline derivative represented by the general formula (4) can be produced as shown below.

Y ^1b represents a chlorine atom, a bromine atom or an iodine atom.
2- (i): General formula (1b) → General formula (4)
The aniline derivative represented by the general formula (4) can be produced by reacting the aniline derivative represented by the general formula (1b) with a suitable fluorinating agent in a suitable solvent or without a solvent. .

  Any solvent may be used as long as it does not significantly inhibit the progress of this reaction. For example, aliphatic hydrocarbons such as hexane, cyclohexane, and methylcyclohexane, aromatic hydrocarbons such as benzene, toluene, and xylene, dichloromethane, chloroform, and the like. Halogenated hydrocarbons such as carbon tetrachloride and 1,2-dichloroethane, chain or cyclic ethers such as diethyl ether, dioxane, tetrahydrofuran and 1,2-dimethoxyethane, esters such as ethyl acetate and butyl acetate, Ketones such as acetone, methyl isobutyl ketone, cyclohexanone, methyl ethyl ketone, nitriles such as acetonitrile, propionitrile, 1,3-dimethyl-2-imidazolidinone, sulfolane, dimethyl sulfoxide, N, N-dimethylformamide , N- methylpyrrolidone, N, can show aprotic polar solvents such as N- dimethylacetamide, these solvents may be used alone or as a mixture of two or more.

As the fluorinating agent, 1,1,2,2-tetrafluoroethyldiethylamine, 2-chloro-1,1,2-trifluoroethyldiethylamine, trifluorodiphenylphosphorane, difluorotriphenylphosphorane, fluoroformate esters, Sulfur tetrafluoride, potassium fluoride, potassium hydrogen fluoride, cesium fluoride, rubidium fluoride, sodium fluoride, lithium fluoride, antimony fluoride (III), antimony fluoride (V), zinc fluoride, fluoride Cobalt, lead fluoride, copper fluoride, mercury fluoride (II), silver fluoride, silver fluoroborate, thallium fluoride (I), molybdenum fluoride (VI), arsenic fluoride (III), bromine fluoride, Selenium tetrafluoride, tris (dimethylamino) sulfonium difluorotrimethylsilicate, sodium hexafluorosilicate, quaternary fluoride Monium, (2-chloroethyl) diethylamine, diethylaminosulfur trifluoride, morpholinosulfur trifluoride, silicon tetrafluoride, hydrogen fluoride, hydrofluoric acid, hydrogen fluoride pyridine complex, hydrogen fluoride triethylamine complex, fluoride Hydrogen salts, bis (2-methoxyethyl) aminosulfur trifluoride, 2,2-difluoro-1,3-dimethyl-2-imidazolidinone, iodine pentafluoride, tris (diethylamino) phosphonium-2,2,3 3,4,4-hexafluoro-cyclobutane ylide, triethylammonium hexafluorocyclobutane ylide, hexafluoropropene and the like can be shown. These fluorinating agents can be used alone or in combination of two or more.
These fluorinating agents may be appropriately selected and used as a solvent in the range of 1 to 10-fold molar equivalent with respect to the compound represented by the general formula (1b).

An additive may be used. Examples of the additive include crown ethers such as 18-crown-6, phase transfer catalysts such as tetraphenylphosphonium salts, non-base salts such as calcium fluoride and calcium chloride, oxidation Metal oxides such as mercury, ion exchange resins and the like can be shown, and these additives can be used not only in the reaction system but also as a pretreatment agent for the fluorinating agent.
What is necessary is just to select reaction temperature suitably in the range of the reflux temperature of the solvent to be used from -80 degreeC. The reaction time may be appropriately selected within the range of several minutes to 96 hours.

<Manufacturing method 3>
Among the aniline derivatives represented by the general formula (1) in the present invention, from the aniline derivative represented by the following general formula (5) in which R ¹ and R ² are hydrogen atoms, the general formula ( An aniline derivative represented by 6) can be produced.

