JP2005200366A - Method for producing tetrahydronaphthalene and naphthalene derivative, and production intermediate - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a simple method for synthesizing a tetrahydronaphthalene derivative and a naphthalene derivative. <P>SOLUTION: Vinyl ethers represented by general formula (2) are reacted in the presence of an acid catalyst to cyclize the vinyl ethers and to produce a dihydronaphthalene derivative represented by general formula (3), and the dihydronaphthalene derivative is reduced by hydrogen or cyclized so as to form an aromatic ring to produce the tetrahydronaphthalene derivative represented by general formula (4) or the naphthalene derivative represented by general formula (5). By the invention, a fluoronaphthalene derivative or a fluorotetrahydronaphthalene derivative of which the production is difficult can be efficiently produced. <P>COPYRIGHT: (C)2005,JPO&NCIPI

Description

  The present invention relates to a process for producing tetrahydronaphthalene and naphthalene derivatives useful as production intermediates for liquid crystal compounds, and production intermediates thereof.

  Tetrahydronaphthalene and naphthalene derivatives are used in various applications as pharmaceuticals, agricultural chemicals, electronic materials, chemicals, etc., or as raw materials and synthetic intermediates thereof, and are particularly important as liquid crystals and liquid crystal raw materials.

  As a production method thereof, the Grignard reagent (7) and the tetralone derivative (8) are reacted and then dehydrated, and the resulting dihydronaphthalene derivative (9) is hydrogenated and reduced to a tetrahydronaphthalene derivative (4) or aromatized. Thus, a method for synthesizing a naphthalene derivative (5) is known (see Patent Document 1). However, this method has limitations on the Grignard reagent that can be used, and it is difficult to produce the corresponding Grignard reagent, particularly when A is a cyclohexyl group.

さらに、テトラロン誘導体（１０）は以下のように製造可能であるが、多工程を要する。

Furthermore, the tetralone derivative (10) can be produced as follows, but requires a number of steps.

このため、目的の一般式（４）又は（５）で表される化合物を製造するにあたり、一般式（１０）で表される化合物から１０工程を要することになる。

For this reason, in order to produce the target compound represented by the general formula (4) or (5), 10 steps are required from the compound represented by the general formula (10).

  Dihydronaphthalene derivatives can also be converted to hydroxy ester by benzyl ketone by rehomatoski reaction, dehydrated and reduced, and then hydrolyzed to carboxylic acid, further converted to carboxylic acid, and then subjected to Friedel-Crafts reaction in the molecule. A method for synthesizing is known. However, this method also has a problem that the reaction route is long (see Non-Patent Document 1).

従って、テトラヒドロナフタレン誘導体及びナフタレン誘導体のより簡便な合成方法が望まれていた。

Therefore, a simpler method for synthesizing tetrahydronaphthalene derivatives and naphthalene derivatives has been desired.

Japanese Patent Application No. 2002-213847 M. Cereghetti, Helvetica Chimica Acta, (Germany), 1982, 65, 4, p. 1319

  The problem to be solved is to provide a simple method for synthesizing tetrahydronaphthalene derivatives and naphthalene derivatives.

  In order to solve the above-mentioned problems, the present invention has been intensively studied. As a result, the general formula (1)

(In the formula, R ¹ is an alkyl group which may contain a linear, branched or cyclic part having 1 to 20 carbon atoms, an alkoxyl group which may contain a linear, branched or cyclic part having 1 to 20 carbon atoms, carbon An alkoxylalkyl group which may contain a straight, branched or cyclic part having 2 to 20 atoms, an alkenyl group which may contain a straight, branched or cyclic part having 2 to 20 carbon atoms, or a straight chain having 2 to 20 carbon atoms. Represents an alkenyloxy group which may contain a chain, a branch or a cyclic part, which may be substituted by an alkoxyl group having 1 to 10 carbon atoms or a halogen atom having 1 to 30 carbon atoms, and A is trans-1,4- A cyclohexylene group, a 1,4-phenylene group in which any one or more hydrogen atoms may be substituted by a halogen atom, trans-2, in which any one or more hydrogen atoms may be substituted by a halogen atom, 6-decahydronaphthyl group or any one or more A hydrogen atom is a 2,6-naphthyl group optionally substituted by a halogen atom, X represents a hydrogen atom or a fluorine atom, and n represents 1 or 2. 6)

（式中、R²は炭素原子数1〜20の直鎖、分岐又は環状部を含んでよいアルキル基、炭素原子数2〜20の直鎖、分岐又は環状部を含んでよいアルコキシルアルキル基、炭素原子数2〜20の直鎖、分岐又は環状部を含んでよいアルケニル基又は炭素原子数2〜20の直鎖、分岐又は環状部を含んでよいアルケニルオキシ基を表し、これらは炭素数1〜10のアルコキシル基又は1〜30個のハロゲン原子によって置換されていてもよい。）で表されるリンイリドと反応させることにより一般式（２）

(In the formula, R ² is an alkyl group which may contain a linear, branched or cyclic part having 1 to 20 carbon atoms, an alkoxylalkyl group which may contain a linear, branched or cyclic part having 2 to 20 carbon atoms, An alkenyl group which may contain a straight, branched or cyclic part having 2 to 20 carbon atoms or an alkenyloxy group which may contain a straight, branched or cyclic part having 2 to 20 carbon atoms, which has 1 carbon atom (Optionally substituted by 10 to 10 alkoxyl groups or 1 to 30 halogen atoms)), by reacting with phosphorus ylide represented by the general formula (2)

(In the formula, R ¹ is an alkyl group which may contain a linear, branched or cyclic part having 1 to 20 carbon atoms, an alkoxyl group which may contain a linear, branched or cyclic part having 1 to 20 carbon atoms, carbon An alkoxylalkyl group which may contain a straight, branched or cyclic part having 2 to 20 atoms, an alkenyl group which may contain a straight, branched or cyclic part having 2 to 20 carbon atoms, or a straight chain having 2 to 20 carbon atoms. Represents an alkenyloxy group which may contain a chain, a branch or a cyclic part, which may be substituted by an alkoxyl group having 1 to 10 carbon atoms or a halogen atom having 1 to 30 carbon atoms, and R ² has 1 to Alkyl group which may contain 20 straight chain, branched or cyclic part, straight chain having 2 to 20 carbon atoms, alkoxylalkyl group which may contain branched or cyclic part, straight chain, branched or 2 to 20 carbon atoms An alkenyl group which may contain a cyclic part or a straight chain, branched or ring having 2 to 20 carbon atoms Represents an alkenyloxy group which may contain a moiety, which may be substituted by an alkoxyl group having 1 to 10 carbon atoms or a halogen atom having 1 to 30 carbon atoms, A is a trans-1,4-cyclohexylene group, 1,2-phenylene group in which any one or more hydrogen atoms may be substituted by halogen atoms, trans-2,6-decahydronaphthyl in which any one or more hydrogen atoms may be substituted by halogen atoms A group or an arbitrary one or more hydrogen atoms represents a 2,6-naphthyl group optionally substituted by a halogen atom, X represents a hydrogen atom or a fluorine atom, and n represents 1 or 2. An acid catalyst is allowed to act on the compound represented by the general formula (2) and an intramolecular cyclization reaction is performed, thereby obtaining the general formula (3).

