JP3632702B2 - 1,7,8-trifluoro-2-naphthol and method for producing liquid crystal compound using the same - Google Patents

Description

  The present invention relates to a method for producing a trifluoronaphthalene compound useful as a liquid crystal display material and a production intermediate thereof.

  As the liquid crystal display element, a TN method or STN method having a twisted structure has been mainly used. Many liquid crystal compounds and liquid crystal compositions having positive dielectric anisotropy that play a major role in these systems have been developed. On the other hand, for the purpose of improving the narrow viewing angle, which is one of the disadvantages of the display system having the above twisted structure, (1) a method of vertically aligning liquid crystal molecules (VA method; Vertical Alignment method, patent document) 1) and (2) display methods such as applying an electric field substantially parallel to the substrate and rotating liquid crystal molecules in a plane parallel to the substrate (IPS method; In-Plane Switching method, see Patent Document 2) Has been proposed. These systems include a liquid crystal compound and a liquid crystal composition having a negative dielectric constant instead of a liquid crystal compound and a liquid crystal composition having a positive dielectric anisotropy, which are essential compounds of the display system having the above twisted structure. As a result, liquid crystal compounds and liquid crystal compositions having negative dielectric anisotropy have been proposed (see Patent Document 3).

  For the above purpose, liquid crystal compounds having a 1,7,8-trifluoronaphthalene-2,6-diyl group have been developed, and several compounds have been disclosed (see Patent Documents 4 and 5). .

  However, the disclosed method for producing the compound has not always been efficient. In Patent Document 4, the trifluoronaphthalene derivative is a compound shown below.

(式中、Rはアルキル基等を表す。)を製造中間体として製造されている。

(Wherein R represents an alkyl group or the like) is produced as a production intermediate.

  On the other hand, in order to avoid the precipitation of the compound in the composition design of the liquid crystal composition, the liquid crystal compound skeleton often uses several compounds called homologues having the same side chain and different side chains. Have been forced. For efficient production, it is preferable to increase the quantity produced at one time. For this purpose, it is advantageous to produce a compound with a common skeleton and introduce different parts at the final stage of production. The following two types of homologues differ only in R in the method using this intermediate.

を製造する場合にはトリフルオロナフタレン骨格を始めから製造し直さなくてはならないため、多数の中間体を必要とするため効率が悪かった。さらに、比較的収率の悪いトリフルオロナフタレン骨格の製造を、製造の最終段階で行うことから、コストの高い中間体の損失が大きくさらに効率を悪化させていた。
また、特許文献５においては次のような経路でトリフルオロナフタレン誘導体を製造している。

In order to produce a trifluoronaphthalene skeleton from the beginning, a large number of intermediates are required, which is inefficient. Further, since the production of a trifluoronaphthalene skeleton having a relatively low yield is performed at the final stage of the production, the cost of the intermediate is high and the efficiency is further deteriorated.
In Patent Document 5, a trifluoronaphthalene derivative is produced by the following route.

(Ｒ^ｘはアルキル基等を表す。)
この製造方法では、前述のホモローグ製造の際に、中間体を多数用意する必要がある上に、Ｒ^ｘは酸素原子を介してナフタレン骨格と結合することはできず、本願発明の目的とする液晶化合物を製造することはできない。

(R ^x represents an alkyl group or the like.)
In this production method, it is necessary to prepare a large number of intermediates in the above-described homolog production, and in addition, R ^x cannot be bonded to the naphthalene skeleton via an oxygen atom. The compound cannot be produced.

  From the above, development of a trifluoronaphthalene derivative in which a trifluoronaphthalene skeleton is formed first and other skeletons can be introduced later and an efficient method for producing a trifluoronaphthalene derivative using this intermediate have been developed. It was desired.

Japanese Patent Laid-Open No. 2-176625 JP-A-5-505247 Japanese Patent Laid-Open No. 2-4725 JP 2001-31597 A German Patent Application Publication No. 19522195

  An object of the present invention is to provide 1,7,8-trifluoro-2-naphthol and derivatives thereof, which are efficient intermediates for producing trifluoronaphthalene-based liquid crystal materials, and trifluoronaphthalene-based liquid crystal materials using the same It is to provide an efficient manufacturing method.

As a result of intensive studies to solve the above problems, the present inventors have found a production method using 1,7,8-trifluoro-2-naphthol and its derivatives as intermediates, and have completed the present invention. It was.
That is, the present invention relates to the general formula (I)

（式中、Xは水素原子、CF₃SO₂-または炭素数１〜１０の飽和または不飽和のアルキル基を表す。）で表される化合物を提供する。
また、式(Ia)

(Wherein X represents a hydrogen atom, CF ₃ SO ₂ — or a saturated or unsaturated alkyl group having 1 to 10 carbon atoms).
And the formula (Ia)

で表される化合物に、一般式（II）

In the compound represented by general formula (II)

（式中、R¹は炭素数１〜１０の飽和または不飽和のアルキル基を表し、Yは単結合、-CH₂CH₂-または-CH₂O-を表し、Aはトランス-1,4-シクロヘキシレン基又は1,4-フェニレン基を表し、nは０または１を表す。）で表される化合物を触媒存在下に反応させることによる一般式（III）

Wherein R ¹ represents a saturated or unsaturated alkyl group having 1 to 10 carbon atoms, Y represents a single bond, —CH ₂ CH ₂ — or —CH ₂ O—, and A represents trans-1,4 -Represents a cyclohexylene group or a 1,4-phenylene group, and n represents 0 or 1).

（式中、R¹、Y、Aおよびnは一般式（II）におけるR¹、Y、Aおよびnと同じ意味を表す。）で表される化合物の製造方法及び一般式(III)で表される化合物を提供する。
さらに、式(Ia)

(Wherein R ¹ , Y, A and n have the same meanings as R ¹ , Y, A and n in formula (II)) and the formula (III) The compound is provided.
Furthermore, the formula (Ia)

で表される化合物に、一般式（II）

In the compound represented by general formula (II)

（式中、R¹は炭素数１〜１０の飽和または不飽和のアルキル基を表し、Yは単結合、-CH₂CH₂-または-CH₂O-を表し、Aはトランス-1,4-シクロヘキシレン基又は1,4-フェニレン基を表し、nは０または１を表す。）で表される化合物を触媒存在下に反応させることにより一般式（III）

Wherein R ¹ represents a saturated or unsaturated alkyl group having 1 to 10 carbon atoms, Y represents a single bond, —CH ₂ CH ₂ — or —CH ₂ O—, and A represents trans-1,4 -Represents a cyclohexylene group or a 1,4-phenylene group, and n represents 0 or 1) by reacting the compound represented by the general formula (III) in the presence of a catalyst.