3- (i): General formula (5) + General formula (7) → General formula (8)
By reacting the compound having the leaving group represented by the general formula (7) with the compound represented by the general formula (5) in an appropriate solvent or without a solvent, the compound represented by the general formula (8) is represented. Compounds can be produced. In this step, an appropriate base can be used.

  Any solvent that does not significantly inhibit the progress of this reaction may be used. For example, water, aromatic hydrocarbons such as benzene, toluene and xylene, halogenated hydrocarbons such as dichloromethane, chloroform and carbon tetrachloride, chain such as diethyl ether, dioxane, tetrahydrofuran and 1,2-dimethoxyethane or Cyclic ethers, esters such as ethyl acetate and butyl acetate, alcohols such as methanol and ethanol, ketones such as acetone, methyl isobutyl ketone and cyclohexanone, amides such as dimethylformamide and dimethylacetamide, nitriles such as acetonitrile, An inert solvent such as 1,3-dimethyl-2-imidazolidinone can be indicated. These solvents can be used alone or in combination of two or more.

Examples of the base include organic bases such as triethylamine, tri-n-butylamine, pyridine, and 4-dimethylaminopyridine, alkali metal hydroxides such as sodium hydroxide and potassium hydroxide, sodium hydrogen carbonate, and potassium carbonate. Carbonates, phosphates such as dipotassium monohydrogen phosphate and trisodium phosphate, alkali metal hydrides such as sodium hydride, alkali metal alcoholates such as sodium methoxide and sodium ethoxide, lithium diisopropylamide, etc. Lithium amides can be shown.
These bases may be appropriately selected and used within a range of 0.01 to 5 molar equivalents relative to the compound represented by the general formula (7).

  What is necessary is just to select reaction temperature suitably in the range of the reflux temperature of the solvent to be used from -20 degreeC. The reaction time may be appropriately selected within the range of several minutes to 96 hours.

  Among the compounds represented by the general formula (7), a carboxylic acid halide derivative or a sulfonic acid halide derivative can be easily produced from a carboxylic acid or a sulfonic acid by a conventional method using a halogenating agent. Examples of the halogenating agent include halogenating agents such as thionyl chloride, thionyl bromide, phosphorus oxychloride, oxalyl chloride, and phosphorus trichloride.

  On the other hand, it is possible to produce the compound represented by the general formula (8) from the carboxylic acid derivative or the sulfonic acid derivative and the compound represented by the general formula (5) without using a halogenating agent. As the method, for example, Chem. Ber. Vol. 103, page 788 (1970). Specifically, a method using an additive such as 1-hydroxybenzotriazole as appropriate and using a condensing agent such as N, N′-dicyclohexylcarbodiimide can be shown. Examples of other condensing agents used in this case include 1-ethyl-3- (3-dimethylaminopropyl) carbodiimide, 1,1'-carbonylbis-1H-imidazole, and the like.

  Moreover, as another method for producing the compound represented by the general formula (8), a mixed acid anhydride method using chloroformates can also be shown. For example, J. et al. Am. Chem. Soc. Vol. 89, page 5012 (1967), and the compound represented by the general formula (8) can be produced. Examples of the chloroformate used in this case include isobutyl chloroformate and isopropyl chloroformate. In addition to the chloroformates, diethylacetyl chloride, trimethylacetyl chloride and the like can be used.

  Both the method using a condensing agent and the mixed acid anhydride method are not limited to the solvent, reaction temperature, and reaction time described in the literature. As the solvent, an inert solvent that does not significantly inhibit the progress of the reaction may be used as appropriate. Further, the reaction temperature and reaction time may be appropriately selected according to the progress of the reaction.

3- (ii): General formula (8) → General formula (9)
The compound represented by the general formula (9) can be produced by reacting the compound represented by the general formula (8) with a suitable fluorinating agent in a suitable solvent or without a solvent.
As the solvent, those exemplified in 2- (i) can be used. Moreover, what was illustrated to 2- (i) can be used also about a fluorinating agent. The reaction temperature, reaction time, etc. can also follow the example of 2- (i).