(In the formula, R ¹ is an alkyl group which may contain a linear, branched or cyclic part having 1 to 20 carbon atoms, an alkoxyl group which may contain a linear, branched or cyclic part having 1 to 20 carbon atoms, carbon An alkoxylalkyl group which may contain a straight, branched or cyclic part having 2 to 20 atoms, an alkenyl group which may contain a straight, branched or cyclic part having 2 to 20 carbon atoms, or a straight chain having 2 to 20 carbon atoms. Represents an alkenyloxy group which may contain a chain, a branch or a cyclic part, which may be substituted by an alkoxyl group having 1 to 10 carbon atoms or a halogen atom having 1 to 30 carbon atoms, and A is trans-1,4- A cyclohexylene group, a 1,4-phenylene group in which any one or more hydrogen atoms may be substituted by a halogen atom, trans-2, in which any one or more hydrogen atoms may be substituted by a halogen atom, 6-decahydronaphthyl group or any one or more A hydrogen atom is a 2,6-naphthyl group optionally substituted by a halogen atom, X represents a hydrogen atom or a fluorine atom, and n represents 1 or 2. . Subsequently, by hydrogenation reduction or aromatic cyclization reaction, the general formula (4)

(In the formula, R ¹ is an alkyl group which may contain a linear, branched or cyclic part having 1 to 20 carbon atoms, an alkoxyl group which may contain a linear, branched or cyclic part having 1 to 20 carbon atoms, carbon An alkoxylalkyl group which may contain a straight, branched or cyclic part having 2 to 20 atoms, an alkenyl group which may contain a straight, branched or cyclic part having 2 to 20 carbon atoms, or a straight chain having 2 to 20 carbon atoms. Represents an alkenyloxy group which may contain a chain, a branch or a cyclic part, which may be substituted by an alkoxyl group having 1 to 10 carbon atoms or a halogen atom having 1 to 30 carbon atoms, and A is trans-1,4- A cyclohexylene group, a 1,4-phenylene group in which any one or more hydrogen atoms may be substituted by a halogen atom, trans-2, in which any one or more hydrogen atoms may be substituted by a halogen atom, 6-decahydronaphthyl group or any one or more A tetrahydronaphthalene derivative represented by the following formula: a hydrogen atom is a 2,6-naphthyl group optionally substituted by a halogen atom, X represents a hydrogen atom or a fluorine atom, and n represents 1 or 2. Formula (5)

（式中、R¹は炭素原子数1〜20の直鎖、分岐又は環状部を含んでよいアルキル基、炭素原子数1〜20の直鎖、分岐又は環状部を含んでよいアルコキシル基、炭素原子数2〜20の直鎖、分岐又は環状部を含んでよいアルコキシルアルキル基、炭素原子数2〜20の直鎖、分岐又は環状部を含んでよいアルケニル基又は炭素原子数2〜20の直鎖、分岐又は環状部を含んでよいアルケニルオキシ基を表し、これらは炭素数1〜10のアルコキシル基又は1〜30個のハロゲン原子によって置換されていてもよく、Aはトランス-1,4-シクロへキシレン基、任意の一個以上の水素原子がハロゲン原子によって置換されていてもよい1,4-フェニレン基、任意の一個以上の水素原子がハロゲン原子によって置換されていてもよいトランス-2,6-デカヒドロナフチル基又は任意の一個以上の水素原子がハロゲン原子によって置換されていてもよい2,6-ナフチル基を表し、Xは水素原子又はフッ素原子を表し、nは1又は2を表す。）で表されるナフタレン誘導体の製造方法を提供し、さらに製造中間体である一般式（１）及び一般式（２）で表される化合物を提供する。

(In the formula, R ¹ is an alkyl group which may contain a linear, branched or cyclic part having 1 to 20 carbon atoms, an alkoxyl group which may contain a linear, branched or cyclic part having 1 to 20 carbon atoms, carbon An alkoxylalkyl group which may contain a straight, branched or cyclic part having 2 to 20 atoms, an alkenyl group which may contain a straight, branched or cyclic part having 2 to 20 carbon atoms, or a straight chain having 2 to 20 carbon atoms. Represents an alkenyloxy group which may contain a chain, a branch or a cyclic part, which may be substituted by an alkoxyl group having 1 to 10 carbon atoms or a halogen atom having 1 to 30 carbon atoms, and A is trans-1,4- A cyclohexylene group, a 1,4-phenylene group in which any one or more hydrogen atoms may be substituted by a halogen atom, trans-2, in which any one or more hydrogen atoms may be substituted by a halogen atom, 6-decahydronaphthyl group or any one or more A hydrogen atom represents a 2,6-naphthyl group optionally substituted by a halogen atom, X represents a hydrogen atom or a fluorine atom, and n represents 1 or 2.) Further provided are compounds represented by general formula (1) and general formula (2) which are production intermediates.

  According to the present invention, a simple process for producing a dihydronaphthalene derivative, which has been difficult to produce due to a large number of conventional processes, and a simple production of a tetrahydronaphthalene derivative and a naphthalene derivative from the obtained dihydronaphthalene derivative can be realized. .

The present invention is described in detail below.
In the present invention, ketones represented by the general formula (1) are used as raw materials for the vinyl ethers represented by the general formula (2).
The compound represented by the general formula (1) can be synthesized as follows.

  A compound represented by the general formula (1) can be synthesized by hydrogenating and reducing an acetylene derivative obtained from the corresponding aldehyde using a transition metal catalyst and further allowing an oxidizing agent to act.

  Phosphorus ylides are usually prepared in the reaction system by adding a base to the corresponding phosphonium salt and allowed to act on the compound represented by the general formula (1) to synthesize the compound represented by the general formula (2). Sodium ethoxide, sodium methoxide, potassium t-butoxide, butyl lithium, phenyl lithium, sodium hydride, trityl sodium and the like are preferable as the base, and potassium t-butoxide or butyl lithium is more preferable. Solvents include hydrocarbons such as hexane, heptane and toluene, halogenated hydrocarbons such as dichloromethane, chloroform and chlorobenzene, diethyl ether, diisopropyl ether (IPE), methyl t-butyl ether, dimethoxymethane (DME), tetrahydrofuran (THF). And ethers such as diethyl ether, diisopropyl ether (IPE), methyl t-butyl ether, dimethoxymethane (DME), tetrahydrofuran (THF), etc. or carbonization such as hexane, heptane, toluene, etc. Hydrogens are more preferred. The reaction temperature is preferably −78 ° to 50 °, more preferably −50 ° to 20 °, and further preferably −20 ° to 20 °.

  In the present invention, a compound represented by the general formula (3) is obtained by intramolecular cyclization of the compound represented by the general formula (2) in the presence of an acid catalyst.

  Acid catalysts for the cyclization reaction include Lewis acids such as boron trifluoride, titanium tetrachloride, tin tetrachloride, aluminum trichloride, hydrochloric acid, sulfuric acid, nitric acid, tetrafluoroboric acid, hexafluorophosphoric acid, paratoluene sulfone. Bronsted acids such as acid and trifluoromethanesulfonic acid are preferred, Bronsted acids such as hydrochloric acid, sulfuric acid, nitric acid, tetrafluoroboric acid, hexafluorophosphoric acid, paratoluenesulfonic acid, and trifluoromethanesulfonic acid are more preferred. More preferred are sulfonic acid and trifluoromethanesulfonic acid.

  Examples of the solvent for the cyclization reaction include hydrocarbons such as hexane, heptane, toluene, halogenated hydrocarbons such as dichloromethane, 1,2-dichloroethane, chloroform, chlorobenzene, diethyl ether, diisopropyl ether (IPE), methyl t- Ethers such as butyl ether, dimethoxymethane (DME) and tetrahydrofuran (THF) and mixed solvents thereof can be preferably used, and halogenated hydrocarbons such as dichloromethane, 1,2-dichloroethane, chloroform and chlorobenzene are more preferable. .

  The reaction temperature is preferably -78 ° C to the reflux temperature of the solvent, more preferably -50 ° C to the reflux temperature of the solvent, and further preferably -20 ° C to 40 ° C.

  By synthesizing the compound represented by the general formula (3) or the compound represented by the general formula (5), the dihydronaphthalene moiety is reduced or aromatic cyclized to the compound represented by the general formula (3). It can be carried out.