（式中、R¹、Y、Aおよびnは一般式（II）におけるR¹、Y、Aおよびnと同じ意味を表す。）で表される化合物を得た後、これをアルキル化またはアルコキシル化することを特徴とする一般式（IV）

(Wherein, R ^1, Y, R ¹ A and n in the general formula (II), Y, represent. The same meanings as A and n) after obtaining the compounds represented by alkylated or alkoxylated this General formula (IV) characterized by

（式中、R¹、Y、Aおよびnは一般式（II）におけるR¹、Y、Aおよびnと同じ意味を表し、R²は炭素数１〜１０の飽和または不飽和のアルキル基またはアルコキシル基を表す。）で表される化合物の製造方法を提供する。
さらに、一般式（Ｉｂ）

(Wherein, R ^1, Y, A and n are in the general formula (II) R ^1, Y, the same meanings as A and n, R ² is or a saturated or unsaturated alkyl group having 1 to 10 carbon atoms Represents an alkoxyl group.) Is provided.
Furthermore, the general formula (Ib)

（式中、Xは炭素数１〜１０の飽和または不飽和のアルキル基を表す。）で表される化合物の６位をリチオ化し、トリメトキシボランを作用させ、得られたボロン酸に、一般式（V）

(Wherein, X represents a saturated or unsaturated alkyl group having 1 to 10 carbon atoms), the 6-position of the compound represented by the formula is reacted with trimethoxyborane. Formula (V)

（式中、Zはヨウ素原子、臭素原子、塩素原子またはトリフルオロメタンスルホニルオキシ基を表し、R¹は炭素数１〜１０の飽和または不飽和のアルキル基を表し、Yは単結合、-CH₂CH₂-または-CH₂O-を表し、Aはトランス-1,4-シクロヘキシレン基又は1,4-フェニレン基を表し、nは０または１を表す。）で表される化合物を触媒存在下に反応させることを特徴とする、一般式（VI）

(In the formula, Z represents an iodine atom, bromine atom, chlorine atom or trifluoromethanesulfonyloxy group, R ¹ represents a saturated or unsaturated alkyl group having 1 to 10 carbon atoms, Y represents a single bond, —CH ₂ CH ₂ — or —CH ₂ O—, A represents a trans-1,4-cyclohexylene group or 1,4-phenylene group, and n represents 0 or 1.) General formula (VI) characterized by reacting below

（式中、XおよびR¹は炭素数１〜１０の飽和または不飽和のアルキル基を表し、Yは単結合、-CH₂CH₂-または-CH₂O-を表し、Aはトランス-1,4-シクロヘキシレン基又は1,4-フェニレン基を表し、nは０または１を表す。）で表される化合物の製造方法を提供する。
さらに、一般式（Ｉｂ）

Wherein X and R ¹ represent a saturated or unsaturated alkyl group having 1 to 10 carbon atoms, Y represents a single bond, —CH ₂ CH ₂ — or —CH ₂ O—, and A represents trans-1 , 4-cyclohexylene group or 1,4-phenylene group, and n represents 0 or 1).
Furthermore, the general formula (Ib)

（式中、Xは炭素数１〜１０の飽和または不飽和のアルキル基を表す。）で表される化合物の６位をリチオ化し、一般式（VII）

(Wherein X represents a saturated or unsaturated alkyl group having 1 to 10 carbon atoms), the 6-position of the compound represented by formula (VII)

（式中、R¹は炭素数１〜１０の飽和または不飽和のアルキル基を表し、Yは単結合、-CH₂CH₂-または-CH₂O-を表し、Aはトランス-1,4-シクロヘキシレン基又は1,4-フェニレン基を表し、nは０または１を表す。）で表されるシクロヘキシルアセトアルデヒド誘導体を反応させた後、脱水し生成する二重結合を水素添加することによる、一般式（VIII）

Wherein R ¹ represents a saturated or unsaturated alkyl group having 1 to 10 carbon atoms, Y represents a single bond, —CH ₂ CH ₂ — or —CH ₂ O—, and A represents trans-1,4 By reacting a cyclohexylacetaldehyde derivative represented by -cyclohexylene group or 1,4-phenylene group, and n represents 0 or 1.) Formula (VIII)

（式中、XおよびR³は炭素数１〜１０の飽和アルキル基を表し、Yは単結合、-CH₂CH₂-または-CH₂O-を表し、Aはトランス-1,4-シクロヘキシレン基又は1,4-フェニレン基を表し、nは０または１を表す。）で表される化合物の製造方法を提供する。

(Wherein X and R ³ represent a saturated alkyl group having 1 to 10 carbon atoms, Y represents a single bond, —CH ₂ CH ₂ — or —CH ₂ O—, and A represents trans-1,4-cyclohexene. Represents a silylene group or a 1,4-phenylene group, and n represents 0 or 1).

  By providing a 1,7,8-trifluoro-2-naphthol derivative and a method for producing a liquid crystal compound using the same according to the present invention, a liquid crystal compound having a trifluoronaphthalene skeleton, which has been conventionally difficult, can be efficiently produced. It became possible to manufacture.

The compound represented by the general formula (I) can be obtained by fluorinating 7,8-difluoro-2-naphthol to obtain a compound of X = H, which is further reacted with trifluoromethanesulfonic anhydride. Thus, a compound of X = CF ₃ SO ₂ — can be obtained. In addition, by reacting a corresponding alkyl halide in the presence of a base such as potassium carbonate, sodium carbonate, sodium hydride or the like, a compound in which X represents a saturated or unsaturated alkyl group having 1 to 10 carbon atoms can be obtained. it can.

  Fluorination is N-fluoropyridinium triflate, N-fluoropyridinium tetrafluoroborate, N-fluoro-2,6-dichloropyridinium triflate, N-fluoro-2,6-dichloropyridinium tetrafluoroborate, N-fluoro-2 , 4,6-Trimethylpyridinium triflate, N-fluoro-2,4,6-trimethylpyridinium tetrafluoroborate, N, N'-difluoro-2,2'-bipyridinium bis (tetrafluoroborate), N-fluoro Fluoropyridiniums such as -4,6-dimethylpyridinium-2-sulfonato, fluoroammoniums such as 1-chloromethyl-4-fluoro-1,4-diazoniabicyclo [2.2.2] octanebis (tetrafluoroborate) Electrophilic fluorinating agents such as fluorine gas, bromine trifluoride and iodine pentafluoride can be used. At that time, in addition to the desired 1,7,8-trifluoro-2-naphthol (general formula (I) X = H), 1,1,7,8-tetrafluoro-1,2-dihydronaphthalene-2- In some cases, ON may be generated, and in that case, it can be easily converted to 1,7,8-trifluoro-2-naphthol by reduction using a reducing agent such as hydrogen.

  Here, the starting 7,8-difluoro-2-naphthol is produced by converting 2,3-difluorophenylacetic acid to acid chloride and then reacting with ethylene in the presence of aluminum chloride as shown in the following formula. It can be produced by allowing an oxidizing agent such as bromine to act on 7,8-difluoro-1,2,3,4-tetrahydronaphthalen-2-one.