3- (iii): General formula (9) → General formula (6)
For example, by following the method described in pages 218 to 287 of Protective Groups in Organic Synthesis (John Wiley and Sons Inc.), the aniline derivative represented by the general formula (6) from the compound represented by the general formula (9) Can be manufactured.
Conditions such as the reaction solvent are not limited to those described in the literature, and an inert solvent that does not significantly inhibit the progress of the reaction may be used as appropriate. Further, the reaction temperature and reaction time may be appropriately selected according to the progress of the reaction.

3- (iv): General formula (9) → General formula (10)
For example, according to the method described in Experimental Chemistry Lecture 19 (4th edition, Maruzen), pages 424 to 427 and 466 to 467, the compound represented by the general formula (9) is reacted with the halogenating agent (general formula (9)). The compound represented by 10) can be produced. As the halogenating agent, for example, those exemplified in 1- (ii) can be used.

3- (v): General formula (10) → General formula (6)
For example, by following the method described in pages 218 to 287 of Protective Groups in Organic Synthesis (John Wiley and Sons Inc.), the aniline derivative represented by the general formula (6) from the compound represented by the general formula (10) Can be manufactured.
Conditions such as the reaction solvent are not limited to those described in the literature, and an inert solvent that does not significantly inhibit the progress of the reaction may be used as appropriate. Further, the reaction temperature and reaction time may be appropriately selected according to the progress of the reaction.

In all the production methods shown above, the target product may be isolated from the reaction system according to a conventional method after completion of the reaction. If necessary, it can be purified by recrystallization, column chromatography, distillation or the like. can do. Moreover, it is also possible to use for the next reaction process, without isolating a target object from a reaction system.
The aniline derivative represented by the general formula (1) obtained by the present invention is an extremely useful production intermediate in a method for producing an amide derivative that exhibits a superior pest control action.

The following examples explain typical examples of the present invention, but the present invention is not limited thereto. The chemical shift value of ¹ H-NMR is a value using tetramethylsilane as an internal reference material unless otherwise specified. Unless otherwise specified, “%” is based on mass.

<Example 1>
Preparation of 2-trifluoromethyl-4- (1-bromo-1,1,2,3,3,3-hexafluoropropan-2-yl) aniline

5.00 g (31.0 mmol) of 2- (trifluoromethyl) aniline, 0.590 g (1.74 mmol) of tetrabutylammonium hydrogen sulfate, 1.35 g (6.20 mmol) of 80% sodium hydrosulfite, and 75. After charging a mixed solution of 0 ml and water 75.0 ml, the pH was adjusted to 5 with a 10% aqueous sodium carbonate solution. While adjusting the reaction solution to pH 5 with 10% aqueous sodium carbonate solution, 17.5 ml of 1,3-dibromo-1,1,2,3,3,3-hexafluoropropane 17.3 g (55.8 mmol) of ethyl acetate After the solution was added dropwise over 30 minutes, 0.680 g (3.10 mmol) of 80% sodium hydrosulfite was added in 7 portions every 30 minutes. After the divided addition, the reaction solution was stirred at room temperature for 5 hours. After separation, the organic layer was washed successively with 1N hydrochloric acid and saturated aqueous sodium hydrogen carbonate solution and dried over anhydrous magnesium sulfate, and the solvent was distilled off under reduced pressure. The resulting residue was treated with an ion exchange resin to remove 2- (trifluoromethyl) aniline and then purified by silica gel column chromatography (developing solvent; hexane) to produce the title compound.
¹ H-NMR (CDCl ₃ , ppm) δ 4.48 (2H, broadcast-s), 6.80 (1H, d, J = 8.8 Hz), 7.50 (1H, d, J = 8.8 Hz) , 7.64 (1H, s).