  The hydrogenation reduction in the synthesis of the compound represented by the general formula (4) is carried out in a hydrogen atmosphere in a solvent in the presence of a hydrogenation reduction catalyst. Examples of the catalyst include Rh, Ru, Pt, Pd, Ir Or the metal of Os or these metal compounds is mentioned. Further, these metals and metal compounds may be used alone or in combination of two or more. For example, specific examples of Pd metal and its compounds include palladium-carbon, palladium powder, palladium oxide, palladium chloride, palladium bromide, palladium iodide, tetraammine palladium chloride, tetraammine palladium nitrate, tetraammine palladium acetate, dichlorobis. Examples thereof include palladium salts such as (triphenylphosphine) palladium (II) or palladium complexes such as tetrakis (triphenylphosphine) palladium (0) and bis (acetylacetonato) palladium (0). Further, in place of the above-mentioned Pd, the same may be mentioned for the metal of Rh, Ru, Pt, Re, Ir, Os and / or its metal compound. In addition, these metals and metal compounds may be used alone or in combination of two or more, and silica gel, alumina, etc. may be added or supported on them, but Pd metal or metal compounds thereof Is more preferable, and palladium-carbon is particularly preferable.

  Solvents for this hydrogenation reduction reaction include alcohols such as methanol, ethanol, 1-propanol, 2-propanol, 1-butanol, 2-butanol and 2-methyl-1-propanol, organic acids such as acetic acid, diethyl ether , Ethers such as methyl-t-butyl ether and tetrahydrofuran, esters such as ethyl acetate, methyl acetate and butyl acetate, saturated hydrocarbons such as pentane, hexane, heptane and octane, and aromatic carbonization such as benzene, toluene and xylene Hydrogens, N, N-dimethylformamide, amides such as DMF are preferably used singly or in combination, and esters, alcohols, organic acids, and mixed solvents containing them are more preferable.

  This hydrogenation reduction reaction can be carried out at a temperature from the solvent freezing point to 300 ° C., preferably 0 ° C. to 200 ° C. The hydrogen pressure is usually preferably from normal pressure (˜0.1 MPa) to 19.6 MPa, particularly preferably from normal pressure to 3.9 MPa.

The aromatic cyclization reaction in the synthesis of the compound represented by the general formula (5) is carried out by adding a halogen to the double bond site and then removing the hydrogen halide.
As the halogen in this halogenation reaction, bromine or chlorine is preferred. Solvents for this halogenation reaction include hydrocarbons such as hexane, heptane and toluene, organic acids such as acetic acid, halogenated hydrocarbons such as dichloromethane, chloroform and carbon tetrachloride, ethyl ether, diisopropyl ether (IPE), dimethoxy Ethers such as methane (DME) and tetrahydrofuran (THF) and mixed solvents thereof are preferable, and ethers such as ethyl ether, diisopropyl ether (IPE), dimethoxymethane (DME), and tetrahydrofuran (THF) or dichloromethane, chloroform, four More preferred are halogenated hydrocarbons such as carbon chloride. The reaction temperature of the halogenation reaction is preferably −78 ° to 50 °, more preferably −50 ° to 20 °, and further preferably −20 ° to 20 °.

  This dehydrohalogenation reaction may be carried out in the presence of a base. Examples of the base include inorganic salts such as sodium hydroxide, potassium hydroxide, potassium acetate, potassium carbonate, sodium methoxide, sodium ethoxide, sodium isopropoxide, Alkoxides such as potassium t-butoxide, tertiary amines such as pyridine and quinoline are preferred, and alkoxides and tertiary amines are more preferred. Solvents for this dehydrohalogenation reaction include alcohols such as methanol, ethanol, propanol, butanol, pentanol, and cyclohexanol, tetrahydrofuran (THF), diethyl ether, diisopropyl ether, dibutyl ether, methyl-t-butyl ether, diethylene glycol Ethers such as dimethyl ether, dimethoxyethane, 1,4-dioxane, halogenated hydrocarbons such as dichloromethane chloroform and carbon tetrachloride, hydrocarbons such as hexane, cyclohexane and toluene, acetonitrile, nitromethane, dimethyl sulfoxide (DMSO), Preferably, aprotic solvents such as N, N′-dimethylformamide (DMF) and N, N′-dimethylacetamide (DMA) are used singly or in combination. Methanol, ethanol, propanol, butanol, pentanol, THF, diethyl ether, diisopropyl ether, diethylene glycol dimethyl ether, 1,4-dioxane, hexane, more preferably toluene, ethanol, propanol, THF, diethyl ether, diisopropyl ether is particularly preferable. The reaction temperature of the present dehydrohalogenation reaction is preferably from -78 ° C to the reflux temperature of the solvent, more preferably from -50 ° C to the reflux temperature of the solvent, and further preferably from -20 ° C to the reflux temperature of the solvent.

  Moreover, the aromatic cyclization reaction in the synthesis of the compound represented by the general formula (5) can be carried out in the presence of a catalytic dehydrogenation catalyst. Examples of the catalyst include Rh, Ru, Pt, Pd, Ir, or Os metals, or metal compounds thereof. Examples of the catalyst include Rh, Ru, Pt, Pd, Ir, or Os metals, or metal compounds thereof. Further, these metals and metal compounds may be used alone or in combination of two or more. For example, specific examples of Pd metal and its compounds include palladium-carbon, palladium powder, palladium oxide, palladium chloride, palladium bromide, palladium iodide, tetraammine palladium chloride, tetraammine palladium nitrate, tetraammine palladium acetate, dichlorobis. Palladium salts such as (triphenylphosphine) palladium (II) or palladium complexes such as tetrakis (triphenylphosphine) palladium (0) and bis (acetylacetonato) palladium (0) can be mentioned. Further, in place of the above-mentioned Pd, the same may be mentioned for the metal of Rh, Ru, Pt, Re, Ir, Os and / or its metal compound. In addition, these metals and metal compounds may be used alone or in combination of two or more, and silica gel, alumina, etc. may be added or supported on them, but Pd metal or metal compounds thereof Is more preferable, and palladium-carbon is particularly preferable.

In this catalytic dehydrogenation reaction, a solvent may or may not be used. Examples of the solvent include methanol, ethanol, 1-propanol, 2-propanol, 1-butanol, 2-butanol, and 2-methyl-1- Alcohols such as propanol, organic acids such as acetic acid, ethers such as diethyl ether, methyl-t-butyl ether and tetrahydrofuran, esters such as ethyl acetate, methyl acetate and butyl acetate, saturation of pentane, hexane, heptane and octane Hydrocarbons, aromatic hydrocarbons such as benzene, toluene, xylene, etc., amides such as N, N-dimethylformamide, DMF, etc. are preferably used alone or in combination, and esters, alcohols, organic acids And mixed solvents containing them are more preferred.
This catalytic dehydrogenation reaction can be carried out at a temperature from the solvent freezing point to 300 ° C, preferably from 0 ° C to 200 ° C.

  The aromatic cyclization reaction in the synthesis of the compound represented by the general formula (5) can also be carried out in the presence of quinones. Examples of quinones include 2,3-dichloro-5,6-dicyano-1,4-benzoquinone (DDQ), tetrachloro-1,2-benzoquinone, and tetrachloro-1,4-benzoquinone.

  Solvents for this aromatic cyclization reaction include ethers such as tetrahydrofuran (THF), diethyl ether, diisopropyl ether, methyl-t-butyl ether, diethylene glycol dimethyl ether, 1,4-dioxane, saturated with pentane, hexane, heptane, octane, etc. Hydrocarbons, aromatic hydrocarbons such as benzene, toluene and xylene are preferably used alone or in combination, and 1,4-dioxane, benzene, toluene and xylene are more preferred.

  This aromatic cyclization reaction can be carried out at a temperature from the solvent freezing point to 300 ° C, preferably 0 ° C to 200 ° C.