また、一般式（I）（Xは炭素数１〜１０の飽和または不飽和のアルキル基を表す）で表される化合物において、Xとしてはメチル基、エチル基、プロピル基、ブチル基、ペンチル基、ヘキシル基、ヘプチル基、オクチル基、ノニル基、デシル基、2-メチルブチル基等の飽和アルキル基、アリル基、クロチル基等の不飽和アルキル基があげられる。ここで、合成に用いるハロゲン化アルキルとしてはヨウ化メチル、ヨウ化ブチル、ヨウ化プロピル、ヨウ化ブチル、ヨウ化ペンチル、ヨウ化ヘキシル、ヨウ化ヘプチル、ヨウ化オクチル、ヨウ化ノニル、ヨウ化デシル、ヨウ化2-メチルブチル、臭化メチル、臭化ブチル、臭化プロピル、臭化ブチル、臭化ペンチル、臭化ヘキシル、臭化ヘプチル、臭化オクチル、臭化ノニル、臭化デシル、臭化2-メチルブチル、塩化メチル、塩化ブチル、塩化プロピル、塩化ブチル、塩化ペンチル、塩化ヘキシル、塩化ヘプチル、塩化オクチル、塩化ノニル、塩化デシル、塩化2-メチルブチル、臭化アリル、臭化クロチル、塩化アリル、塩化クロチル等があげられる。

In the compound represented by the general formula (I) (X represents a saturated or unsaturated alkyl group having 1 to 10 carbon atoms), X is a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group. And saturated alkyl groups such as hexyl group, heptyl group, octyl group, nonyl group, decyl group and 2-methylbutyl group, and unsaturated alkyl groups such as allyl group and crotyl group. Here, alkyl halides used for synthesis include methyl iodide, butyl iodide, propyl iodide, butyl iodide, pentyl iodide, hexyl iodide, heptyl iodide, octyl iodide, nonyl iodide, decyl iodide. 2-methylbutyl iodide, methyl bromide, butyl bromide, propyl bromide, butyl bromide, pentyl bromide, hexyl bromide, heptyl bromide, octyl bromide, nonyl bromide, decyl bromide, bromide 2 -Methylbutyl, methyl chloride, butyl chloride, propyl chloride, butyl chloride, pentyl chloride, hexyl chloride, heptyl chloride, octyl chloride, nonyl chloride, decyl chloride, 2-methylbutyl chloride, allyl bromide, crotyl bromide, allyl chloride, chloride Crotyl and the like.

In the production of the compound represented by the general formula (IV), the triflate of the general formula (I) (X = CF ₃ SO _2- ) is reacted with the boronic acid of the general formula (II), and the general formula (III) The type of reaction that yields the compound represented is called Suzuki coupling.

  In this reaction, a mixed system (two-phase system) of water and an organic solvent can be used as a reaction solvent. As the organic solvent. Reaction solvents include nitriles such as acetonitrile and benzonitrile, halogenated solvents such as dichloromethane, chloroform, carbon tetrachloride, 1,2-dichloroethane, 1,1,1-trichloroethane, diethyl ether, methyl-t-butyl ether, Ethers such as tetrahydrofuran, esters such as ethyl acetate, methyl acetate and butyl acetate, saturated hydrocarbons such as pentane, hexane, heptane and octane, benzenes such as benzene, toluene, xylene and chlorobenzene, N, N-dimethyl Amides such as formamide and N, N-dimethylacetamide can be used singly or in combination, and tetrahydrofuran, toluene or xylene is preferred.

  This reaction can be carried out at a temperature equal to or higher than the boiling point or azeotropic temperature of organic solvent or water at normal pressure. For example, in a water-THF two-phase system, 80 to 200 ° C is preferable, and 90 to 130 ° C is particularly preferable.

  As the base used in this reaction, inorganic bases such as sodium carbonate, potassium carbonate, sodium hydroxide, potassium hydroxide, sodium hydrogen carbonate, potassium hydrogen carbonate, magnesium carbonate, calcium carbonate can be used. Sodium hydroxide and potassium hydroxide are preferred, and sodium carbonate and potassium carbonate are particularly preferred.

  Catalysts used in this reaction include tetrakis (triphenylphosphine) palladium, dichlorobis (triphenylphosphine) palladium, dichloro [bis (diphenylphosphino) ethane] palladium, dichloro [bis (diphenylphosphino) propane] palladium, dichloro [ Palladium complexes such as bis (diphenylphosphino) butane] palladium, dichloro [bis (diphenylphosphino) ferrocene] palladium, tetrakis (triphenylphosphine) nickel, dichlorobis (triphenylphosphine) nickel, dichloro [bis (diphenylphosphino) Ethane] nickel, dichloro [bis (diphenylphosphino) propane] nickel, dichloro [bis (diphenylphosphino) butane] nickel, dichloro [bis (diphenylphosphino) ferrocene] ni Although it is possible to increase the nickel complex such as Kell, palladium complexes are preferred.

  Further, in this reaction, a method in which a two-phase solvent of tetrahydrofuran, benzene, toluene or xylene and water is used and heated under reflux using a palladium catalyst in the presence of sodium carbonate or potassium carbonate is particularly preferable.

In the production of the phenylnaphthalene compound represented by the general formula (IV) (when R ² is an alkyl group) by the alkylation of the general formula (III), the alkylation can be carried out as follows.

  A phenylnaphthalene compound represented by the general formula (IV) is obtained by selectively lithiating the 6-position of the naphthalene ring of the general formula (III) and reacting this with an alkyl iodide or reacting with an allyl halide. To manufacture.

  In this reaction, lithiation is preferably performed using alkyllithium such as butyllithium, s-butyllithium or t-butyllithium or lithium amide such as lithium diisopropoxide or lithium hexamethyldisilazide.

  The reaction is preferably carried out in an organic solvent, and non-aqueous polar solvents such as tetrahydrofuran, diethyl ether and dimethoxyethane, and hydrocarbon solvents such as benzene, toluene or xylene, hexane and heptane are preferred.

  Specific examples of the alkyl iodide include methyl iodide, ethyl iodide, propyl iodide, butyl iodide and the like. Examples of the allyl halide include allyl chloride, allyl bromide, crotyl chloride, crotyl bromide and the like.

In the production of the phenylnaphthalene compound represented by the general formula (IV) (when R ² is an alkoxyl group) by the alkoxylation of the general formula (III), the alkoxylation can be carried out as follows.

  A naphthol having a hydroxyl group introduced at the 6-position can be produced by selectively lithiating the 6-position of the naphthalene ring of the general formula (III), reacting with trimethylborane and allowing hydrogen peroxide to act. A phenylnaphthalene compound represented by the general formula (IV) can be produced by reacting this with an alkyl halide or an allyl halide.

  In this reaction, lithiation is preferably performed using alkyllithium such as butyllithium, s-butyllithium or t-butyllithium or lithium amide such as lithium diisopropoxide or lithium hexamethyldisilazide.

  The reaction is preferably carried out in an organic solvent, and non-aqueous polar solvents such as tetrahydrofuran, diethyl ether and dimethoxyethane, and hydrocarbon solvents such as benzene, toluene or xylene, hexane and heptane are preferred.