<Example 2>
Preparation of 2-iodo-6-trifluoromethyl-4- (1-bromo-1,1,2,3,3,3-hexafluoropropan-2-yl) aniline

1.21 g (3.10 mmol) of 2-trifluoromethyl-4- (1-bromo-1,1,2,3,3,3-hexafluoropropan-2-yl) aniline obtained in Example 1 After adding 0.320 g (3.26 mmol) of concentrated sulfuric acid to 10 ml of ethanol solution, 1.05 g (4.65 mmol) of N-iodosuccinimide was added and stirred at 60 ° C. for 2 hours. The reaction solution was stirred at the same temperature for 9 hours while adding 0.350 g (1.55 mmol) of N-iodosuccinimide three times. The reaction mixture was cooled to room temperature, water and ethyl acetate were added, and the organic layer was washed with water and saturated brine. The organic layer was dried over anhydrous magnesium sulfate, the solvent was distilled off under reduced pressure, and the resulting residue was purified by silica gel column chromatography (developing solvent; hexane) to give 1.41 g of the title compound (yield 88%). ) Was manufactured.
¹ H-NMR (CDCl ₃ , ppm) δ 5.03 (2H, broadcast-s), 7.64 (1H, s), 7.99 (1H, s).
¹⁹ F-NMR (CDCl ₃ , ppm) δ-57.1 (1F), -59.6 (1F), -64.0 (3F), -72.9 (3F), -171.2 (1F) .

<Reference Example 1>
2-Fluoro-3- (4-fluoro-N-methylbenzamide) -N- (2-iodo-4- (1-bromo-1,1,2,3,3,3-hexafluoropropan-2-yl) ) -6- (Trifluoromethyl) phenyl) benzamide

(Reference Example 1-1)
Preparation of methyl 2-chloro-3-nitrobenzoate

544 g (2.70 mol) of 2-chloro-3-nitrobenzoic acid was suspended in 3425 ml of methanol, 109 ml of concentrated sulfuric acid was charged, and the mixture was heated to reflux for 6 hours. After cooling to room temperature, the solvent was distilled off under reduced pressure, and the resulting residue was charged into a saturated aqueous sodium bicarbonate solution. The precipitated solid was filtered and washed with water. The obtained solid was dissolved in ethyl acetate, washed with saturated brine, and dried over anhydrous sodium sulfate. The solvent was distilled off under reduced pressure, and the resulting residue was washed with n-hexane to produce 543 g (yield 93%) of the title compound.
¹ H-NMR (CDCl ₃ , ppm) δ 3.98 (3H, s), 7.46-7.50 (1H, m), 7.83-7.86 (1H, m), 7.94-7 .98 (1H, m).

(Reference Example 1-2)
Preparation of methyl 2-fluoro-3-nitrobenzoate

Under a nitrogen stream, 499 g (3.19 mol) of cesium fluoride was charged into a flask equipped with a stirrer, and stirred at 110 ° C. for 1 hour under stirring. Into this, 229 g (1.06 mol) of methyl 2-chloro-3-nitrobenzoate obtained in Reference Example 1-1 and 2000 ml of N, N-dimethylformamide were charged and stirred at 140 ° C. for 1 hour. After allowing to cool to room temperature, the reaction solution is filtered, and the residue obtained by evaporating the solvent under reduced pressure is poured into water. After stirring for a while, the precipitated solid is collected by filtration and dried under reduced pressure to give the title compound. 160 g (76% yield) were produced.
_{^{1 H-NMR (CDCl 3,}} ppm) δ3.99 (3H, s), 7.36-7.40 (1H, m), 8.14-8.25 (2H, m).