In the present invention, in the compounds represented by the general formulas (1) to (6), R ¹ is an alkyl group having 1 to 20 carbon atoms, which may contain a linear, branched or cyclic part, and 1 to 20 carbon atoms. An alkoxyl group which may contain a straight, branched or cyclic part, an alkoxylalkyl group which may contain a straight, branched or cyclic part having 2 to 20 carbon atoms, a straight, branched or cyclic which has 2 to 20 carbon atoms Represents an alkenyl group which may contain a moiety or an alkenyloxy group which may contain a linear, branched or cyclic part having 2 to 20 carbon atoms, these being an alkoxyl group having 1 to 10 carbon atoms or a halogen atom having 1 to 30 carbon atoms The linear alkyl group having 1 to 20 carbon atoms, the straight chain alkoxyl group having 1 to 20 carbon atoms, and the straight chain alkoxyl alkyl group having 2 to 20 carbon atoms are preferable. More preferably, a linear alkyl group having 1 to 8 carbon atoms More preferably an alkoxyl group having a straight chain of 1 to 8 carbon atoms. R ² is an alkyl group which may contain a straight, branched or cyclic part having 1 to 20 carbon atoms, an alkoxylalkyl group which may contain a straight, branched or cyclic part having 2 to 20 carbon atoms, and 2 carbon atoms. Represents an alkenyl group which may contain a linear, branched or cyclic part of -20 or an alkenyloxy group which may contain a linear, branched or cyclic part of 2 to 20 carbon atoms, which are alkoxyl having 1 to 10 carbon atoms A linear alkyl group having 1 to 20 carbon atoms, a linear alkoxyl alkyl group having 2 to 20 carbon atoms, and more preferably A straight-chain alkyl group having 1 to 8 atoms is more preferable. A is a trans-1,4-cyclohexylene group, any one or more hydrogen atoms may be substituted with halogen atoms, and any one or more hydrogen atoms may be substituted with halogen atoms. A trans-2,6-decahydronaphthyl group which may optionally be substituted, or a 2,6-naphthyl group in which any one or more hydrogen atoms may be substituted by a halogen atom, preferably trans-1,4-cyclohexylene More preferably, the group is a 1,4-phenylene group in which any one or more hydrogen atoms may be substituted by a halogen atom. X is preferably a hydrogen atom or a fluorine atom. n is preferably 1 or 2.

EXAMPLES Hereinafter, although an Example is given and this invention is further explained in full detail, this invention is not limited to these Examples. The product was analyzed by gas chromatography, mass spectrometry gas chromatography and NMR to determine the structure.
Example 1-1 Synthesis of 3- (2,3,4, -trifluorophenyl) -1- [trans-4- (trans-4-propylcyclohexyl) cyclohexyl] -2-propyn-1-ol

In a 300 ml reaction vessel equipped with a dropping funnel, 2,3,4-trifluorophenylacetylene (11.3 g) and THF (50 ml) were added and stirred. The reaction vessel was placed in an ice bath and 2.7 M methylmagnesium bromide was added. A THF solution (40 ml) was added dropwise, and the mixture was stirred for 30 minutes. Then, a THF (50 ml) solution of trans, trans-4'-propylbicyclohexyl-4-carbaldehyde (16.0 g) was added dropwise on an ice bath. Stir for 2 hours. The completion of the reaction was confirmed by GC, the reaction solution was poured into 10% hydrochloric acid to stop the reaction, extracted three times with ethyl acetate, the organic layers were combined, and washed with an aqueous sodium chloride solution. After drying over anhydrous magnesium sulfate and filtration, the solvent was distilled off, and the residue was purified by silica gel column chromatography (hexane: ethyl acetate = 20: 1, followed by toluene), and 3- (2,3,4, -Trifluorophenyl) -1- [trans-4- (trans-4-propylcyclohexyl) cyclohexyl] -2-propyn-1-ol (23.0 g, yield 97%) was obtained.
MS m / s: 392 (M ⁺ ), 69 (100).
Example 1-2 3- (2,3,4-trifluorophenyl) -1- [trans-4- (trans-4-propylcyclohexyl) cyclohexyl] -1-propanol

To a 300 ml autoclave 3- (2,3,4, -trifluorophenyl) -1- [trans-4- (trans-4-propylcyclohexyl) cyclohexyl] -2-propyn-1-ol (10 g), 5 % Palladium-carbon (containing 50 wt% water, 1 g) and ethyl acetate (70 ml) were added, and the mixture was stirred under hydrogen (0.4 MPa) at room temperature for 4.5 hours. After confirming the completion of the reaction by GC, the reaction mixture was filtered and the solvent was distilled off. The residue was purified by silica gel column chromatography (hexane: ethyl acetate = 20: 1, followed by toluene) to give 3- (2,3,4-trifluorophenyl) -1- [trans-4- (trans-4- Propylcyclohexyl) cyclohexyl] -1-propanol (10.0 g, 99% yield) was obtained.
MS m / s: (M ⁺ ), 378, 149 (100).
Example 1-3a Synthesis of 3- (2,3,4-trifluorophenyl) -1- [trans-4-trans- (4-propylcyclohexyl) cyclohexyl] -1-propanone

A 200 ml eggplant flask was charged with 3- (2,3,4-trifluorophenyl) -1- [trans-4- (trans-4-propylcyclohexyl) cyclohexyl] -1-propanol (8.9 g) and dichloromethane (65 ml). ) While stirring at room temperature, PCC (10 g) was added in small portions and stirred for 5 hours. After confirming the completion of the reaction by GC, the reaction solution was decanted and the solvent was distilled off. The residue was purified by silica gel column chromatography (developing solvent hexane: toluene = 1: 1), and 3- (2,3,4-trifluorophenyl) -1- [trans-4- (trans-4-propylcyclohexyl) Cyclohexyl] -1-propanone (8.3 g, 94% yield) was obtained.
MS m / s: 394 (M ⁺ ), 69 (100).
Example 1-3b Synthesis of 3- (2,3,4-trifluorophenyl) -1- [trans-4-trans- (4-propylcyclohexyl) cyclohexyl] -1-propanone

In a 50 ml eggplant flask, add 3- (2,3,4-trifluorophenyl) -1- [trans-4- (trans-4-propylcyclohexyl) cyclohexyl] -1-propanol (3.0 g), acetic acid (15 ml ) And acetone (15 ml). An 8% aqueous sodium hypochlorite solution (4.0 g) was added dropwise with stirring at an internal temperature of 10 ° C. The mixture was stirred at an internal temperature of 15 to 20 ° C. for 4 hours. After confirming the completion of the reaction by GC, a saturated aqueous sodium hydrogen sulfite solution was added to the reaction solution until the potassium iodide-starch reaction became negative. Ethyl acetate and saturated aqueous sodium hydrogen carbonate solution were poured into the reaction mixture to stop the reaction, and the mixture was extracted 3 times with ethyl acetate. The organic layers were combined, washed sequentially with a saturated aqueous sodium hydrogen carbonate solution and a saturated aqueous sodium chloride solution, dried over anhydrous sodium sulfate and filtered, and then the solvent was distilled off. The residue was purified by silica gel column chromatography (developing solvent hexane: toluene = 1: 1), and 3- (2,3,4-trifluorophenyl) -1- [trans-4- (trans-4-propylcyclohexyl) Cyclohexyl] -1-propanone (2.5 g, 84% yield) was obtained.
MS m / s: 394 (M ⁺ ), 69 (100).
Example 1-4) Synthesis of 4- (2,3,4-trifluorophenyl) -1-methoxy-2- (trans-4- (trans-4-propylcyclohexyl) -1-butene

In a 50 ml reaction vessel, methoxymethyltriphenylphosphonium chloride (3.6 g) and THF (12 ml) were added, and potassium tert-butoxide (1 g) was added in several portions in an ice bath and stirred. 3- (2,3,4-trifluorophenyl) -1- [trans-4- (trans-4-propylcyclohexyl) cyclohexyl] -1-propanone (3.1 g) in THF (7 ml) was added dropwise. In addition, the mixture was stirred for 4 hours in an ice bath. The completion of the reaction was confirmed by GC, and water was added to stop the reaction. Extracted with hexane three times, and the organic layers were combined, washed sequentially with a water-methanol mixed solvent, water, and a saturated aqueous sodium chloride solution, dried over anhydrous sodium sulfate and filtered. 3,4-trifluorophenyl) -1-methoxy-2- (trans-4- (trans-4-propylcyclohexyl) -1-butene (3.3 g, yield 99%) was obtained.
Example 1-5 Synthesis of 5,6,7-trifluoro-2- [trans-4- (trans-4-propylcyclohexyl) cyclohexyl] -3,4-dihydronaphthalene