  Specific examples of alkyl halides include methyl iodide, ethyl iodide, propyl iodide, butyl iodide and the like. Specific examples of allyl halides include allyl chloride, allyl bromide, crotyl chloride, crotyl bromide and the like. Can be mentioned.

  The boronic acid represented by the general formula (II) is often used as an intermediate for producing liquid crystals. For example, the general formula (Va)

（式中、R¹、Y、Aおよびnは一般式（II）におけるR¹、Y、Aおよびnと同じ意味を表す。）で表されるフェニルブロミドにマグネシウムを反応させグリニャール反応剤として後、トリメトキシボランと反応させることによって容易に製造できる。

(Wherein R ¹ , Y, A and n have the same meanings as R ¹ , Y, A and n in formula (II)), magnesium is reacted with the phenyl bromide represented by formula (II) as a Grignard reactant. It can be easily produced by reacting with trimethoxyborane.

  In the production of the compound represented by the general formula (VI), the 6-position of the compound of the general formula (I) (X represents a saturated or unsaturated alkyl group having 1 to 10 carbon atoms) was selectively lithiated. Thereafter, it can be synthesized by Suzuki coupling in which a boronic acid that can be easily produced by reacting with trimethoxyborane is reacted with a compound represented by the general formula (V).

  Regarding the Suzuki coupling, the reaction conditions in the production of the compound represented by the general formula (IV) can be used as they are.

  Selective lithiation at the 6-position of a compound of the general formula (I) (X represents a saturated or unsaturated alkyl group having 1 to 10 carbon atoms) can be performed using butyllithium, s-butyllithium, t-butyllithium, It is preferable to use lithium amides such as alkyl lithium or lithium diisopropoxide and lithium hexamethyldisilazide.

  The lithiation reaction is preferably carried out by using a non-aqueous polar solvent such as tetrahydrofuran, diethyl ether or dimethoxyethane, or a hydrocarbon solvent such as benzene, toluene or xylene, hexane or heptane, alone or in combination.

  The lithiation reaction temperature may be 0 ° C. or lower and the freezing point of the solvent, but is preferably between −20 ° C. and −90 ° C., particularly preferably −40 ° C. to −78 ° C.

  In addition, the compound represented by the general formula (V) is often used as a liquid crystal production intermediate and is easily available.

  In the production of the compound represented by the general formula (VIII), the compound 6-position of the general formula (I) (X represents a saturated or unsaturated alkyl group having 1 to 10 carbon atoms) was selectively lithiated. Thereafter, by reacting with cyclohexylacetaldehyde represented by the general formula (VII), the general formula (IX)

（式中、Xは炭素数１〜１０の飽和または不飽和のアルキル基を表し、R¹は炭素数１〜１０の飽和または不飽和のアルキル基を表し、Yは単結合、-CH₂CH₂-または-CH₂O-を表し、Aはトランス-1,4-シクロヘキシレン基又は1,4-フェニレン基を表し、nは０または１を表す。）で表されるアルコールを得、これを脱水することによって、一般式（X）

(Wherein X represents a saturated or unsaturated alkyl group having 1 to 10 carbon atoms, R ¹ represents a saturated or unsaturated alkyl group having 1 to 10 carbon atoms, Y represents a single bond, —CH ₂ CH _2- or -CH ₂ O-, A represents a trans-1,4-cyclohexylene group or 1,4-phenylene group, and n represents 0 or 1. By dehydrating the general formula (X)

（式中、X、R¹、Y、Aおよびnは化合物（IX）に記載のX、R¹、Y、Aおよびnと同じ意味を表す。）であらわされる化合物を得、さらにオレフィン部位を水素添加する製造方法をあげることができる。

(Wherein, X, R ^1, Y, X according to A and n are the compounds (IX), R ^1, Y, the same meanings as A and n.) To give the compounds represented by the further olefin site A production method for hydrogenation can be mentioned.

  The conditions for selective lithiation at the 6-position of the compound of the general formula (I) are the same as those of the method for producing the compound represented by the general formula (VI).

  The reaction with cyclohexylacetaldehyde represented by the general formula (VII) after lithiation may be carried out by dissolving the aldehyde in the same solvent after lithiation. The reaction temperature in this case can be carried out in the range from room temperature to the freezing point of the solvent, but is preferably 0 ° C to -60 ° C.

  The dehydration reaction is not a problem under generally well-known conditions. For example, in toluene, a method of heating to reflux in the presence of an acid catalyst such as sulfuric acid or p-toluenesulfonic acid, presence of a base such as pyridine, The method of making it react with mesyl chloride, tosyl chloride, etc. is mentioned.

  Also, hydrogenation of olefins is well known, and can be easily performed by using a catalyst such as palladium-carbon or Raney nickel under a hydrogen atmosphere or under pressure.

  EXAMPLES Hereinafter, although an Example is given and this invention is further explained in full detail, this invention is not limited to these Examples.

  Example 1 Production of 1,7,8-trifluoro-2-naphthol (general formula (I): X = hydrogen atom)

7,8-ジフルオロ-2-ナフトール（26 g）のアセトニトリル（240 ml）溶液に、N,N'-ジフルオロ-2,2'-ビピリジニウムビス（テトラフルオロボラート）（53 g）を加え、3.5時間加熱還流した。反応液を水にあけ、有機層を分取し、水層を酢酸エチルで３回抽出した。有機層を合わせ、飽和食塩水で２回洗浄し、濃縮し、残渣として1,1,7,8-テトラフルオロ-1,2-ジヒドロナフタレン-2-オンの粗生成物を得た。オートクレーブに先の残渣、5%パラジウム-炭素（50%含水、5 g）、シリカゲル（5 g）および酢酸エチル（200 ml）を加え、水素圧下（4 kg/cm²）、室温で４時間攪拌した。反応液をセライトでろ別し、ろ液を濃縮した。残渣をヘキサン／トルエン混合溶媒から再結晶し、1,7,8-トリフルオロ-2-ナフトール（25 g）を淡黄色結晶として得た。
融点 91℃
¹H NMR (CDCl₃)δ 5.0-6.5 (broad, 1 H), 7.14-7.24 (m, 2 H), 7.45-7.55 (m, 2 H)
MS m/z：198 (M⁺, 100)

To a solution of 7,8-difluoro-2-naphthol (26 g) in acetonitrile (240 ml) was added N, N'-difluoro-2,2'-bipyridinium bis (tetrafluoroborate) (53 g). Heated to reflux for hours. The reaction solution was poured into water, the organic layer was separated, and the aqueous layer was extracted three times with ethyl acetate. The organic layers were combined, washed twice with saturated brine, and concentrated to obtain a crude product of 1,1,7,8-tetrafluoro-1,2-dihydronaphthalen-2-one as a residue. Add the previous residue, 5% palladium-carbon (50% water content, 5 g), silica gel (5 g) and ethyl acetate (200 ml) to the autoclave, and stir at room temperature for 4 hours under hydrogen pressure (4 kg / cm ² ). did. The reaction solution was filtered through celite, and the filtrate was concentrated. The residue was recrystallized from a hexane / toluene mixed solvent to obtain 1,7,8-trifluoro-2-naphthol (25 g) as pale yellow crystals.
Melting point 91 ° C
¹ H NMR (CDCl ₃ ) δ 5.0-6.5 (broad, 1 H), 7.14-7.24 (m, 2 H), 7.45-7.55 (m, 2 H)
MS m / z: 198 (M ⁺ , 100)