(Reference Example 1-3)
Preparation of methyl 3-amino-2-fluorobenzoate hydrochloride

9.10 g (0.0460 mol) of 2-fluoro-3-nitrobenzoic acid methyl ester obtained in Reference Example 1-2, 10% hydrochloric acid / methanol 25 ml, methanol 60 ml, 5% palladium / carbon (50% wet product) 2.70 g was charged and hydrogenated at room temperature. After completion of the reaction, the catalyst was filtered, the solvent was distilled off under reduced pressure, and the resulting residue was washed with diisopropyl ether to produce 8.01 g (yield 85%) of the title compound.
¹ H-NMR (DMSO-d ₆ , ppm) δ 3.86 (3H, s), 7.21-7.25 (1H, m), 7.27 (3H, broadcast-s), 7.42-7 .53 (2H, m).

(Reference Example 1-4)
Preparation of methyl 2-fluoro-3- (4-fluorobenzamido) benzoate

44.6 g (0.213 mol) of methyl 3-amino-2-fluorobenzoate obtained in Reference Example 1-3 was suspended in 446 ml of methylene chloride, and 39.1 g (0.489 mol) of pyridine was added dropwise. Under cooling, 38.2 g (0.234 mol) of p-fluorobenzoic acid chloride was added dropwise to the reaction solution and stirred overnight at room temperature. After completion of the reaction, the reaction solution was washed successively with 1N aqueous hydrochloric acid solution, saturated aqueous sodium hydrogen carbonate and saturated brine, and dried over anhydrous sodium sulfate. The solvent was distilled off under reduced pressure and the resulting residue was washed with n-hexane / ethyl acetate = 4/1 to produce 61.9 g (yield 97%) of the title compound.
¹ H-NMR (CDCl ₃ , ppm) δ 3.95 (3H, s), 7.17-7.27 (3H, m), 7.66-7.70 (1H, m), 7.89-7 .94 (2H, m), 8.11 (1H, broadcast-s), 8.63-8.68 (1H, m).

(Reference Example 1-5)
Preparation of methyl 2-fluoro-3- (4-fluoro-N-methylbenzamide) benzoate

59.0 g (0.203 mol) of methyl 2-fluoro-3- (4-fluorobenzamido) benzoate obtained in Reference Example 1-4 was dissolved in 1180 ml of acetonitrile, and 39.1 g (0.304 mol) of dimethyl sulfate was obtained. Potassium hydroxide 16.0 g (0.243 mol) was sequentially charged, and then stirred at 60 ° C. for 30 minutes. After cooling to room temperature, the solvent was distilled off under reduced pressure, ethyl acetate and n-hexane were added to the resulting residue, washed with water, and dried over anhydrous sodium sulfate. The residue obtained by distilling off the solvent under reduced pressure was washed with n-hexane to produce 61.8 g (yield 76%) of the title compound.
¹ H-NMR (CDCl ₃ , ppm) δ 3.42 (3H, s), 3.88 (3H, s), 6.86-6.90 (2H, m), 7.09-7.13 (1H M), 7.32-7.38 (3H, m), 7.78-7.82 (1H, m).

(Reference Example 1-6)
Preparation of 2-fluoro-3- (4-fluoro-N-methylbenzamido) benzoic acid

38.5 g (0.126 mol) of methyl 2-fluoro-3- (4-fluoro-N-methylbenzamide) benzoate obtained in Reference Example 1-5 was added to 192 ml of methanol and dissolved at 65 ° C. To this was added 192 ml of an aqueous solution of 7.28 g (0.177 mol) of sodium hydroxide, and the mixture was stirred at the same temperature for 1 hour. After the reaction, methanol was distilled off under reduced pressure, and dichloromethane and water were added to the obtained aqueous solution for extraction and liquid separation. The aqueous layer was further washed with dichloromethane and separated, and then the aqueous layer was acidified with 6N hydrochloric acid to obtain crystals. The obtained crystals were washed with water and dried to produce 36.7 g (yield 96%) of the title compound.
¹ H-NMR (CDCl ₃ , ppm) δ 3.45 (3H, s), 6.87-6.91 (2H, m), 7.10-7.18 (1H, m), 7.30-7 .37 (3H, m), 7.87-7.92 (1H, m). No proton detected in carboxylic acid.