In a 50 ml reaction vessel, add 4- (2,3,4-trifluorophenyl) -1-methoxy-2- (trans-4- (trans-4-propylcyclohexyl) -1-butene (19.2 g), dichloromethane (100 trifluoromethanesulfonic acid (4 ml) was added and stirred for 5 hours, the reaction was confirmed by GC, and the reaction was stopped with a saturated aqueous solution of sodium bicarbonate, extracted three times with a hexane-toluene mixed solvent, The organic layers were combined, washed with saturated brine, dried over anhydrous magnesium sulfate, filtered, the solvent was distilled off, the residue was separated by silica gel column chromatography (developing solvent hexane), and 5,6,7 -Trifluoro-2- [trans-4- (trans-4-propylcyclohexyl) cyclohexyl] -3,4-dihydronaphthalene (11.5 g, yield 65%) was obtained.
¹ H NMR (400 MHz, CDCl ₃ ) d: 6.58 (ddd, J = 2.0, 7.1, 10.5 Hz, 1 H), 6.06 (s, 1H), 2.75 (t, J = 8.2 Hz, 2 H), 2.22 (t, J = 8.2 Hz, 2 H), 1.97 (broad t, J = 11.7 Hz, 1 H), 1.85-1.70 (m, 9 H), 1.33-0.81 (m, 14 H), 0.87 (t, J = 7.33 Hz, 3H).
MS m / s: 390 (M ⁺ ), 184 (100).
Example 1-6 Synthesis of 5,6,7-trifluoro-2- [trans-4- (trans-4-propylcyclohexyl) cyclohexyl] -1,2,3,4-tetrahydronaphthalene

In a 50 ml reaction vessel, 5,6,7-trifluoro-2- [trans-4- (trans-4-propylcyclohexyl) cyclohexyl] -3,4-dihydronaphthalene (0.25 g), 5% palladium-carbon (50 wt. % Water content, 25 mg) and ethyl acetate (4 ml) were added, and the mixture was stirred under a hydrogen atmosphere for 4 hours. After confirming the completion of the reaction by GC, the reaction mixture was filtered and the solvent was distilled off. The residue was separated by silica gel column chromatography (developing solvent hexane), and 5,6,7-trifluoro-2- [trans-4- (trans-4-propylcyclohexyl) cyclohexyl] -1,2,3,4- Tetrahydronaphthalene (0.25 g, quantitative) was obtained.
¹ H NMR (400 MHz, CDCl ₃ ) d: 6.65 (t, J = 8.3 Hz, 1 H), 2.87 (broad d, J = 17.3 Hz, 1 H), 2.70 (dd, J = 4.3, 16.5 Hz, 1 H), 2.56-2.41 (m, 2 H), 1.99-1.95 (m, 1 H), 1.85-1.69 (m, 8 H), 1.49-1.26 (m, 5 H), 1.15-1.12 (m, 4 H), 1.08-0.83 (m, 9 H), 0.87 (t, J = 7.3 Hz, 3 H).
MS m / s: 392 (M ⁺ ), 69 (100). (Example 2) Synthesis of 1,2,3-trifluoro-6- (4-propylphenyl) naphthalene

5,6,7-trifluoro-2- (4-propylphenyl) -3,4-dihydronaphthalene synthesized in a 50 ml reaction vessel in the same manner as described in Examples 1-1) to 1-5) (20.0 g) and dichloromethane (100 ml) were added, and a solution of bromine (4 ml) in dichloromethane (12 ml) was added dropwise in an ice bath, and the mixture was stirred in an ice bath for 2 hours. After confirming the completion of the reaction by GC, a saturated aqueous sodium hydrogen carbonate solution was added to stop the reaction. Extraction was performed 3 times with hexane, and the organic layers were combined, washed with saturated brine, and then dried over anhydrous magnesium sulfate. Filter and remove the solvent. The residue was separated by silica gel column chromatography (developing solvent hexane) to obtain 1,2,3-trifluoro-6- (4-propylphenyl) naphthalene (10.7 g, yield 54%).
¹ H NMR (400 MHz, CDCl ₃ ) d: 8.09 (d, J = 8.5 Hz, 1 H), 7.92 (s, 1 H), 7.79 (d, J = 8.6 Hz, 1 H), 7.60 (d, J = 8.1 Hz, 2 H), 7.44-7.39 (broad ddd, J = 1.8, 6.8, 9.5 Hz, 1 H), 7.31 (d, J = 8.1 Hz, 2 H), 2.66 (t, J = 7.6 Hz , 2 H), 1.70 (broad sextet, J = 7.5 Hz, 2 H), 0.99 (t, J = 7.3 Hz, 3 H).
MS m / s: 300 (M ⁺ ), 271 (100).
(Comparative Example) Synthesis of 1,2,3-trifluoro-6- (4-propylphenyl) naphthalene

  According to the production method described in Non-Patent Document 1, 1,2,3-trifluoro-6- (4-propylphenyl) naphthalene was synthesized. As a result, 10 steps were required and the total yield was 19%.

In Example 2 of the present invention, the reaction step was as short as 6 steps, and the target product could be obtained with a good overall yield of 31%.

Claims (16)

General formula (2)

(In the formula, R ¹ is an alkyl group which may contain a linear, branched or cyclic part having 1 to 20 carbon atoms, an alkoxyl group which may contain a linear, branched or cyclic part having 1 to 20 carbon atoms, carbon An alkoxylalkyl group which may contain a straight, branched or cyclic part having 2 to 20 atoms, an alkenyl group which may contain a straight, branched or cyclic part having 2 to 20 carbon atoms, or a straight chain having 2 to 20 carbon atoms. Represents an alkenyloxy group which may contain a chain, a branch or a cyclic part, which may be substituted by an alkoxyl group having 1 to 10 carbon atoms or a halogen atom having 1 to 30 carbon atoms, and R ² has 1 to Alkyl group which may contain 20 straight chain, branched or cyclic part, straight chain having 1 to 20 carbon atoms, alkoxylalkyl group which may contain straight chain, branched or cyclic part of 2 to 20 carbon atoms, carbon atom An alkenyl group or carbon atoms of 2 to 20 which may contain a linear, branched or cyclic part of 2 to 20 Represents an alkenyloxy group which may contain a linear, branched or cyclic part of ˜20, which may be substituted by an alkoxyl group having 1 to 10 carbon atoms or a halogen atom of 1 to 30 carbon atoms, 1,4-cyclohexylene group, any one or more hydrogen atoms may be substituted by halogen atoms, 1,4-phenylene group, any one or more hydrogen atoms may be substituted by halogen atoms A trans-2,6-decahydronaphthyl group or a 2,6-naphthyl group in which any one or more hydrogen atoms may be substituted by a halogen atom, X represents a hydrogen atom or a fluorine atom, and n represents 1 Or a compound represented by formula (3) by cyclizing the compound represented by (2) in the presence of an acid catalyst.