Example 2 Production of 1,7,8-trifluoronaphthalen-2-yltrifluoromethanesulfonate (general formula (I): X = CF ₃ SO ₂ —)

1,7,8-トリフルオロ-2-ナフトール（10 g）、トリフルオロメタンスルホン酸無水物（10.3 ml）のジクロロメタン（60 ml）溶液に、氷冷下でピリジン（10 ml）をゆっくりと滴下し、さらに30分間攪拌した。反応液に水とジクロロメタンをゆっくりと加え、有機層を分取し、水層をジクロロメタンで抽出した。有機層を合わせ、水、10%塩酸、飽和炭化水素ナトリウム水溶液、水、飽和食塩水の順に洗浄し、濃縮した。残渣をカラムクロマトグラフィー（シリカゲル、ヘキサン／酢酸エチル＝19／１）で精製し、1,7,8-トリフルオロナフタレン-2-イルトリフルオロメタンスルホナト（15 g）を淡黄色結晶として得た。
MS m/z：330 (M⁺), 169 (100)

Pyridine (10 ml) was slowly added dropwise to a solution of 1,7,8-trifluoro-2-naphthol (10 g) and trifluoromethanesulfonic anhydride (10.3 ml) in dichloromethane (60 ml) under ice-cooling. The mixture was further stirred for 30 minutes. Water and dichloromethane were slowly added to the reaction solution, the organic layer was separated, and the aqueous layer was extracted with dichloromethane. The organic layers were combined, washed successively with water, 10% hydrochloric acid, saturated aqueous sodium hydrocarbon solution, water and saturated brine, and concentrated. The residue was purified by column chromatography (silica gel, hexane / ethyl acetate = 19/1) to obtain 1,7,8-trifluoronaphthalen-2-yltrifluoromethanesulfonate (15 g) as pale yellow crystals.
MS m / z: 330 (M ⁺ ), 169 (100)

  Example 3 Production of 2-ethoxy-1,7,8-trifluoronaphthalene (general formula (I): X = ethyl group)

1,7,8-トリフルオロ-2-ナフトール（15 g）、炭酸カリウム（16 g）、ヨウ化エチエル（26 g）のアセトン（80 ml）溶液を室温で10時間攪拌した。これにトルエン（200 ml）を加え、有機層を分取し、水層をトルエンで抽出した。有機層を合わせ、飽和食塩水で洗浄し、濃縮した。残渣を減圧蒸留して、2-エトキシ-1,7,8-トリフルオロナフタレン（16 g）を得た。
融点 96.5−98.5℃
¹H NMR (CDCl₃)δ 1.48 (t, J = 7.1 Hz, 3 H), 4.27 (q, J = 7.1 Hz, 2H), 7.15-7.35 (m, 2 H), 7.45-7.60 (m, 2 H)
MS m/z：226 (M⁺), 198 (100)

A solution of 1,7,8-trifluoro-2-naphthol (15 g), potassium carbonate (16 g) and ethyl iodide (26 g) in acetone (80 ml) was stirred at room temperature for 10 hours. Toluene (200 ml) was added thereto, the organic layer was separated, and the aqueous layer was extracted with toluene. The organic layers were combined, washed with saturated brine, and concentrated. The residue was distilled under reduced pressure to give 2-ethoxy-1,7,8-trifluoronaphthalene (16 g).
Melting point 96.5-98.5 ℃
¹ H NMR (CDCl ₃ ) δ 1.48 (t, J = 7.1 Hz, 3 H), 4.27 (q, J = 7.1 Hz, 2H), 7.15-7.35 (m, 2 H), 7.45-7.60 (m, 2 H)
MS m / z: 226 (M ⁺ ), 198 (100)

(Example 4) 2- (4-propylphenyl) -1,7,8- trifluoro-naphthalene (formula ^(III): R 1 = n- propyl, A = phenyl, Y = single bond, n = 1) Production

オートクレーブに1,7,8-トリフルオロナフタレン-2-イルトリフルオロメタンスルホナト（15 g）、4-プロピルフェニルホウ酸（11.2 g）、炭酸カリウム（18.8 g）、テトラキス(トリフェニルホスフィン)パラジウム(0)（1 g）、トルエン（50 ml）、テトラヒドロフラン（50 ml）、水（20 ml）を加え、窒素加圧下（2 kg/cm²）、90℃で４時間反応させた。反応液を水にあけ、有機層を分取し、水層をトルエンで抽出した。有機層を合わせ、10%塩酸、飽和食塩水で洗浄し、濃縮した。残渣を絡むクロマトグラフィー（シリカゲル、ヘキサン）で精製し、2-(4-プロピルフェニル)-1,7,8-トリフルオロナフタレン（13 g）を得た。
MS m/z：300 (M⁺), 271 (100)

Autoclave with 1,7,8-trifluoronaphthalen-2-yltrifluoromethanesulfonate (15 g), 4-propylphenylboric acid (11.2 g), potassium carbonate (18.8 g), tetrakis (triphenylphosphine) palladium ( 0) (1 g), toluene (50 ml), tetrahydrofuran (50 ml) and water (20 ml) were added, and the mixture was reacted at 90 ° C. for 4 hours under nitrogen pressure (2 kg / cm ² ). The reaction solution was poured into water, the organic layer was separated, and the aqueous layer was extracted with toluene. The organic layers were combined, washed with 10% hydrochloric acid and saturated brine, and concentrated. Purification by chromatography (silica gel, hexane) involving the residue gave 2- (4-propylphenyl) -1,7,8-trifluoronaphthalene (13 g).
MS m / z: 300 (M ⁺ ), 271 (100)

Example 5 3-Methyl-7- (4-propylphenyl) -1,2,8-trifluoronaphthalene (General formula (IV): R ¹ = n-propyl group, A = phenyl group, Y = simple Bond, n = 1, R ¹ = methyl group)

2-(4-プロピルフェニル)-1,7,8-トリフルオロナフタレン（6.5 g）のテトラヒドロフラン（25 ml）溶液に-65℃で1.58 Mブチルリチウム／ヘキサン溶液（16.4 ml）を滴下し、１時間攪拌した。これに、ヨウ化メチル（3.7 g）のテトラヒドロフラン（10 ml）溶液を30分かけて滴下し、その後室温まで昇温した。反応液に水を加え、攪拌後、少量の塩酸を加え中和し、有機層を分取した。水層を酢酸エチルで抽出し、有機層を合わせ、水、チオ硫酸ナトリウム水溶液、飽和食塩水で洗浄し、濃縮した。残渣をカラムクロマトグラフィー（シリカゲル、ヘキサン）で精製し、エタノールから再結晶（２回）して、3-メチル-7-(4-プロピルフェニル)-1,2,8-トリフルオロナフタレン（4.8 g）を無色針状晶として得た。
融点 99℃
¹H NMR (CDCl₃)δ 0.99 (t, J = 7.3 Hz, 3 H), 1.70 (sextet, J = 7.3 Hz, 2 H), 2.49 (s, 3 H), 2.66 (t, J = 7.3 Hz, 2 H), 7.2-7.6 (m, 7 H)
MS m/z：314 (M⁺), 285 (100)
ヨウ化メチルに代えヨウ化エチルを用いる以外は同様にして6-メチル-2-(4-プロピルフェニル)-1,7,8-トリフルオロナフタレンを得た。