(Reference Example 1-7)
2-Fluoro-3- (4-fluoro-N-methylbenzamide) -N- (2-iodo-4- (1-bromo-1,1,2,3,3,3-hexafluoropropan-2-yl) ) -6- (Trifluoromethyl) phenyl) benzamide

0.230 g (0.770 mmol) of 2-fluoro-3- (4-fluoro-N-methylbenzamide) benzoic acid obtained in Reference Example 1-6 and 0.460 g (3.85 mmol) of thionyl chloride were added to 5 ml of dehydrated toluene. And stirred at 90 ° C. for 1 hour. After the toluene was distilled off under reduced pressure, the resulting residue was dissolved in 1 ml of dehydrated 1,3-dimethyl-2-imidazolidinone, and 2-iodo-6-trifluoromethyl-4- ( 1-bromo-1,1,2,3,3,3-hexafluoropropan-2-yl) aniline 0.300 g (0.580 mmol), triethylamine 0.110 g (1.04 mmol), N, N-dimethylamino After adding 0.0900 g (0.700 mmol) of pyridine to 1 ml of dehydrated 1,3-dimethyl-2-imidazolidinone, the mixture was stirred at room temperature for 30 minutes and then stirred at 70 ° C. for 7 hours. After cooling to room temperature, water and ethyl acetate were added to the reaction solution, and the organic layer was washed successively with 1N hydrochloric acid, saturated aqueous sodium hydrogen carbonate solution and saturated brine, and dried over anhydrous sodium sulfate. The filtrate was evaporated under reduced pressure, and the resulting residue was purified by silica gel column chromatography (developing solvent; hexane: ethyl acetate = 4: 1) to produce 0.230 g (yield 50%) of the title compound. .
¹ H-NMR (CDCl ₃ , ppm) δ3.50 (3H, s), 6.88-6.93 (2H, m), 7.28-7.35 (3H, m), 7.46 (1H , T, J = 7.3 Hz), 7.93 (1H, s), 8.01-8.08 (2H, m), 8.34 (1H, s).

2-Fluoro-3- (4-fluoro-N-methylbenzamide) -N- (2-iodo-4), which is an amide derivative produced using the aniline derivative represented by the general formula (1) as an intermediate -(1-Bromo-1,1,2,3,3,3-hexafluoropropan-2-yl) -6- (trifluoromethyl) phenyl) benzamide showed excellent effects on pest control action.

Claims (5)

The following general formula (1)

(In General Formula (1), R ¹ and R ² are each independently a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, or a group represented by C (═O) R ³ (R ³ is a hydrogen atom, Y ¹ represents a hydrogen atom, a chlorine atom, a bromine atom, or an iodine atom, and Y ⁵ represents a trifluoromethyl group, which represents an alkyl group having 1 to 6 carbon atoms, or an optionally substituted phenyl group. , A pentafluoroethyl group, or a trifluoromethoxy group, Y ² and Y ^{4 each} represent a hydrogen atom, and X ¹ represents a bromine atom. The following general formula (2)

(In General Formula (2), R ¹ and R ² are each independently a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, or a group represented by C (═O) R ³ (R ³ is a hydrogen atom, Y ¹ represents a hydrogen atom, a chlorine atom, a bromine atom, or an iodine atom, and Y ⁵ represents trifluoromethyl, and represents an alkyl group having 1 to 6 carbon atoms or an optionally substituted phenyl group. A compound represented by the following formula (3): a group, a pentafluoroethyl group, or a trifluoromethoxy group, and Y ² , Y ^3, and Y ⁴ represent a hydrogen atom.