(In the formula, R ¹ is an alkyl group which may contain a linear, branched or cyclic part having 1 to 20 carbon atoms, an alkoxyl group which may contain a linear, branched or cyclic part having 1 to 20 carbon atoms, carbon An alkoxylalkyl group which may contain a straight, branched or cyclic part having 2 to 20 atoms, an alkenyl group which may contain a straight, branched or cyclic part having 2 to 20 carbon atoms, or a straight chain having 2 to 20 carbon atoms. Represents an alkenyloxy group which may contain a chain, a branch or a cyclic part, which may be substituted by an alkoxyl group having 1 to 10 carbon atoms or a halogen atom having 1 to 30 carbon atoms, and A is trans-1,4- A cyclohexylene group, a 1,4-phenylene group in which any one or more hydrogen atoms may be substituted by a halogen atom, trans-2, in which any one or more hydrogen atoms may be substituted by a halogen atom, 6-decahydronaphthyl group or any one or more A hydrogen atom represents a 2,6-naphthyl group optionally substituted by a halogen atom, X represents a hydrogen atom or a fluorine atom, and n represents 1 or 2.) . General formula (1)

(In the formula, R ¹ is an alkyl group which may contain a linear, branched or cyclic part having 1 to 20 carbon atoms, an alkoxyl group which may contain a linear, branched or cyclic part having 1 to 20 carbon atoms, carbon An alkoxylalkyl group which may contain a straight, branched or cyclic part having 2 to 20 atoms, an alkenyl group which may contain a straight, branched or cyclic part having 2 to 20 carbon atoms, or a straight chain having 2 to 20 carbon atoms. Represents an alkenyloxy group which may contain a chain, a branch or a cyclic part, which may be substituted by an alkoxyl group having 1 to 10 carbon atoms or a halogen atom having 1 to 30 carbon atoms, and A is trans-1,4- A cyclohexylene group, a 1,4-phenylene group in which any one or more hydrogen atoms may be substituted by a halogen atom, trans-2, in which any one or more hydrogen atoms may be substituted by a halogen atom, 6-decahydronaphthyl group or any one or more A hydrogen atom is a 2,6-naphthyl group optionally substituted by a halogen atom, X represents a hydrogen atom or a fluorine atom, and n represents 1 or 2. 6)

(Wherein R ² is a linear, branched or cyclic alkyl group having 1 to 20 carbon atoms, a linear chain having 1 to 20 carbon atoms, a straight chain having 2 to 20 carbon atoms, branched or An alkoxylalkyl group which may contain a cyclic part, a straight chain having 2 to 20 carbon atoms, an alkenyl group which may contain a branched or cyclic part or an alkenyl which may contain a linear, branched or cyclic part having 2 to 20 carbon atoms An oxy group, which may be substituted by an alkoxyl group having 1 to 10 carbon atoms or a halogen atom having 1 to 30 carbon atoms), and reacting with a phosphorus ylide represented by the general formula (2)

(In the formula, R ¹ is an alkyl group which may contain a linear, branched or cyclic part having 1 to 20 carbon atoms, an alkoxyl group which may contain a linear, branched or cyclic part having 1 to 20 carbon atoms, carbon An alkoxylalkyl group which may contain a straight, branched or cyclic part having 2 to 20 atoms, an alkenyl group which may contain a straight, branched or cyclic part having 2 to 20 carbon atoms, or a straight chain having 2 to 20 carbon atoms. Represents an alkenyloxy group which may contain a chain, a branch or a cyclic part, which may be substituted by an alkoxyl group having 1 to 10 carbon atoms or a halogen atom having 1 to 30 carbon atoms, and R ² has 1 to Alkyl group which may contain 20 straight chain, branched or cyclic part, straight chain having 1 to 20 carbon atoms, alkoxylalkyl group which may contain straight chain, branched or cyclic part of 2 to 20 carbon atoms, carbon atom An alkenyl group or carbon atoms of 2 to 20 which may contain a linear, branched or cyclic part of 2 to 20 Represents an alkenyloxy group which may contain a linear, branched or cyclic part of ˜20, which may be substituted by an alkoxyl group having 1 to 10 carbon atoms or a halogen atom of 1 to 30 carbon atoms, 1,4-cyclohexylene group, any one or more hydrogen atoms may be substituted by halogen atoms, 1,4-phenylene group, any one or more hydrogen atoms may be substituted by halogen atoms A trans-2,6-decahydronaphthyl group or a 2,6-naphthyl group in which any one or more hydrogen atoms may be substituted by a halogen atom, X represents a hydrogen atom or a fluorine atom, and n represents 1 Or a process for producing a dihydronaphthalene derivative represented by the general formula (3) according to claim 1, wherein the compound represented by formula (3) is produced. General formula (1)

(In the formula, R ¹ is an alkyl group which may contain a linear, branched or cyclic part having 1 to 20 carbon atoms, an alkoxyl group which may contain a linear, branched or cyclic part having 1 to 20 carbon atoms, carbon An alkoxylalkyl group which may contain a straight, branched or cyclic part having 2 to 20 atoms, an alkenyl group which may contain a straight, branched or cyclic part having 2 to 20 carbon atoms, or a straight chain having 2 to 20 carbon atoms. Represents an alkenyloxy group which may contain a chain, a branch or a cyclic part, which may be substituted by an alkoxyl group having 1 to 10 carbon atoms or a halogen atom having 1 to 30 carbon atoms, and A is trans-1,4- A cyclohexylene group, a 1,4-phenylene group in which any one or more hydrogen atoms may be substituted by a halogen atom, trans-2, in which any one or more hydrogen atoms may be substituted by a halogen atom, 6-decahydronaphthyl group or any one or more Is a hydrogen atom represents optionally substituted 2,6-naphthyl group by a halogen atom, X represents a hydrogen atom or a fluorine atom, n represents represented by representative.) 1 or 2 compounds. General formula (2)

(In the formula, R ¹ is an alkyl group which may contain a linear, branched or cyclic part having 1 to 20 carbon atoms, an alkoxyl group which may contain a linear, branched or cyclic part having 1 to 20 carbon atoms, carbon An alkoxylalkyl group which may contain a straight, branched or cyclic part having 2 to 20 atoms, an alkenyl group which may contain a straight, branched or cyclic part having 2 to 20 carbon atoms, or a straight chain having 2 to 20 carbon atoms. Represents an alkenyloxy group which may contain a chain, a branch or a cyclic part, which may be substituted by an alkoxyl group having 1 to 10 carbon atoms or a halogen atom having 1 to 30 carbon atoms, and R ² has 1 to Alkyl group which may contain 20 straight chain, branched or cyclic part, straight chain having 2 to 20 carbon atoms, alkoxylalkyl group which may contain branched or cyclic part, straight chain, branched or 2 to 20 carbon atoms An alkenyl group which may contain a cyclic part or a straight chain, branched or ring having 2 to 20 carbon atoms Represents an alkenyloxy group which may contain a moiety, which may be substituted by an alkoxyl group having 1 to 10 carbon atoms or a halogen atom having 1 to 30 carbon atoms, A is a trans-1,4-cyclohexylene group, 1,2-phenylene group in which any one or more hydrogen atoms may be substituted by halogen atoms, trans-2,6-decahydronaphthyl in which any one or more hydrogen atoms may be substituted by halogen atoms A group or an arbitrary one or more hydrogen atoms represents a 2,6-naphthyl group optionally substituted by a halogen atom, X represents a hydrogen atom or a fluorine atom, and n represents 1 or 2. Compound. General formula (2)

(In the formula, R ¹ is an alkyl group which may contain a linear, branched or cyclic part having 1 to 20 carbon atoms, an alkoxyl group which may contain a linear, branched or cyclic part having 1 to 20 carbon atoms, carbon An alkoxylalkyl group which may contain a straight, branched or cyclic part having 2 to 20 atoms, an alkenyl group which may contain a straight, branched or cyclic part having 2 to 20 carbon atoms, or a straight chain having 2 to 20 carbon atoms. Represents an alkenyloxy group which may contain a chain, a branch or a cyclic part, which may be substituted by an alkoxyl group having 1 to 10 carbon atoms or a halogen atom having 1 to 30 carbon atoms, and R ² has 1 to Alkyl group which may contain 20 straight chain, branched or cyclic part, straight chain having 2 to 20 carbon atoms, alkoxylalkyl group which may contain branched or cyclic part, straight chain, branched or 2 to 20 carbon atoms An alkenyl group which may contain a cyclic part or a straight chain, branched or ring having 2 to 20 carbon atoms Represents an alkenyloxy group which may contain a moiety, which may be substituted by an alkoxyl group having 1 to 10 carbon atoms or a halogen atom having 1 to 30 carbon atoms, A is a trans-1,4-cyclohexylene group, 1,2-phenylene group in which any one or more hydrogen atoms may be substituted by halogen atoms, trans-2,6-decahydronaphthyl in which any one or more hydrogen atoms may be substituted by halogen atoms A group or an arbitrary one or more hydrogen atoms represents a 2,6-naphthyl group optionally substituted by a halogen atom, X represents a hydrogen atom or a fluorine atom, and n represents 1 or 2. Is cyclized in the presence of an acid catalyst to give a compound of the general formula (3)