To a solution of 2- (4-propylphenyl) -1,7,8-trifluoronaphthalene (6.5 g) in tetrahydrofuran (25 ml) was added 1.58 M butyllithium / hexane solution (16.4 ml) dropwise at -65 ° C. Stir for hours. To this, a solution of methyl iodide (3.7 g) in tetrahydrofuran (10 ml) was added dropwise over 30 minutes, and then the temperature was raised to room temperature. Water was added to the reaction solution, and after stirring, a small amount of hydrochloric acid was added to neutralize, and the organic layer was separated. The aqueous layer was extracted with ethyl acetate, and the organic layers were combined, washed with water, aqueous sodium thiosulfate solution and saturated brine, and concentrated. The residue was purified by column chromatography (silica gel, hexane) and recrystallized from ethanol (twice) to give 3-methyl-7- (4-propylphenyl) -1,2,8-trifluoronaphthalene (4.8 g ) Were obtained as colorless needles.
Melting point 99 ℃
¹ H NMR (CDCl ₃ ) δ 0.99 (t, J = 7.3 Hz, 3 H), 1.70 (sextet, J = 7.3 Hz, 2 H), 2.49 (s, 3 H), 2.66 (t, J = 7.3 Hz , 2 H), 7.2-7.6 (m, 7 H)
MS m / z: 314 (M ⁺ ), 285 (100)
6-Methyl-2- (4-propylphenyl) -1,7,8-trifluoronaphthalene was obtained in the same manner except that ethyl iodide was used instead of methyl iodide.

  This method is efficient because when a compound having a different side chain (in this case, a methyl group) is produced, another compound can be obtained only by changing the raw material used in the final step.

  Comparative Example 1 Production of 3-methyl-7- (4-propylphenyl) -1,2,8-trifluoronaphthalene

7,8-ジフルオロ-1,2,3,4-テトラヒドロナフタレン-2-オンを出発原料として、特許文献4に記載の方法で3-メチル-7-(4-プロピルフェニル)-1,2,8-トリフルオロナフタレンの製造を行った。この方法では、2-クロロ-6-メチル-7,8-ジフルオロナフタレンの収率が悪く、工程も長いため効率的な製造はできなかった。又、側鎖(この場合メチル基)が異なった化合物を製造する場合はあらかじめ側鎖の異なった中間体を製造する必要があり効率が悪かった。

Using 7,8-difluoro-1,2,3,4-tetrahydronaphthalen-2-one as a starting material, 3-methyl-7- (4-propylphenyl) -1,2, by the method described in Patent Document 4 8-Trifluoronaphthalene was produced. In this method, the yield of 2-chloro-6-methyl-7,8-difluoronaphthalene was poor and the production process was long, so that efficient production was not possible. Further, when producing compounds having different side chains (in this case, methyl groups), it is necessary to produce intermediates having different side chains in advance, resulting in poor efficiency.

Example 6 3-Ethoxy-7- (4-propylphenyl) -1,2,8-trifluoronaphthalene (general formula (IV): R ¹ = n-propyl group, A = phenyl group, Y = simple Bond, n = 1, R ¹ = ethoxy group)

2-(4-プロピルフェニル)-1,7,8-トリフルオロナフタレン（6.5 g）のテトラヒドロフラン（25 ml）溶液に-65℃で1.58 Mブチルリチウム／ヘキサン溶液（16.4 ml）を滴下し、１時間攪拌した。これに、トリメトキシボラン（2.7 g）のテトラヒドロフラン（10 ml）溶液を30分かけて滴下し、その後０℃まで昇温した。反応液に酢酸（1.85 ml）および30%過酸化水素（3 ml）を加え、しばらく攪拌した。反応液に水を加え、有機層を分取し、水層を酢酸エチルで抽出した。有機層を合わせ、水、飽和食塩水で洗浄後、濃縮し、6-(4-プロピルフェニル)-3,4,5-トリフルオロ-2-ナフトール（8.5 g）を得た。
MS m/z：316 (M⁺), 287 (100)
水素化ナトリウム（60%油性、1.3 g）のN,N-ジメチルホルムアミド（5 ml）懸濁液に、氷冷下、6-(4-プロピルフェニル)-3,4,5-トリフルオロ-2-ナフトール（8.5 g）のN,N-ジメチルホルムアミド（30 ml）溶液を滴下した。これに、ヨウ化エチル（6.3 g）のN,N-ジメチルホルムアミド（20 ml）溶液を30分かけて滴下し、さらに30分攪拌した。反応液を水にあけ、チオ硫酸ナトリウムを加えてしばらく攪拌した。有機層を分取し、水層を酢酸エチルで抽出後、有機層を合わせ、飽和食塩水で洗浄し、濃縮した。残渣をカラムクロマトグラフィー（シリカゲル、トルエン）で精製し、エタノールから再結晶（３回）して、3-エトキシ-7-(4-プロピルフェニル)-1,2,8-トリフルオロナフタレン（3.8 g）を無色針状晶として得た。
融点 122℃
¹H NMR (CDCl₃)δ 0.99 (t, J = 7.3 Hz, 3 H), 1.55 (t, J = 7.1 Hz, 3 H), 1.72 (broad sextet, J = 7.6 Hz, 2 H), 2.65 (t, J = 7.6 Hz, 2 H), 4.23 (q, J = 7.1 Hz, 2 H), 7.0-7.6 (m, 7 H)
MS m/z：344 (M⁺), 287 (100)