(In the general formula (3), X ¹ and X ² represent a bromine atom.), Which comprises reacting with a compound represented by the following general formula (1)

(In General Formula (1), R ¹ and R ² are each independently a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, or a group represented by C (═O) R ³ (R ³ is a hydrogen atom, Y ¹ represents a hydrogen atom, a chlorine atom, a bromine atom, or an iodine atom, and Y ⁵ represents trifluoromethyl, and represents an alkyl group having 1 to 6 carbon atoms or an optionally substituted phenyl group. Group, a pentafluoroethyl group, or a trifluoromethoxy group, Y ² and Y ^{4 each} represent a hydrogen atom, and X ¹ represents a bromine atom. The following general formula (2a)

(In General Formula (2a), R ¹ and R ² are each independently a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, or a group represented by C (═O) R ³ (R ³ is a hydrogen atom, Y ^1a represents a hydrogen atom, Y ⁵ represents a trifluoromethyl group, a pentafluoroethyl group, or a trifluoromethoxy group, which represents an alkyl group having 1 to 6 carbon atoms or an optionally substituted phenyl group. And a compound represented by the following general formula (3): Y ² , Y ³ and Y ⁴ represent a hydrogen atom.

(In the general formula (3), X ¹ and X ^{2 each} represent a bromine atom.), Which comprises reacting with a compound represented by the following general formula (1a)

(In General Formula (1a), R ¹ and R ² are each independently a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, or a group represented by C (═O) R ³ (R ³ is a hydrogen atom, Y ^1a represents a hydrogen atom, Y ⁵ represents a trifluoromethyl group, a pentafluoroethyl group, or a trifluoromethoxy group, and represents an alkyl group having 1 to 6 carbon atoms or an optionally substituted phenyl group. And Y ² and Y ^{4 each} represent a hydrogen atom, and X ¹ represents a bromine atom.) The following general formula (1a)

(In General Formula (1a), R ¹ and R ² are each independently a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, or a group represented by C (═O) R ³ (R ³ is a hydrogen atom, Y ^1a represents a hydrogen atom, Y ⁵ represents a trifluoromethyl group, a pentafluoroethyl group, or a trifluoromethoxy group, and represents an alkyl group having 1 to 6 carbon atoms or an optionally substituted phenyl group. Wherein Y ² and Y ^{4 each} represent a hydrogen atom, and X ¹ represents a bromine atom) and a halogenating agent, and the following general formula (1b)

(In General Formula (1b), R ¹ and R ² are each independently a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, or a group represented by C (═O) R ³ (R ³ is a hydrogen atom, Y ^1b represents a chlorine atom, a bromine atom, or an iodine atom, Y ⁵ represents a trifluoromethyl group, a penta group, or an alkyl group having 1 to 6 carbon atoms, or an optionally substituted phenyl group. A fluoroethyl group or a trifluoromethoxy group, Y ² and Y ^{4 each} represent a hydrogen atom, and X ¹ represents a bromine atom.) The following general formula (2b)

(In General Formula (2b), R ¹ and R ² are each independently a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, or a group represented by C (═O) R ³ (R ³ is a hydrogen atom, Y ^1b represents a chlorine atom, a bromine atom, or an iodine atom, and Y ⁵ represents a trifluoromethyl group or a pentafluoro group, which represents a C 1-6 alkyl group or an optionally substituted phenyl group. An ethyl group or a trifluoromethoxy group, Y ² , Y ³ and Y ⁴ represent a hydrogen atom), and a compound represented by the following general formula (3):

(In the general formula (3), X ¹ and X ^{2 each} represent a bromine atom.), Which comprises reacting with a compound represented by the following general formula (1b)

(In General Formula (1b), R ¹ and R ² are each independently a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, or a group represented by C (═O) R ³ (R ³ is a hydrogen atom, Y ^1b represents a chlorine atom, a bromine atom, or an iodine atom, Y ⁵ represents a trifluoromethyl group, an alkyl group having 1 to 6 carbon atoms, or an optionally substituted phenyl group. A pentafluoroethyl group or a trifluoromethoxy group, Y ² and Y ^{4 each} represent a hydrogen atom, and X ¹ represents a bromine atom.