(In the formula, R ¹ is an alkyl group which may contain a linear, branched or cyclic part having 1 to 20 carbon atoms, an alkoxyl group which may contain a linear, branched or cyclic part having 1 to 20 carbon atoms, carbon An alkoxylalkyl group having a straight chain, branched or cyclic part having 2 to 20 atoms, an alkenyl group having a straight chain, branched or cyclic part having 2 to 20 carbon atoms, or a straight chain having 2 to 20 carbon atoms Represents an alkenyloxy group which may contain a chain, a branch or a cyclic part, which may be substituted by an alkoxyl group having 1 to 10 carbon atoms or a halogen atom having 1 to 30 carbon atoms, and A is trans-1,4- A cyclohexylene group, a 1,4-phenylene group in which any one or more hydrogen atoms may be substituted by a halogen atom, trans-2, in which any one or more hydrogen atoms may be substituted by a halogen atom, 6-decahydronaphthyl group or any one or more A hydrogen atom represents a 2,6-naphthyl group optionally substituted by a halogen atom, X represents a hydrogen atom or a fluorine atom, and n represents 1 or 2, and a dihydronaphthalene derivative represented by Furthermore, the general formula (4) obtained by hydrogenating and reducing the compound represented by the general formula (3)

(In the formula, R ¹ is an alkyl group which may contain a linear, branched or cyclic part having 1 to 20 carbon atoms, an alkoxyl group which may contain a linear, branched or cyclic part having 1 to 20 carbon atoms, carbon An alkoxylalkyl group which may contain a straight, branched or cyclic part having 2 to 20 atoms, an alkenyl group which may contain a straight, branched or cyclic part having 2 to 20 carbon atoms, or a straight chain having 2 to 20 carbon atoms. Represents an alkenyloxy group which may contain a chain, a branch or a cyclic part, which may be substituted by an alkoxyl group having 1 to 10 carbon atoms or a halogen atom having 1 to 30 carbon atoms, and A is trans-1,4- A cyclohexylene group, a 1,4-phenylene group in which any one or more hydrogen atoms may be substituted by a halogen atom, trans-2, in which any one or more hydrogen atoms may be substituted by a halogen atom, 6-decahydronaphthyl group or any one or more A hydrogen atom represents a 2,6-naphthyl group optionally substituted by a halogen atom, X represents a hydrogen atom or a fluorine atom, and n represents 1 or 2.) . General formula (1)

(In the formula, R ¹ is an alkyl group which may contain a linear, branched or cyclic part having 1 to 20 carbon atoms, an alkoxyl group which may contain a linear, branched or cyclic part having 1 to 20 carbon atoms, carbon An alkoxylalkyl group which may contain a straight, branched or cyclic part having 2 to 20 atoms, an alkenyl group which may contain a straight, branched or cyclic part having 2 to 20 carbon atoms, or a straight chain having 2 to 20 carbon atoms. Represents an alkenyloxy group which may contain a chain, a branch or a cyclic part, which may be substituted by an alkoxyl group having 1 to 10 carbon atoms or a halogen atom having 1 to 30 carbon atoms, and A is trans-1,4- A cyclohexylene group, a 1,4-phenylene group in which any one or more hydrogen atoms may be substituted by a halogen atom, trans-2, in which any one or more hydrogen atoms may be substituted by a halogen atom, 6-decahydronaphthyl group or any one or more A hydrogen atom is a 2,6-naphthyl group optionally substituted by a halogen atom, X represents a hydrogen atom or a fluorine atom, and n represents 1 or 2. 6)

(In the formula, R ² is an alkyl group which may contain a linear, branched or cyclic part having 1 to 20 carbon atoms, an alkoxylalkyl group which may contain a linear, branched or cyclic part having 2 to 20 carbon atoms, An alkenyl group which may contain a straight, branched or cyclic part having 2 to 20 carbon atoms or an alkenyloxy group which may contain a straight, branched or cyclic part having 2 to 20 carbon atoms, which has 1 carbon atom (Optionally substituted by 10 to 10 alkoxyl groups or 1 to 30 halogen atoms)), by reacting with phosphorus ylide represented by the general formula (2)

(In the formula, R ¹ is an alkyl group which may contain a linear, branched or cyclic part having 1 to 20 carbon atoms, an alkoxyl group which may contain a linear, branched or cyclic part having 1 to 20 carbon atoms, carbon An alkoxylalkyl group which may contain a straight, branched or cyclic part having 2 to 20 atoms, an alkenyl group which may contain a straight, branched or cyclic part having 2 to 20 carbon atoms, or a straight chain having 2 to 20 carbon atoms. Represents an alkenyloxy group which may contain a chain, a branch or a cyclic part, which may be substituted by an alkoxyl group having 1 to 10 carbon atoms or a halogen atom having 1 to 30 carbon atoms, and R ² has 1 to Alkyl group which may contain 20 straight chain, branched or cyclic part, straight chain having 2 to 20 carbon atoms, alkoxylalkyl group which may contain branched or cyclic part, straight chain, branched or 2 to 20 carbon atoms An alkenyl group which may contain a cyclic part or a straight chain, branched or ring having 2 to 20 carbon atoms Represents an alkenyloxy group which may contain a moiety, which may be substituted by an alkoxyl group having 1 to 10 carbon atoms or a halogen atom having 1 to 30 carbon atoms, A is a trans-1,4-cyclohexylene group, 1,2-phenylene group in which any one or more hydrogen atoms may be substituted by halogen atoms, trans-2,6-decahydronaphthyl in which any one or more hydrogen atoms may be substituted by halogen atoms A group or an arbitrary one or more hydrogen atoms represents a 2,6-naphthyl group optionally substituted by a halogen atom, X represents a hydrogen atom or a fluorine atom, and n represents 1 or 2. 6. The production method according to claim 5, wherein the compound is produced. General formula (2)

(In the formula, R ¹ is an alkyl group which may contain a linear, branched or cyclic part having 1 to 20 carbon atoms, an alkoxyl group which may contain a linear, branched or cyclic part having 1 to 20 carbon atoms, carbon An alkoxylalkyl group which may contain a straight, branched or cyclic part having 2 to 20 atoms, an alkenyl group which may contain a straight, branched or cyclic part having 2 to 20 carbon atoms, or a straight chain having 2 to 20 carbon atoms. Represents an alkenyloxy group which may contain a chain, a branch or a cyclic part, which may be substituted by an alkoxyl group having 1 to 10 carbon atoms or a halogen atom having 1 to 30 carbon atoms, and R ² has 1 to Alkyl group which may contain 20 straight chain, branched or cyclic part, straight chain having 2 to 20 carbon atoms, alkoxylalkyl group which may contain branched or cyclic part, straight chain, branched or 2 to 20 carbon atoms An alkenyl group which may contain a cyclic part or a straight chain, branched or ring having 2 to 20 carbon atoms Represents an alkenyloxy group which may contain a moiety, which may be substituted by an alkoxyl group having 1 to 10 carbon atoms or a halogen atom having 1 to 30 carbon atoms, A is a trans-1,4-cyclohexylene group, 1,2-phenylene group in which any one or more hydrogen atoms may be substituted by halogen atoms, trans-2,6-decahydronaphthyl in which any one or more hydrogen atoms may be substituted by halogen atoms A group or an arbitrary one or more hydrogen atoms represents a 2,6-naphthyl group optionally substituted by a halogen atom, X represents a hydrogen atom or a fluorine atom, and n represents 1 or 2. Is cyclized in the presence of a catalyst to give a compound of the general formula (3)