To a solution of 2- (4-propylphenyl) -1,7,8-trifluoronaphthalene (6.5 g) in tetrahydrofuran (25 ml) was added 1.58 M butyllithium / hexane solution (16.4 ml) dropwise at -65 ° C. Stir for hours. A solution of trimethoxyborane (2.7 g) in tetrahydrofuran (10 ml) was added dropwise thereto over 30 minutes, and then the temperature was raised to 0 ° C. Acetic acid (1.85 ml) and 30% hydrogen peroxide (3 ml) were added to the reaction mixture and stirred for a while. Water was added to the reaction solution, the organic layer was separated, and the aqueous layer was extracted with ethyl acetate. The organic layers were combined, washed with water and saturated brine, and concentrated to give 6- (4-propylphenyl) -3,4,5-trifluoro-2-naphthol (8.5 g).
MS m / z: 316 (M +), 287 (100)
To a suspension of sodium hydride (60% oily, 1.3 g) in N, N-dimethylformamide (5 ml) under ice-cooling, 6- (4-propylphenyl) -3,4,5-trifluoro-2 -A solution of naphthol (8.5 g) in N, N-dimethylformamide (30 ml) was added dropwise. To this, a solution of ethyl iodide (6.3 g) in N, N-dimethylformamide (20 ml) was added dropwise over 30 minutes, and the mixture was further stirred for 30 minutes. The reaction mixture was poured into water, sodium thiosulfate was added, and the mixture was stirred for a while. The organic layer was separated, and the aqueous layer was extracted with ethyl acetate. The organic layers were combined, washed with saturated brine, and concentrated. The residue was purified by column chromatography (silica gel, toluene) and recrystallized from ethanol (three times) to give 3-ethoxy-7- (4-propylphenyl) -1,2,8-trifluoronaphthalene (3.8 g ) Were obtained as colorless needles.
Melting point 122 ° C
¹ H NMR (CDCl ₃ ) δ 0.99 (t, J = 7.3 Hz, 3 H), 1.55 (t, J = 7.1 Hz, 3 H), 1.72 (broad sextet, J = 7.6 Hz, 2 H), 2.65 ( t, J = 7.6 Hz, 2 H), 4.23 (q, J = 7.1 Hz, 2 H), 7.0-7.6 (m, 7 H)
MS m / z: 344 (M ⁺ ), 287 (100)

(Example 7) 7-ethoxy-3- [4- (trans-4-propylcyclohexyl) phenyl] -1,2,8-trifluoronaphthalene (general formula (VI): R ¹ = n-propyl group, A = Cyclohexyl group, Y = single bond, n = 1, X = ethyl group)

2-エトキシ-1,7,8-トリフルオロナフタレン（16 g）のテトラヒドロフラン（80 ml）溶液を-60℃に冷却し、1.58 Mブチルリチウム／ヘキサン溶液（47 ml）を滴下し、１時間攪拌した。これに、トリメトキシボラン（8.8 g）を30分かけて滴下し、その後室温まで昇温した。反応液を10%塩酸にあけ、有機層を分取し、水層をトルエンで抽出した。有機層を合わせ、飽和食塩水で洗浄し、無水硫酸マグネシウムで乾燥した後、溶媒を減圧留去した。オートクレーブに残渣（12 g）、4-(トランス-4-プロピルシクロヘキシル）ブロモベンゼン（11.4 g）、炭酸カリウム（16.8 g）、テトラキス(トリフェニルホスフィン)パラジウム(0)（1 g）、トルエン（80 ml）、テトラヒドロフラン（80 ml）、水（40 ml）を加え、窒素加圧下（2 kg/cm²）、90℃で５時間反応させた。反応液を水にあけ、有機層を分取し、水層をトルエンで抽出した。有機層を合わせ、10%塩酸、飽和食塩水で洗浄し、濃縮した。残渣を絡むクロマトグラフィー（アルミナ、トルエン／ヘキサン＝１／３）で精製し、さらに再結晶（トルエン／ヘキサン＝１／３）し、7-エトキシ-3-[4-(トランス-4-プロピルシクロヘキシル）フェニル]-1,2,8-トリフルオロナフタレン（6 g）を得た。
相転移温度 Cr 134 N 248 I
¹H NMR (CDCl₃)δ 0.92 (t, J = 7.1 Hz, 3 H), 1.00-1.15 (m, 2 H), 1.45 (m, 5 H), 1.45-1.60 (m, 5 H), 1.92 (t, J = 16.4 Hz, 4 H), 2.54 (t, J = 12.5 Hz, 1 H), 4.28 (q, J = 6.8 Hz, 2H), 7.20-7.35 (m, 3 H) , 7.50-7.60 (m, 4 H)
MS m/z：426 (M⁺, 100)

A solution of 2-ethoxy-1,7,8-trifluoronaphthalene (16 g) in tetrahydrofuran (80 ml) is cooled to -60 ° C, 1.58 M butyllithium / hexane solution (47 ml) is added dropwise, and the mixture is stirred for 1 hour. did. To this, trimethoxyborane (8.8 g) was added dropwise over 30 minutes, and then the temperature was raised to room temperature. The reaction solution was poured into 10% hydrochloric acid, the organic layer was separated, and the aqueous layer was extracted with toluene. The organic layers were combined, washed with saturated brine, and dried over anhydrous magnesium sulfate, and the solvent was evaporated under reduced pressure. The residue (12 g), 4- (trans-4-propylcyclohexyl) bromobenzene (11.4 g), potassium carbonate (16.8 g), tetrakis (triphenylphosphine) palladium (0) (1 g), toluene (80 ml), tetrahydrofuran (80 ml) and water (40 ml) were added and reacted at 90 ° C. for 5 hours under nitrogen pressure (2 kg / cm ² ). The reaction solution was poured into water, the organic layer was separated, and the aqueous layer was extracted with toluene. The organic layers were combined, washed with 10% hydrochloric acid and saturated brine, and concentrated. Purification by chromatography involving the residue (alumina, toluene / hexane = 1/3), recrystallization (toluene / hexane = 1/3), 7-ethoxy-3- [4- (trans-4-propylcyclohexyl) ) Phenyl] -1,2,8-trifluoronaphthalene (6 g) was obtained.
Phase transition temperature Cr 134 N 248 I
¹ H NMR (CDCl ₃ ) δ 0.92 (t, J = 7.1 Hz, 3 H), 1.00-1.15 (m, 2 H), 1.45 (m, 5 H), 1.45-1.60 (m, 5 H), 1.92 (t, J = 16.4 Hz, 4 H), 2.54 (t, J = 12.5 Hz, 1 H), 4.28 (q, J = 6.8 Hz, 2H), 7.20-7.35 (m, 3 H), 7.50-7.60 (m, 4 H)
MS m / z: 426 (M ⁺ , 100)

Example 8 7-Ethoxy-3- [2- [trans-4- (trans-4-butylcyclohexyl) cyclohexyl] ethyl] -1,2,8-trifluoronaphthalene (general formula (VIII): R ³ = N-butyl group, A = cyclohexyl group, Y = single bond, n = 1, R ¹ = ethyl group)

2-エトキシ-1,7,8-トリフルオロナフタレン（9.4 g）のテトラヒドロフラン（50 ml）溶液を-60℃に冷却し、1.58 Mブチルリチウム／ヘキサン溶液（47 ml）を滴下し、２時間攪拌した。これにトランス-4-(トランス-4-ブチルシクロヘキシル）シクロヘキシルアセトアルデヒド（13.2 g）のテトラヒドロフラン（50 ml）溶液を-50℃で滴下し、２時間攪拌後、０℃まで昇温した。反応液に10%塩酸を加え、酢酸エチルで抽出し、飽和食塩水で洗浄後、濃縮した。残渣を酢酸エチルから再結晶し、7-エトキシ-3-[2-[トランス-4-(トランス-4-ブチルシクロヘキシル）シクロヘキシル]-1-ヒドロキシエチル]-1,2,8-トリフルオロナフタレン（17 g）を得た。