(In the formula, R ¹ is an alkyl group which may contain a linear, branched or cyclic part having 1 to 20 carbon atoms, an alkoxyl group which may contain a linear, branched or cyclic part having 1 to 20 carbon atoms, carbon An alkoxylalkyl group which may contain a straight, branched or cyclic part having 2 to 20 atoms, an alkenyl group which may contain a straight, branched or cyclic part having 2 to 20 carbon atoms, or a straight chain having 2 to 20 carbon atoms. Represents an alkenyloxy group which may contain a chain, a branch or a cyclic part, which may be substituted by an alkoxyl group having 1 to 10 carbon atoms or a halogen atom having 1 to 30 carbon atoms, and A is trans-1,4- A cyclohexylene group, a 1,4-phenylene group in which any one or more hydrogen atoms may be substituted by a halogen atom, trans-2, in which any one or more hydrogen atoms may be substituted by a halogen atom, 6-decahydronaphthyl group or any one or more A hydrogen atom represents a 2,6-naphthyl group optionally substituted by a halogen atom, X represents a hydrogen atom or a fluorine atom, and n represents 1 or 2, and a dihydronaphthalene derivative represented by General formula (5) by aromatizing the compound represented by general formula (3)

(In the formula, R ¹ is an alkyl group which may contain a linear, branched or cyclic part having 1 to 20 carbon atoms, an alkoxyl group which may contain a linear, branched or cyclic part having 1 to 20 carbon atoms, carbon An alkoxylalkyl group which may contain a straight, branched or cyclic part having 2 to 20 atoms, an alkenyl group which may contain a straight, branched or cyclic part having 2 to 20 carbon atoms, or a straight chain having 2 to 20 carbon atoms. Represents an alkenyloxy group which may contain a chain, a branch or a cyclic part, which may be substituted by an alkoxyl group having 1 to 10 carbon atoms or a halogen atom having 1 to 30 carbon atoms, and A is trans-1,4- A cyclohexylene group, a 1,4-phenylene group in which any one or more hydrogen atoms may be substituted by a halogen atom, trans-2, in which any one or more hydrogen atoms may be substituted by a halogen atom, 6-decahydronaphthyl group or any one or more Is a hydrogen atom represents optionally substituted 2,6-naphthyl group by a halogen atom, X represents a hydrogen atom or a fluorine atom, n represents the production method of the naphthalene derivative represented by the representative.) 1 or 2. General formula (1)

(In the formula, R ¹ is an alkyl group which may contain a linear, branched or cyclic part having 1 to 20 carbon atoms, an alkoxyl group which may contain a linear, branched or cyclic part having 1 to 20 carbon atoms, carbon An alkoxylalkyl group which may contain a straight, branched or cyclic part having 2 to 20 atoms, an alkenyl group which may contain a straight, branched or cyclic part having 2 to 20 carbon atoms, or a straight chain having 2 to 20 carbon atoms. Represents an alkenyloxy group which may contain a chain, a branch or a cyclic part, which may be substituted by an alkoxyl group having 1 to 10 carbon atoms or a halogen atom having 1 to 30 carbon atoms, and A is trans-1,4- A cyclohexylene group, a 1,4-phenylene group in which any one or more hydrogen atoms may be substituted by a halogen atom, trans-2, in which any one or more hydrogen atoms may be substituted by a halogen atom, 6-decahydronaphthyl group or any one or more A hydrogen atom is a 2,6-naphthyl group optionally substituted by a halogen atom, X represents a hydrogen atom or a fluorine atom, and n represents 1 or 2. 6)

(In the formula, R ² is an alkyl group which may contain a linear, branched or cyclic part having 1 to 20 carbon atoms, an alkoxylalkyl group which may contain a linear, branched or cyclic part having 2 to 20 carbon atoms, An alkenyl group which may contain a straight, branched or cyclic part having 2 to 20 carbon atoms or an alkenyloxy group which may contain a straight, branched or cyclic part having 2 to 20 carbon atoms, which has 1 carbon atom (Optionally substituted by 10 to 10 alkoxyl groups or 1 to 30 halogen atoms)), by reacting with phosphorus ylide represented by the general formula (2)

(In the formula, R ¹ is an alkyl group which may contain a linear, branched or cyclic part having 1 to 20 carbon atoms, an alkoxyl group which may contain a linear, branched or cyclic part having 1 to 20 carbon atoms, carbon An alkoxylalkyl group which may contain a straight, branched or cyclic part having 2 to 20 atoms, an alkenyl group which may contain a straight, branched or cyclic part having 2 to 20 carbon atoms, or a straight chain having 2 to 20 carbon atoms. Represents an alkenyloxy group which may contain a chain, a branch or a cyclic part, which may be substituted by an alkoxyl group having 1 to 10 carbon atoms or a halogen atom having 1 to 30 carbon atoms, and R ² has 1 to Alkyl group which may contain 20 straight chain, branched or cyclic part, straight chain having 2 to 20 carbon atoms, alkoxylalkyl group which may contain branched or cyclic part, straight chain, branched or 2 to 20 carbon atoms An alkenyl group which may contain a cyclic part or a straight chain, branched or ring having 2 to 20 carbon atoms Represents an alkenyloxy group which may contain a moiety, which may be substituted by an alkoxyl group having 1 to 10 carbon atoms or a halogen atom having 1 to 30 carbon atoms, A is a trans-1,4-cyclohexylene group, 1,2-phenylene group in which any one or more hydrogen atoms may be substituted by halogen atoms, trans-2,6-decahydronaphthyl in which any one or more hydrogen atoms may be substituted by halogen atoms A group or an arbitrary one or more hydrogen atoms represents a 2,6-naphthyl group optionally substituted by a halogen atom, X represents a hydrogen atom or a fluorine atom, and n represents 1 or 2. The production method according to claim 7, comprising producing a compound. The method for producing a dihydronaphthalene derivative according to any one of claims 1, 2, 5, 6, 7 and 8, wherein a Lewis acid or a Bronsted acid is used as an acid catalyst for the cyclization reaction. As an acid catalyst for the cyclization reaction, Lewis acid such as boron trifluoride, titanium tetrachloride, tin tetrachloride, aluminum trichloride, hydrochloric acid, sulfuric acid, nitric acid, tetrafluoroboric acid, hexafluorophosphoric acid, paratoluenesulfonic acid, The method for producing a dihydronaphthalene derivative according to any one of claims 1, 2, 5, 6, 7 and 8, wherein a Bronsted acid such as trifluoromethanesulfonic acid is used. The method for producing a dihydronaphthalene derivative according to any one of claims 1, 2, 5, 6, 7 and 8, wherein a Bronsted acid such as paratoluenesulfonic acid or trifluoromethanesulfonic acid is used as an acid catalyst for the cyclization reaction. The tetrahydro of claim 5 or 6, wherein one or more of Rh, Ru, Pt, Re, Pd, Ir, Os and / or one of the metal compounds is used alone or in combination of two or more as a hydrogenation reduction catalyst. A method for producing a naphthalene derivative. The process for producing a tetrahydronaphthalene derivative according to claim 5 or 6, wherein the hydrogenation reduction catalyst is a carrier-supported catalyst. The method for producing a naphthalene derivative according to claim 7 or 8, wherein the aromatic cyclization reaction is a reaction in which halogen is added to a double bond site and then hydrogen halide is eliminated in the presence of a base. The method for producing a naphthalene derivative according to claim 7 or 8, wherein the aromatic cyclization reaction is an oxidation reaction with quinones. Claims to use Rh, Ru, Pt, Re, Pd, Ir, Os metal supported on a carrier and / or one of the metal compounds alone or in combination of two or more as a catalyst in an aromatic cyclization reaction Item 9. A method for producing a naphthalene derivative according to Item 7 or 8.