A solution of 2-ethoxy-1,7,8-trifluoronaphthalene (9.4 g) in tetrahydrofuran (50 ml) is cooled to -60 ° C, 1.58 M butyllithium / hexane solution (47 ml) is added dropwise, and the mixture is stirred for 2 hours. did. A solution of trans-4- (trans-4-butylcyclohexyl) cyclohexylacetaldehyde (13.2 g) in tetrahydrofuran (50 ml) was added dropwise thereto at −50 ° C., and the mixture was stirred for 2 hours and then heated to 0 ° C. 10% Hydrochloric acid was added to the reaction mixture, and the mixture was extracted with ethyl acetate, washed with saturated brine, and concentrated. The residue was recrystallized from ethyl acetate to give 7-ethoxy-3- [2- [trans-4- (trans-4-butylcyclohexyl) cyclohexyl] -1-hydroxyethyl] -1,2,8-trifluoronaphthalene ( 17 g) was obtained.

  7-ethoxy-3- [2- [trans-4- (trans-4-butylcyclohexyl) cyclohexyl] -1-hydroxyethyl] -1,2,8-trifluoronaphthalene (16.2 g), p-toluene in the autoclave A solution of sulfonic acid (0.6 g) in toluene (100 ml) was heated to reflux for 1 hour. The reaction mixture was washed with water and saturated brine, concentrated, and (E) -7-ethoxy-3- [2- [trans-4- (trans-4-butylcyclohexyl) cyclohexyl] ethenyl] -1,2 , 8-trifluoronaphthalene crude product (16.6 g) was obtained.

(E) -7-Ethoxy-3- [2- [trans-4- (trans-4-butylcyclohexyl) cyclohexyl] ethenyl] -1,2,8-trifluoronaphthalene crude product (16.6 g), 5% Palladium-carbon (containing 50% water) (3.1 g) and tetrahydrofuran (100 ml) were added and reacted at room temperature under 4 atmospheres of hydrogen for 4 hours. The reaction solution was filtered through celite, the filtrate was concentrated, and 7-ethoxy-3- [2- [trans-4- (trans-4-butylcyclohexyl) cyclohexyl] ethyl] -1,2,8-trifluoronaphthalene. Crude product (15.4 g) was obtained. Further, recrystallization from hexane gave 7-ethoxy-3- [2- [trans-4- (trans-4-butylcyclohexyl) cyclohexyl] ethyl] -1,2,8-trifluoronaphthalene (9 g). .
Phase transition temperature Cr 94 N 209 I
¹ H NMR (CDCl ₃ ) δ 0.82-0.89 (m, 5 H), 0.94-1.01 (m, 8 H), 1.12-1.27 (m, 8 H), 1.46 (t, J = 7.0 Hz, 3 H) , 1.52-1.57 (m, 2 H), 1.67-1.75 (m, 6 H), 1.83-1.85 (m, 2 H), 2.74-2.78 (m, 2 H), 4.24 (q, J = 7.0 Hz, 2 H), 7.20 (dd, J = 9.0 and 6.6 Hz, 1 H), 7.29-7.30 (broad d, J = 8 Hz, 1 H), 7.24-7.44 (broad dt, J = 9.0 and 1.0 Hz, 1 H)
MS m / z: 474 (M ⁺ , 100)

Claims (8)

Formula (I)

(Wherein X represents a hydrogen atom, CF ₃ SO ₂ — or a saturated or unsaturated alkyl group having 1 to 10 carbon atoms). 2. The compound according to claim 1, wherein X represents a hydrogen atom. The compound according to claim 1, wherein X represents CF ₃ SO _2- . 2. The compound according to claim 1, wherein X represents a saturated or unsaturated alkyl group having 1 to 10 carbon atoms. Formula (Ia)

In the compound represented by general formula (II)

Wherein R ¹ represents a saturated or unsaturated alkyl group having 1 to 10 carbon atoms, Y represents a single bond, —CH ₂ CH ₂ — or —CH ₂ O—, and A represents trans-1,4 -Represents a cyclohexylene group or a 1,4-phenylene group, and n represents 0 or 1).

^{(Wherein, R 1, Y, R 1} A and n in the general formula (II), Y, represents the same meaning as A and n.) The production method of the compound represented by. Formula (Ia)

In the compound represented by general formula (II)

Wherein R ¹ represents a saturated or unsaturated alkyl group having 1 to 10 carbon atoms, Y represents a single bond, —CH ₂ CH ₂ — or —CH ₂ O—, and A represents trans-1,4 -Represents a cyclohexylene group or a 1,4-phenylene group, and n represents 0 or 1) by reacting the compound represented by the general formula (III) in the presence of a catalyst.

(Wherein, R ^1, Y, R ¹ A and n in the general formula (II), Y, represent. The same meanings as A and n) after obtaining the compounds represented by alkylated or alkoxylated this General formula (IV) characterized by

(Wherein, R ^1, Y, A and n are in the general formula (II) R ^1, Y, the same meanings as A and n, R ² is or a saturated or unsaturated alkyl group having 1 to 10 carbon atoms Represents an alkoxyl group.). Formula (Ib)

(Wherein, X represents a saturated or unsaturated alkyl group having 1 to 10 carbon atoms), the 6-position of the compound represented by the formula is reacted with trimethoxyborane. Formula (V)

(Wherein, Z is represents a iodine atom, a bromine atom, a chlorine atom or a trifluoromethanesulfonyloxy group, R ¹ represents a saturated or unsaturated alkyl group having 1 to 10 carbon atoms, Y represents a single bond, -CH ₂ CH ₂ — or —CH ₂ O—, A represents a trans-1,4-cyclohexylene group or 1,4-phenylene group, and n represents 0 or 1.) General formula (VI) characterized by reacting below

Wherein X and R ¹ represent a saturated or unsaturated alkyl group having 1 to 10 carbon atoms, Y represents a single bond, —CH ₂ CH ₂ — or —CH ₂ O—, and A represents trans-1 Represents a 1,4-cyclohexylene group or a 1,4-phenylene group, and n represents 0 or 1.). Formula (Ib)

(Wherein X represents a saturated or unsaturated alkyl group having 1 to 10 carbon atoms), the 6-position of the compound represented by formula (VII)

Wherein R ¹ represents a saturated or unsaturated alkyl group having 1 to 10 carbon atoms, Y represents a single bond, —CH ₂ CH ₂ — or —CH ₂ O—, and A represents trans-1,4 By reacting a cyclohexylacetaldehyde derivative represented by -cyclohexylene group or 1,4-phenylene group, and n represents 0 or 1.) Formula (VIII)

(Wherein X and R ³ represent a saturated alkyl group having 1 to 10 carbon atoms, Y represents a single bond, —CH ₂ CH ₂ — or —CH ₂ O—, and A represents trans-1,4-cyclohexene. Represents a silene group or a 1,4-phenylene group, and n represents 0 or 1.)